Stable iron isotopes and microbial mediation in red pigmentation of the Rosso Ammonitico (mid-late Jurassic, Verona area, Italy).

PubMed

Préat, Alain R; de Jong, Jeroen T M; Mamet, Bernard L; Mattielli, Nadine

2008-08-01

The iron (Fe) isotopic composition of 17 Jurassic limestones from the Rosso Ammonitico of Verona (Italy) have been analyzed by Multiple-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). Such analysis allowed for the recognition of a clear iron isotopic fractionation (mean -0.8 per thousand, ranging between -1.52 to -0.06 per thousand) on a millimeter-centimeter scale between the red and grey facies of the studied formation. After gentle acid leaching, measurements of the Fe isotopic compositions gave delta(56)Fe values that were systematically lower in the red facies residues (median: -0.84 per thousand, range: -1.46 to +0.26 per thousand) compared to the grey facies residues (median: -0.08 per thousand, range: -0.34 to +0.23 per thousand). In addition, the red facies residues were characterized by a lighter delta(56)Fe signal relative to their corresponding leachates. These Fe isotopic fractionations could be a sensitive fingerprint of a biotic process; systematic isotopic differences between the red and grey facies residues, which consist of hematite and X-ray amorphous iron hydroxides, respectively, are hypothesized to have resulted from the oxidizing activity of iron bacteria and fungi in the red facies. The grey Fe isotopic data match the Fe isotopic signature of the terrestrial baseline established for igneous rocks and low-C(org) clastic sedimentary rocks. The Fe isotopic compositions of the grey laminations are consistent with the influx of detrital iron minerals and lack of microbial redox processes at the water-interface during deposition. Total Fe concentration measurements were performed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) (confirmed by concentration estimations obtained by MC-ICP-MS analyses of microdrilled samples) on five samples, and resultant values range between 0.30% (mean) in the grey facies and 1.31% (mean) in the red facies. No correlation was observed between bulk Fe content and pigmentation or between bulk Fe content and Fe isotopic compositions. The rapid transformation of the original iron oxyhydroxides to hematite could have preserved the original isotopic composition if it had occurred at about the same temperature. This paper supports the use of Fe isotopes as sensitive tracers of biological activities recorded in old sedimentary sequences that contain microfossils of iron bacteria and fungi. However, a careful interpretation of the iron isotopic fractionation in terms of biotic versus abiotic processes requires supporting data or direct observations to characterize the biological, (geo)chemical, or physical context in relation to the geologic setting. This will become even more pertinent when Fe isotopic studies are expanded to the interplanetary realm.

Iron and nickel isotope compositions of presolar silicon carbide grains from supernovae

NASA Astrophysics Data System (ADS)

Kodolányi, János; Stephan, Thomas; Trappitsch, Reto; Hoppe, Peter; Pignatari, Marco; Davis, Andrew M.; Pellin, Michael J.

2018-01-01

We report the carbon, silicon, iron, and nickel isotope compositions of twenty-five presolar SiC grains of mostly supernova (SN) origin. The iron and nickel isotope compositions were measured with the new Chicago Instrument for Laser Ionization, CHILI, which allows the analysis of all iron and nickel isotopes without the isobaric interferences that plagued previous measurements with the NanoSIMS. Despite terrestrial iron and nickel contamination, significant isotopic anomalies in 54Fe/56Fe, 57Fe/56Fe, 60Ni/58Ni, 61Ni/58Ni, 62Ni/58Ni, and 64Ni/58Ni were detected in nine SN grains (of type X). Combined multi-isotope data of three grains with the largest nickel isotope anomalies (>100‰ or <-100‰ in at least one isotope ratio, when expressed as deviation from the solar value) are compared with the predictions of two SN models, one with and one without hydrogen ingestion in the He shell prior to SN explosion. One grain's carbon-silicon-iron-nickel isotope composition is consistent with the prediction of the model without hydrogen ingestion, whereas the other two grains' isotope anomalies could not be reproduced using either SN models. The discrepancies between the measured isotope compositions and model predictions may indicate element fractionation in the SN ejecta prior to or during grain condensation, and reiterate the need for three-dimensional SN models.

Iron isotope fractionation during hydrothermal ore deposition and alteration

NASA Astrophysics Data System (ADS)

Markl, Gregor; von Blanckenburg, Friedhelm; Wagner, Thomas

2006-06-01

Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (<100 °C). Measured iron isotope compositions are variable and cover a range in δ56Fe between -2.3‰ and +1.3‰. Primary hematite ( δ56Fe: -0.5‰ to +0.5‰) precipitated by mixing oxidizing surface waters with a hydrothermal fluid that contained moderately light Fe ( δ56Fe: -0.5‰) leached from the crystalline basement. Occasional input of CO 2-rich waters resulted in precipitation of isotopically light siderite ( δ56Fe: -1.4 to -0.7‰). The difference between hematite and siderite is compatible with published Fe isotope fractionation factors. The observed range in isotopic compositions can be accounted for by variable fractions of Fe precipitating from the fluid. Therefore, both fluid processes and mass balance can be inferred from Fe isotopes. Supergene weathering of siderite by oxidizing surface waters led to replacement of isotopically light primary siderite by similarly light secondary hematite and goethite, respectively. Because this replacement entails quantitative transfer of iron from precursor mineral to product, no significant isotope fractionation is produced. Hence, Fe isotopes potentially serve to identify precursors in ore alteration products. Goethites from oolitic sedimentary iron ores were also analyzed. Their compositional range appears to indicate oxidative precipitation from relatively uniform Fe dissolved in coastal water. This comprehensive iron isotope study illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.

Geochemical and iron isotopic insights into hydrothermal iron oxyhydroxide deposit formation at Loihi Seamount

NASA Astrophysics Data System (ADS)

Rouxel, Olivier; Toner, Brandy; Germain, Yoan; Glazer, Brian

2018-01-01

Low-temperature hydrothermal vents, such as those encountered at Loihi Seamount, harbor abundant microbial communities and provide ideal systems to test hypotheses on biotic versus abiotic formation of hydrous ferric oxide (FeOx) deposits at the seafloor. Hydrothermal activity at Loihi Seamount produces abundant microbial mats associated with rust-colored FeOx deposits and variably encrusted with Mn-oxyhydroxides. Here, we applied Fe isotope systematics together with major and trace element geochemistry to study the formation mechanisms and preservation of such mineralized microbial mats. Iron isotope composition of warm (<60 °C), Fe-rich and H2S-depleted hydrothermal fluids yielded δ56Fe values near +0.1‰, indistinguishable from basalt values. Suspended particles in the vent fluids and FeOx deposits recovered nearby active vents yielded systematically positive δ56Fe values. The enrichment in heavy Fe isotopes between +1.05‰ and +1.43‰ relative to Fe(II) in vent fluids suggest partial oxidation of Fe(II) during mixing of the hydrothermal fluid with seawater. By comparing the results with experimentally determined Fe isotope fractionation factors, we determined that less than 20% of Fe(II) is oxidized within active microbial mats, although this number may reach 80% in aged or less active deposits. These results are consistent with Fe(II) oxidation mediated by microbial processes considering the expected slow kinetics of abiotic Fe oxidation in low oxygen bottom water at Loihi Seamount. In contrast, FeOx deposits recovered at extinct sites have distinctly negative Fe-isotope values down to -1.77‰ together with significant enrichment in Mn and occurrence of negative Ce anomalies. These results are best explained by the near-complete oxidation of an isotopically light Fe(II) source produced during the waning stage of hydrothermal activity under more oxidizing conditions. Light Fe isotope values of FeOx are therefore generated by subsurface precipitation of isotopically heavy Fe-oxides rather than by the activity of dissimilatory Fe reduction in the subsurface. Overall, Fe-isotope compositions of microbial mats at Loihi Seamount display a remarkable range between -1.2‰ and +1.6‰ which indicate that Fe isotope compositions of hydrothermal Fe-oxide precipitates are particularly sensitive to local environmental conditions where they form, and are less sensitive to abiotic versus biotic origins. It follows that FeOx deposits at Loihi Seamount provides important modern analogues for ancient seafloor Fe-rich deposits allowing for testing hypotheses about the biogeochemical cycling of Fe isotopes on early Earth.

Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

NASA Astrophysics Data System (ADS)

Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

2013-05-01

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

Effects of spin crossover on iron isotope fractionation in Earth's mantle

NASA Astrophysics Data System (ADS)

Qin, T.; Shukla, G.; Wu, Z.; Wentzcovitch, R.

2017-12-01

Recent studies have revealed that the iron isotope composition of mid-ocean ridge basalts (MORBs) is +0.1‰ richer in heavy Fe (56Fe) relative to chondrites, while basalts from Mars and Vesta have similar Fe isotopic composition as chondrites. Several hypotheses could explain these observations. For instance, iron isotope fractionation may have occurred during core formation or Earth may have lost some light Fe isotope during the high temperature event in the early Earth. To better understand what drove these isotopic observations, it is important to obtain accurate Fe isotope fractionation factors among mantle and core phases at the relevant P-T conditions. In bridgmanite, the most voluminous mineral in the lower mantle, Fe can occupy more than one crystalline site, be in ferrous and/or ferric states, and may undergo a spin crossover in the lower mantle. Iron isotopic fractionation properties under spin crossover are poorly constrained, while this may be relevant to differentiation of Earth's magma ocean. In this study we address the effect of these multiple states on the iron isotope fractionation factors between mantle and core phases.

Iron isotopic systematics of oceanic basalts

NASA Astrophysics Data System (ADS)

Teng, Fang-Zhen; Dauphas, Nicolas; Huang, Shichun; Marty, Bernard

2013-04-01

The iron isotopic compositions of 93 well-characterized basalts from geochemically and geologically diverse mid-ocean ridge segments, oceanic islands and back arc basins were measured. Forty-three MORBs have homogeneous Fe isotopic composition, with δ56Fe ranging from +0.07‰ to +0.14‰ and an average of +0.105 ± 0.006‰ (2SD/√n, n = 43, MSWD = 1.9). Three back arc basin basalts have similar δ56Fe to MORBs. By contrast, OIBs are slightly heterogeneous with δ56Fe ranging from +0.05‰ to +0.14‰ in samples from Koolau and Loihi, Hawaii, and from +0.09‰ to +0.18‰ in samples from the Society Islands and Cook-Austral chain, French Polynesia. Overall, oceanic basalts are isotopically heavier than mantle peridotite and pyroxenite xenoliths, reflecting Fe isotope fractionation during partial melting of the mantle. Iron isotopic variations in OIBs mainly reflect Fe isotope fractionation during fractional crystallization of olivine and pyroxene, enhanced by source heterogeneity in Koolau samples.

Coupled extremely light Ca and Fe isotopes in peridotites

NASA Astrophysics Data System (ADS)

Zhao, Xinmiao; Zhang, Zhaofeng; Huang, Shichun; Liu, Yufei; Li, Xin; Zhang, Hongfu

2017-07-01

Large metal stable isotopic variations have been observed in both extraterrestrial and terrestrial samples. For example, Ca exhibits large mass-dependent isotopic variation in terrestrial igneous rocks and mantle minerals (on the order of ∼2‰ variation in 44Ca/40Ca). A thorough assessment and understanding of such isotopic variations in peridotites provides important constraints on the evolution and compositon of the Earth's mantle. In order to better understand the Ca and Fe isotopic variations in terrestrial silicate rocks, we report Ca isotopic compositions in a set of peridotitic xenoliths from North China Craton (NCC), which have been studied for Fe isotopes. These NCC peridotites have large Ca and Fe isotopic variations, with δ44/40Ca ranging from -0.08 to 0.92 (delta value relative to SRM915a) and δ57/54Fe (delta value relative to IRMM-014) ranging from -0.61 to 0.16, and these isotopic variations are correlated with large Mg# (100 × Mg/(Mg + Fe) molar ratio) variation, ranging from 80 to 90. Importantly, NCC Fe-rich peridotites have the lowest 44Ca/40Ca and 57Fe/54Fe ratios in all terrestrial silicate rocks. In contrast, although ureilites, mantle rocks from a now broken differentiated asteroid(s), have large Mg# variation, from 70 to 92, they have very limited δ57Fe/54Fe variation (0.03-0.21, delta value relative to IRMM-014). Our model calculations show that the coupled extremely light Ca-Fe isotopic signatures in NCC Fe-rich peridotites most likely reflect kinetic isotopic fractionation during melt-peridotite reaction on a timescale of several to 104 years. In addition, our new data and compiled literature data show a possible compositional effect on the inter-mineral Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene pairs.

Diffusion-driven magnesium and iron isotope fractionation in Hawaiian olivine

USGS Publications Warehouse

Teng, F.-Z.; Dauphas, N.; Helz, R.T.; Gao, S.; Huang, S.

2011-01-01

Diffusion plays an important role in Earth sciences to estimate the timescales of geological processes such as erosion, sediment burial, and magma cooling. In igneous systems, these diffusive processes are recorded in the form of crystal zoning. However, meaningful interpretation of these signatures is often hampered by the fact that they cannot be unambiguously ascribed to a single process (e.g., magmatic fractionation, diffusion limited transport in the crystal or in the liquid). Here we show that Mg and Fe isotope fractionations in olivine crystals can be used to trace diffusive processes in magmatic systems. Over sixty olivine fragments from Hawaiian basalts show isotopically fractionated Mg and Fe relative to basalts worldwide, with up to 0.4??? variation in 26Mg/24Mg ratios and 1.6??? variation in 56Fe/54Fe ratios. The linearly and negatively correlated Mg and Fe isotopic compositions [i.e., ??56Fe=(??3.3??0.3)????26Mg], co-variations of Mg and Fe isotopic compositions with Fe/Mg ratios of olivine fragments, and modeling results based on Mg and Fe elemental profiles demonstrate the coupled Mg and Fe isotope fractionation to be a manifestation of Mg-Fe inter-diffusion in zoned olivines during magmatic differentiation. This characteristic can be used to constrain the nature of mineral zoning in igneous and metamorphic rocks, and hence determine the residence times of crystals in magmas, the composition of primary melts, and the duration of metamorphic events. With improvements in methodology, in situ isotope mapping will become an essential tool of petrology to identify diffusion in crystals. ?? 2011 Elsevier B.V.

Isotopic composition of Mg and Fe in garnet peridotites from the Kaapvaal and Siberian cratons

NASA Astrophysics Data System (ADS)

An, Yajun; Huang, Jin-Xiang; Griffin, W. L.; Liu, Chuanzhou; Huang, Fang

2017-03-01

We present Mg and Fe isotopic data for whole rocks and separated minerals (olivine, clinopyroxene, orthopyroxene, garnet, and phlogopite) of garnet peridotites that equilibrated at depths of 134-186 km beneath the Kaapvaal and Siberian cratons. There is no clear difference in δ26Mg and δ56Fe of garnet peridotites from these two cratons. δ26Mg of whole rocks varies from -0.243‰ to -0.204‰ with an average of -0.225 ± 0.037‰ (2σ, n = 19), and δ56Fe from -0.038‰ to 0.060‰ with an average of -0.003 ± 0.068‰ (2σ, n = 19). Both values are indistinguishable from the fertile upper mantle, indicating that there is no significant Mg-Fe isotopic difference between the shallow and deep upper mantle. The garnet peridotites from ancient cratons show δ26Mg similar to komatiites and basalts, further suggesting that there is no obvious Mg isotopic fractionation during different degrees of partial melting of deep mantle peridotites and komatiite formation. The precision of the Mg and Fe isotope data (⩽±0.05‰ for δ26Mg and δ56Fe, 2σ) allows us to distinguish inter-mineral isotopic fractionations. Olivines are in equilibrium with opx in terms of Mg and Fe isotopes. Garnets have the lowest δ26Mg and δ56Fe among the coexisting mantle minerals, suggesting the dominant control of crystal structure on the Mg-Fe isotopic compositions of garnets. Elemental compositions and mineralogy suggest that clinopyroxene and garnet were produced by later metasomatic processes as they are not in chemical equilibrium with olivine or orthopyroxene. This is consistent with the isotopic disequilibrium of Mg and Fe isotopes between orthopyroxene/olivine and garnet/clinopyroxene. Combined with one sample showing slightly heavy δ26Mg and much lighter δ56Fe, these disequilibrium features in the garnet peridotites reveal kinetic isotopic fractionation due to Fe-Mg inter-diffusion during reaction between peridotites and percolating melts in the Kaapvaal craton.

Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn

Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.« less

Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma

DOE PAGES

Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn; ...

2015-09-05

Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.« less

Can Biomass Burning Explain Isotopically Light Fe in Marine Aerosols?

NASA Astrophysics Data System (ADS)

Sherry, A. M.; Anbar, A. D.; Herckes, P.; Romaniello, S. J.

2016-02-01

Iron (Fe) is an important micronutrient that limits primary productivity in large parts of the ocean. In these regions, atmospheric aerosol deposition is an important source of Fe to the surface ocean and thus has a critical impact on ocean biogeochemistry. Fe-bearing aerosols originate from many sources with potentially distinct Fe isotopic compositions. Consequently, Fe isotopes may provide a new tool to trace the sources of aerosol Fe to the oceans. Mead et al. (2013) first discovered that Fe in the fine fraction of Bermuda aerosols is often isotopically lighter than Fe from known anthropogenic and crustal sources. 1 These authors suggested that this light isotopic signature was likely the result of biomass burning, since Fe in plants is the only known source of isotopically light Fe. More recently, Conway et al. found that Fe in the soluble fraction of aerosols collected during 2010-2011 North Atlantic GEOTRACES cruises also showed light isotope values, which they likewise attributed to biomass burning.2 These studies are further supported by new modeling work which suggests that biomass burning aerosols should contribute significant amounts of soluble Fe to tropical and southern oceans.3To test if biomass burning releases aerosols with a light Fe isotope composition, we are conducting lab-scale biomass burning experiments using natural samples of vegetation and leaf litter. Burn aerosols were collected on cellulose filters, then digested and analyzed for trace metal concentrations using inductively-coupled mass spectrometry (ICP-MS). Fe isotopes were determined by using multiple collector ICP-MS following separation and purification of Fe using anion exchange chromatography. We will discuss metal concentration and isotope data from these experiments with implications for the interpretation of Fe isotope signals in aerosol samples. 1Mead, C et al. GRL, 2013, 40, 5722-5727. 2 Conway, T et al. Goldschmidt Abs 2015 593. 3Ito, A. ES&T Lett, 2015, 2, 70-75.

Cenozoic marine geochemistry of thallium deduced from isotopic studies of ferromanganese crusts and pelagic sediments

USGS Publications Warehouse

Rehkamper, M.; Frank, M.; Hein, J.R.; Halliday, A.

2004-01-01

Cenozoic records of Tl isotope compositions recorded by ferromanganese (Fe-Mn) crusts have been obtained. Such records are of interest because recent growth surfaces of Fe-Mn crusts display a nearly constant Tl isotope fractionation relative to seawater. The time-series data are complemented by results for bulk samples and leachates of various marine sediments. Oxic pelagic sediments and anoxic marine deposits can be distinguished by their Tl isotope compositions. Both pelagic clays and biogenic oozes are typically characterized by ??205Tl greater than +2.5, whereas anoxic sediments have ??205Tl of less than -1.5 (??205Tl is the deviation of the 205Tl/203Tl isotope ratio of a sample from NIST SRM 997 Tl in parts per 104). Leaching experiments indicate that the high ??205Tl values of oxic sediments probably reflect authigenic Fe-Mn oxyhydroxides. Time-resolved Tl isotope compositions were obtained from six Fe-Mn crusts from the Atlantic, Indian, and Pacific oceans and a number of observations indicate that these records were not biased by diagenetic alteration. Over the last 25 Myr, the data do not show isotopic variations that significantly exceed the range of Tl isotope compositions observed for surface layers of Fe-Mn crusts distributed globally (??205 Tl=+12.8??1.2). This indicates that variations in deep-ocean temperature were not recorded by Tl isotopes. The results most likely reflect a constant Tl isotope composition for seawater. The growth layers of three Fe-Mn crusts that are older than 25 Ma show a systematic increase of ??205Tl with decreasing age, from about +6 at 60-50 Ma to about +12 at 25 Ma. These trends are thought to be due to variations in the Tl isotope composition of seawater, which requires that the oceans of the early Cenozoic either had smaller output fluxes or received larger input fluxes of Tl with low ??205Tl. Larger inputs of isotopically light Tl may have been supplied by benthic fluxes from reducing sediments, rivers, and/or volcanic emanations. Alternatively, the Tl isotope trends may reflect the increasing importance of Tl fluxes to altered ocean crust through time. ?? 2004 Elsevier B.V. All rights reserved.

Partial melting and melt percolation in the mantle: The message from Fe isotopes

NASA Astrophysics Data System (ADS)

Weyer, Stefan; Ionov, Dmitri A.

2007-07-01

High precision Fe isotope measurements have been performed on various mantle peridotites (fertile lherzolites, harzburgites, metasomatised Fe-enriched peridotites) and volcanic rocks (mainly oceanic basalts) from different localities and tectonic settings. The peridotites yield an average δ 56Fe = 0.01‰ and are significantly lighter than the basalts (average δ 56Fe = 0.11‰). Furthermore, the peridotites display a negative correlation of δ 56Fe with Mg# indicating a link between δ 56Fe and degrees of melt extraction. Taken together, these findings imply that Fe isotopes fractionate during partial melting, with heavy isotopes preferentially entering the melt. The slope of depletion trends (δ 56Fe versus Mg#) of the peridotites was used to model Fe isotope fractionation during partial melting, resulting in αmantle-melt ≈ 1.0001-1.0003 or ln αmantle-melt ≈ 0.1-0.3‰. In contrast to most other peridotites investigated in this study, spinel lherzolites and harzburgites from three localities (Horoman, Kamchatka and Lherz) are virtually unaffected by metasomatism. These three sites display a particularly good correlation and define an isotope fractionation factor of ln αmantle-melt ≈ 0.3‰. This modelled value implies Fe isotope fractionation between residual mantle and mantle-derived melts corresponding to Δ56Fe mantle-basalt ≈ 0.2-0.3‰, i.e. significantly higher than the observed difference between averages for all the peridotites and the basalts in this study (corresponding to Δ56Fe mantle-basalt ≈ 0.1‰). Either disequilibrium melting increased the modelled αmantle-melt for these particular sites or the difference between average peridotite and basalt may be reduced by partial re-equilibration between the isotopically heavy basalts and the isotopically light depleted lithospheric mantle during melt ascent. The slope of the weaker δ 56Fe-Mg# trend defined by the combined set of all mantle peridotites from this study is more consistent with the generally observed difference between peridotites and basalts; this slope was used here to estimate the Fe isotope composition of the fertile upper mantle (at Mg# = 0.894, δ 56Fe ≈ 0.02 ± 0.03‰). Besides partial melting, the Fe isotope composition of mantle peridotites can also be significantly modified by metasomatic events, e.g. melt percolation. At two localities (Tok, Siberia and Tariat, Mongolia) δ 56Fe correlates with iron contents of the peridotites, which was increased from about 8% to up to 14.5% FeO by post-melting melt percolation. This process produced a range of Fe isotope compositions in the percolation columns, from extremely light (δ 56Fe = - 0.42‰) to heavy (δ 56Fe = + 0.17‰). We propose reaction with isotopically heavy melts and diffusion (enrichment of light Fe isotopes) as the most likely processes that produced the large isotope variations at these sites. Thus, Fe isotopes might be used as a sensitive tracer to identify such metasomatic processes in the mantle.

The effect of bonding environment on iron isotope fractionation between minerals at high temperature

NASA Astrophysics Data System (ADS)

Sossi, Paolo A.; O'Neill, Hugh St. C.

2017-01-01

Central to understanding the processes that drive stable isotope fractionation in nature is their quantification under controlled experimental conditions. The polyvalent element iron, given its abundance in terrestrial rocks, exerts controls on the structural and chemical properties of minerals and melts. The iron isotope compositions of typical high temperature minerals are, however, poorly constrained and their dependence on intensive (e.g. fO2) and extensive (e.g. compositional) variables is unknown. In this work, experiments involving a reference phase, 2 M FeCl2·4H2O(l), together with an oxide mix corresponding to the bulk composition of the chosen mineral were performed in a piston cylinder in Ag capsules. The oxide mix crystallised in situ at 1073 K and 1 GPa, in equilibrium with the iron chloride, and was held for 72 h. In order to characterise the effect of co-ordination and oxidation state on the isotope composition independently, exclusively Fe2+ minerals were substituted in: VIII-fold almandine, VI-fold ilmenite, fayalite and IV-fold chromite and hercynite. Δ57FeMin-FeCl2 increases in the order VIII < VI < IV, consistent with a decrease in the mean Fe-O bond length. Magnetite, which has mixed VI- and IV-fold co-ordination, has the heaviest Δ57Fe by virtue of 2/3 of its iron being the smaller, ferric ion. The composition of the VIFe2+-bearing minerals is similar to that of the aqueous FeCl2 fluid. To the degree that this represents the speciation of iron in fluids exsolving from magmas, the fractionation between them should be small, unless the iron is hosted in magnetite. By contrast, predominantly Fe2+-bearing mantle garnets should preserve a much lighter δ57Fe than their lower pressure spinel counterparts, a signature that may be reflected in partial melts from these lithologies. As the Fe-O bond lengths in fayalite and ilmenite are comparable, their isotope compositions overlap, suggesting that high Ti mare basalts acquired their heavy isotopic signature from ilmenite that crystallised late during lunar magma ocean solidification.

Spinel-olivine-pryoxene equilibrium iron isotopic fractionation and applications to natural peridotites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roskosz, Mathieu; Sio, Corliss K. I.; Dauphas, Nicolas

2015-11-15

Eight spinel-group minerals were synthesized by a flux-growth method producing spinels with varying composition and Fe3+/Fe-tot ratios. The mean force constants of iron bonds in these minerals were determined by synchrotron nuclear resonant inelastic X-ray scattering (NRIXS) in order to determine the reduced isotopic partition function ratios (beta-factors) of these spinels. The mean force constants are strongly dependent on the Fe3+/Fe-tot of the spinel but are independent, or weakly dependent on other structural and compositional parameters. From our spectroscopic data, it is found that a single redox-dependent calibration line accounts for the effects of Fe3+/Fe-tot on the beta-factors of spinels.more » This calibration successfully describes the equilibrium Fe isotopes fractionation factors between spinels and silicates (olivine and pyroxenes). Our predictions are in excellent agreement with independent determinations for the equilibrium Fe isotopic fractionations for the magnetite- fayalite and the magnetite-hedenbergite couples. Our calibration applies to the entire range of Fe3+/Fe-tot ratios found in natural spinels and provides a basis for interpreting iron isotopic variations documented in mantle peridotites. Except for a few exceptions, most of the samples measured so far are in isotopic disequilibrium, reflecting metasomatism and partial melting processes.« less

Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9-10°N

USGS Publications Warehouse

Rouxel, O.; Shanks, Wayne C.; Bach, W.; Edwards, K.J.

2008-01-01

In this study, we report on coupled Fe- and S-isotope systematics of hydrothermal fluids and sulfide deposits from the East Pacific Rise at 9–10°N to better constrain processes affecting Fe-isotope fractionation in hydrothermal environments. We aim to address three fundamental questions: (1) Is there significant Fe-isotope fractionation during sulfide precipitation? (2) Is there significant variability of Fe-isotope composition of the hydrothermal fluids reflecting sulfide precipitation in subsurface environments? (3) Are there any systematics between Fe- and S-isotopes in sulfide minerals? The results show that chalcopyrite, precipitating in the interior wall of a hydrothermal chimney displays a limited range of δ56Fe values and δ34S values, between − 0.11 to − 0.33‰ and 2.2 to 2.6‰ respectively. The δ56Fe values are, on average, slightly higher by 0.14‰ relative to coeval vent fluid composition while δ34S values suggest significant S-isotope fractionation (− 0.6 ± 0.2‰) during chalcopyrite precipitation. In contrast, systematically lower δ56Fe and δ34S values relative to hydrothermal fluids, by up to 0.91‰ and 2.0‰ respectively, are observed in pyrite and marcasite precipitating in the interior of active chimneys. These results suggest isotope disequilibrium in both Fe- and S-isotopes due to S-isotopic exchange between hydrothermal H2S and seawater SO42− followed by rapid formation of pyrite from FeS precursors, thus preserving the effects of a strong kinetic Fe-isotope fractionation during FeS precipitation. In contrast, δ56Fe and δ34S values of pyrite from inactive massive sulfides, which show evidence of extensive late-stage reworking, are essentially similar to the hydrothermal fluids. Multiple stages of remineralization of ancient chimney deposits at the seafloor appear to produce minimal Fe-isotope fractionation. Similar affects are indicated during subsurface sulfide precipitation as demonstrated by the lack of systematic differences between δ56Fe values in both high-temperature, Fe-rich black smokers and lower-temperature, Fe-depleted vents.

Experimental Constraints on Fe Isotope Fractionation in Carbonatite Melt Systems

NASA Astrophysics Data System (ADS)

Stuff, M.; Schuessler, J. A.; Wilke, M.

2015-12-01

Iron isotope data from carbonatite rocks show the largest variability found in igneous rocks to date [1]. Thus, stable Fe isotopes are promising tracers for the interaction of carbonate and silicate magmas in the mantle, particularly because their fractionation is controlled by oxidation state and bonding environment. The interpretation of Fe isotope data from carbonatite rocks remains hampered, since Fe isotope fractionation factors between silicate and carbonate melts are unknown and inter-mineral fractionation can currently only be assessed by theoretical calculations [1;2]. We present results from equilibration experiments in three natrocarbonatite systems between immiscible silicate and carbonate melts, performed at 1200°C and 0.7 GPa in an internally heated gas pressure vessel at intrinsic redox conditions. The Fe isotope compositions of the silicate melt (sil.m.), quenched to a glass, and the carbonate melt (carb.m.), forming fine-grained quench crystals, were analysed by solution MC-ICP-MS. Our first data indicate a remarkable fractionation of Δ56Fesil.m.‒carb.m.= 0.29 ±0.07 ‰ near equilibrium. At short run durations, even stronger fractionation up to Δ56Fesil.m.‒carb.m. = 0.41 ±0.07 ‰ occurs, due to kinetic effects. Additionally, Δ56Fesil.m.‒carb.m. changes with bulk chemical composition, likely reflecting considerable differences between the studied systems in terms of the Fe3+/Fe2+-ratios in the two immiscible liquids. Our findings provide experimental support for a carbonatite genesis model, in which extremely negative δ56Fe values in carbonatites result from differentiation processes, such as liquid immiscibility [1]. This effect can be enhanced by disequilibrium during fast ascent of carbonatite magmas. Their sensitivity to chemical and redox composition makes Fe isotopes a potential tool for constraining the original compositions of carbonatite magmas. [1] Johnson et al. (2010) Miner. Petrol. 98, 91-110. [2] Polyakov & Mineev (2000) Geochim. Cosmochim. Acta 64, 849-865.

Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Beard, Brian L.; Rosso, Kevin M.

2015-07-01

The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Femore » isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II) aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II) aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II) aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous solutions, but presents a challenge for utilizing such an approach to determine equilibrium isotope fractionation factors. Despite the uncertainty from extrapolation, there is consistency in goethite-water fractionation factors for our reversal approach to equilibrium, with final weighted average fractionation factor values of Δ¹⁸O Gth-wate r = 0.2 (±0.9‰) and 3.0 (±2.5‰) at 22 °C and -1.6 (±0.8‰) and 1.9 (±1.5‰) at 50 °C for micron-sized and nano-particulate goethite, respectively (errors at 2σ level). Reaction of ferrihydrite with Fe(II) aq in two distinct waters resulted in a quantitative conversion to goethite and complete O isotope exchange in each case, and similar fractionation factors were observed for experiments using the two waters. Comparison of our results with previous studies of O isotope fractionation between goethite and water suggests that particle size may be a contributing factor to the disparity among experimental studies.« less

Iron isotope biogeochemistry of Neoproterozoic marine shales

NASA Astrophysics Data System (ADS)

Kunzmann, Marcus; Gibson, Timothy M.; Halverson, Galen P.; Hodgskiss, Malcolm S. W.; Bui, Thi Hao; Carozza, David A.; Sperling, Erik A.; Poirier, André; Cox, Grant M.; Wing, Boswell A.

2017-07-01

Iron isotopes have been widely applied to investigate the redox evolution of Earth's surface environments. However, it is still unclear whether iron cycling in the water column or during diagenesis represents the major control on the iron isotope composition of sediments and sedimentary rocks. Interpretation of isotopic data in terms of oceanic redox conditions is only possible if water column processes dominate the isotopic composition, whereas redox interpretations are less straightforward if diagenetic iron cycling controls the isotopic composition. In the latter scenario, iron isotope data is more directly related to microbial processes such as dissimilatory iron reduction. Here we present bulk rock iron isotope data from late Proterozoic marine shales from Svalbard, northwestern Canada, and Siberia, to better understand the controls on iron isotope fractionation in late Proterozoic marine environments. Bulk shales span a δ 56Fe range from -0.45 ‰ to +1.04 ‰ . Although δ 56Fe values show significant variation within individual stratigraphic units, their mean value is closer to that of bulk crust and hydrothermal iron in samples post-dating the ca. 717-660 Ma Sturtian glaciation compared to older samples. After correcting for the highly reactive iron content in our samples based on iron speciation data, more than 90% of the calculated δ 56Fe compositions of highly reactive iron falls in the range from ca. -0.8 ‰ to +3 ‰ . An isotope mass-balance model indicates that diagenetic iron cycling can only change the isotopic composition of highly reactive iron by < 1 ‰ , suggesting that water column processes, namely the degree of oxidation of the ferrous seawater iron reservoir, control the isotopic composition of highly reactive iron. Considering a long-term decrease in the isotopic composition of the iron source to the dissolved seawater Fe(II) reservoir to be unlikely, we offer two possible explanations for the Neoproterozoic δ 56Fe trend. First, a decreasing supply of Fe(II) to the ferrous seawater iron reservoir could have caused the reservoir to decrease in size, allowing a higher degree of partial oxidation, irrespective of increasing environmental oxygen levels. Alternatively, increasing oxygen levels would have led to a higher proportion of Fe(II) being oxidized, without decreasing the initial size of the ferrous seawater iron pool. We consider the latter explanation as the most likely. According to this hypothesis, the δ 56Fe record reflects the redox evolution of Earth's surface environments. δ 56Fe values in pre-Sturtian samples significantly heavier than bulk crust and hydrothermal iron imply partial oxidation of a ferrous seawater iron reservoir. In contrast, mean δ 56Fe values closer to that of hydrothermal iron in post-Sturtian shales reflects oxidation of a larger proportion of the ferrous seawater iron reservoir, and by inference, higher environmental oxygen levels. Nevertheless, significant iron isotopic variation in post-Sturtian shales suggest redox heterogeneity and possibly a dominantly anoxic deep ocean, consistent with results from recent studies using iron speciation and redox sensitive trace metals. However, the interpretation of generally increasing environmental oxygen levels after the Sturtian glaciation highlights the need to better understand the sensitivity of different redox proxies to incremental changes in oxygen levels to enable us to reconcile results from different paleoredox proxies.

High Precision Iron Isotope Compositions in Components From the Allende CV3 Meteorite by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Mullane, E.; Russell, S. S.; Weiss, D.; Mason, T. F.; Gounelle, M.

2001-12-01

Four chondrules and one matrix sample of Allende were examined for Fe-isotope frac-tionation, using multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Iron is the most volatile major constituent of chondrules and a recent study [1] suggested that solar system Fe was initially isotopically homogeneous. Thus, any isotopic variation is likely due to mass fractionation during nebular process-ing. The chondrule samples were split. One portion was subject to a standard acid dis-solution whilst the other was polished, ena-bling textural and compositional characteri-zation. Fe, Cu and Zn are separated from the remaining matrix elements [2], removing potential interfering ions from the solution. 100 % elemental recovery (within error) is achieved, ensuring that chromatographic fractionation does not occur [2]. Hydrogen is bled into the collision cell, minimising Ar polyatomic species interferences. Typical precisions of 0.1‰ (2σ ) for 54Fe/56Fe ratios are achieved for 75 replicates. Instrumental mass bias is assessed using (1) sample-standard brack-eting and (2) doping with Cu. A variation of 0.8‰ /amu is observed, which is approximately 18 times the analyti-cal uncertainty at the 2σ level. Our high precision data show that: (1) Allende chondrules and matrix exhibit clear isotopic variation in iron. (2) δ 54Fe val-ues appear to be correlated to the bulk FeO content, with the more iron rich samples enriched in the lighter 54Fe isotope. (3) δ 54Fe values appear to be unre-lated to texture, and consequently to the temperature of chondrule formation. Bulk Fe-content may be a proxy for the amount of volatilisation experienced, and volatilisation of Fe in chondrule precursor material has resulted in a residue of the heavier Fe isotopes. Chondrules are known to have often experienced several heating events, and their texture primarily reflects the nature of the last event. Thus, the lack of correlation between the δ 54Fe value and chondrule texture suggests that Fe-isotope composi-tion was derived from chondrule precursor material. [1] Zhu et al. (2001) Nature 412, p.311 [2] Mullane et al. (2001) LPS XXXII, No.1545.

Strontium isotopes reveal weathering processes in lateritic covers in southern China with implications for paleogeographic reconstructions

PubMed Central

Wei, Xiao; Wang, Shijie; Ji, Hongbing; Shi, Zhenhua

2018-01-01

The isotope ratios of Sr are useful tracers for studying parent material sources, weathering processes, and biogeochemical cycling. Mineralogical and geochemical investigations of two lateritic weathering covers, in an area close to the Tropic of Cancer (Guangxi Province, southern China), were undertaken to study the regional weathering processes and Sr isotopic sources. We found that weathering and decomposition of Rb- and Sr-bearing minerals change the Sr isotopic composition in weathering products (lateritic soils). Weathering of illite lowered the 87Sr/86Sr ratio whereas dissolving and leaching of carbonate minerals increased the 87Sr/86Sr ratio. An Fe nodular horizon is widely developed on the top of the weathering covers in the studied area and it differs from the lateritic soil horizon in mineral composition, construction, and elemental concentration. Furthermore, both Fe2O3 and P2O5 (concentrations) are negatively correlated with the 87Sr/86Sr ratios, suggesting fixation of apatite by Fe oxides is a controlling factor of the Sr isotopic composition in the Fe nodular horizon. The 87Sr/86Sr and Nb/Sr ratios imply the contents and proportions of Fe nodules and clay are critical in controlling the changes of Sr isotopic composition in the Fe nodular horizon. The two stages of the weathering process of carbonate rocks are revealed by the87Sr/86Sr versus Nb/Sr diagram. The 87Sr/86Sr and Rb/Sr ratios suggest that Sr isotopes in the weathering covers within the studied area are derived mainly from parent rock weathering and that the contributions from allothogenic Sr isotopes are limited. A comparison of Sr isotopic composition signatures in the weathering covers of the studied area and Guizhou Province provided insight into the Sr isotopic source and paleogeographic evolution of southern China. From the Permian to the Triassic, the continental fragment sources of the South China sedimentary basin changed significantly. In the Permian, Southern China presented the paleogeographic pattern that the north was higher (in elevation) than the south. PMID:29373592

Strontium isotopes reveal weathering processes in lateritic covers in southern China with implications for paleogeographic reconstructions.

PubMed

Wei, Xiao; Wang, Shijie; Ji, Hongbing; Shi, Zhenhua

2018-01-01

The isotope ratios of Sr are useful tracers for studying parent material sources, weathering processes, and biogeochemical cycling. Mineralogical and geochemical investigations of two lateritic weathering covers, in an area close to the Tropic of Cancer (Guangxi Province, southern China), were undertaken to study the regional weathering processes and Sr isotopic sources. We found that weathering and decomposition of Rb- and Sr-bearing minerals change the Sr isotopic composition in weathering products (lateritic soils). Weathering of illite lowered the 87Sr/86Sr ratio whereas dissolving and leaching of carbonate minerals increased the 87Sr/86Sr ratio. An Fe nodular horizon is widely developed on the top of the weathering covers in the studied area and it differs from the lateritic soil horizon in mineral composition, construction, and elemental concentration. Furthermore, both Fe2O3 and P2O5 (concentrations) are negatively correlated with the 87Sr/86Sr ratios, suggesting fixation of apatite by Fe oxides is a controlling factor of the Sr isotopic composition in the Fe nodular horizon. The 87Sr/86Sr and Nb/Sr ratios imply the contents and proportions of Fe nodules and clay are critical in controlling the changes of Sr isotopic composition in the Fe nodular horizon. The two stages of the weathering process of carbonate rocks are revealed by the87Sr/86Sr versus Nb/Sr diagram. The 87Sr/86Sr and Rb/Sr ratios suggest that Sr isotopes in the weathering covers within the studied area are derived mainly from parent rock weathering and that the contributions from allothogenic Sr isotopes are limited. A comparison of Sr isotopic composition signatures in the weathering covers of the studied area and Guizhou Province provided insight into the Sr isotopic source and paleogeographic evolution of southern China. From the Permian to the Triassic, the continental fragment sources of the South China sedimentary basin changed significantly. In the Permian, Southern China presented the paleogeographic pattern that the north was higher (in elevation) than the south.

Fractionation of Fe isotopes during Fe(II) oxidation by a marine photoferrotroph is controlled by the formation of organic Fe-complexes and colloidal Fe fractions

NASA Astrophysics Data System (ADS)

Swanner, Elizabeth D.; Wu, Wenfang; Schoenberg, Ronny; Byrne, James; Michel, F. Marc; Pan, Yongxin; Kappler, Andreas

2015-09-01

Much interest exists in finding mineralogical, organic, morphological, or isotopic biosignatures for Fe(II)-oxidizing bacteria (FeOB) that are retained in Fe-rich sediments, which could indicate the activity of these organisms in Fe-rich seawater, more common in the Precambrian Era. To date, the effort to establish a clear Fe isotopic signature in Fe minerals produced by Fe(II)-oxidizing metabolisms has been thwarted by the large kinetic fractionation incurred as freshly oxidized aqueous Fe(III) rapidly precipitates as Fe(III) (oxyhydr)oxide minerals at near neutral pH. The Fe(III) (oxyhydr)oxide minerals resulting from abiotic Fe(II) oxidation are isotopically heavy compared to the Fe(II) precursor and are not clearly distinguishable from minerals formed by FeOB isotopically. However, in marine hydrothermal systems and Fe(II)-rich springs the minerals formed are often isotopically lighter than expected considering the fraction of Fe(II) that has been oxidized and experimentally-determined fractionation factors. We measured the Fe isotopic composition of aqueous Fe (Feaq) and the final Fe mineral (Feppt) produced in batch experiment using the marine Fe(II)-oxidizing phototroph Rhodovulum iodosum. The δ56Feaq data are best described by a kinetic fractionation model, while the evolution of δ56Feppt appears to be controlled by a separate fractionation process. We propose that soluble Fe(III), and Fe(II) and Fe(III) extracted from the Feppt may act as intermediates between Fe(II) oxidation and Fe(III) precipitation. Based on 57Fe Mössbauer spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray total scattering, we suggests these Fe phases, collectively Fe(II/III)interm, may consist of organic-ligand bound, sorbed, and/or colloidal Fe(II) and Fe(III) mineral phases that are isotopically lighter than the final Fe(III) mineral product. Similar intermediate phases, formed in response to organic carbon produced by FeOB and inorganic ligands (e.g., SiO44- or PO43-), may form in many natural Fe(II)-oxidizing environments. We propose that the formation of these intermediates is likely to occur in organic-rich systems, and thus may have controlled the ultimate isotopic composition of Fe minerals in systems where Fe(II) was being oxidized by or in the presence of microbes in Earth's past.

Thallium isotope variations in seawater and hydrogenetic, diagenetic, and hydrothermal ferromanganese deposits

USGS Publications Warehouse

Rehkamper, M.; Frank, M.; Hein, J.R.; Porcelli, D.; Halliday, A.; Ingri, J.; Liebetrau, V.

2002-01-01

Results are presented for the first in-depth investigation of TI isotope variations in marine materials. The TI isotopic measurements were conducted by multiple collector-inductively coupled plasma mass spectrometry for a comprehensive suite of hydrogenetic ferromanganese crusts, diagenetic Fe-Mn nodules, hydrothermal manganese deposits and seawater samples. The natural variability of TI isotope compositions in these samples exceeds the analytical reproducibility (?? 0.05???) by more than a factor of 40. Hydrogenetic Fe-Mn crusts have ??205TI of + 10 to + 14, whereas seawater is characterized by values as low as -8 (??205TI represents the deviation of the 205TI/203TI ratio of a sample from the NIST SRM 997 TI isotope standard in parts per 104). This ~ 2??? difference in isotope composition is thought to result from the isotope fractionation that accompanies the adsorption of TI onto ferromanganese particles. An equilibrium fractionation factor of ?? ~ 1.0021 is calculated for this process. Ferromanganese nodules and hydrothermal manganese deposits have variable TI isotope compositions that range between the values obtained for seawater and hydrogenetic Fe-Mn crusts. The variability in ??205TI in diagenetic nodules appears to be caused by the adsorption of TI from pore fluids, which act as a closed-system reservoir with a TI isotope composition that is inferred to be similar to seawater. Nodules with ??205TI values similar to seawater are found if the scavenging of TI is nearly quantitative. Hydrothermal manganese deposits display a positive correlation between ??205TI and Mn/Fe. This trend is thought to be due to the derivation of TI from distinct hydrothermal sources. Deposits with low Mn/Fe ratios and low ??205TI are produced by the adsorption of TI from fluids that are sampled close to hydrothermal sources. Such fluids have low Mn/Fe ratios and relatively high temperatures, such that only minor isotope fractionation occurs during adsorption. Hydrothermal manganese deposits with high Mn/Fe and high ??205Ti are generated by scavenging of TI from colder, more distal hydrothermal fluids. Under such conditions, adsorption is associated with significant isotope fractionation, and this produces deposits with higher ??205TI values coupled with high Mn/Fe. ?? 2002 Elsevier Science B.V. All rights reserved.

Magnesium and iron isotopes in 2.7 Ga Alexo komatiites: Mantle signatures, no evidence for Soret diffusion, and identification of diffusive transport in zoned olivine

NASA Astrophysics Data System (ADS)

Dauphas, Nicolas; Teng, Fang-Zhen; Arndt, Nicholas T.

2010-06-01

Komatiites from Alexo, Canada, are well preserved and represent high-degree partial mantle melts (˜50%). They are thus well suited for investigating the Mg and Fe isotopic compositions of the Archean mantle and the conditions of magmatic differentiation in komatiitic lavas. High precision Mg and Fe isotopic analyses of 22 samples taken along a 15-m depth profile in a komatiite flow are reported. The δ 25Mg and δ 26Mg values of the bulk flow are -0.138 ± 0.021‰ and -0.275 ± 0.042‰, respectively. These values are indistinguishable from those measured in mantle peridotites and chondrites, and represent the best estimate of the composition of the silicate Earth from analysis of volcanic rocks. Excluding the samples affected by secondary Fe mobilization, the δ 56Fe and δ 57Fe values of the bulk flow are +0.044 ± 0.030‰, and +0.059 ± 0.044‰, respectively. These values are consistent with a near-chondritic Fe isotopic composition of the silicate Earth and minor fractionation during komatiite magma genesis. In order to explain the early crystallization of pigeonite relative to augite in slowly cooled spinifex lavas, it was suggested that magmas trapped in the crystal mush during spinifex growth differentiated by Soret effect, which should be associated with large and coupled variations in the isotopic compositions of Mg and Fe. The lack of variations in Mg and Fe isotopic ratios either rules out the Soret effect in the komatiite flow or the effect is effaced as the solidification front migrates downward through the flow crust. Olivine separated from a cumulate sample has light δ 56Fe and slightly heavy δ 26Mg values relative to the bulk flow, which modeling shows can be explained by kinetic isotope fractionation associated with Fe-Mg inter-diffusion in olivine. Such variations can be used to identify diffusive processes involved in the formation of zoned minerals.

Opposing authigenic controls on the isotopic signature of dissolved iron in hydrothermal plumes

NASA Astrophysics Data System (ADS)

Lough, A. J. M.; Klar, J. K.; Homoky, W. B.; Comer-Warner, S. A.; Milton, J. A.; Connelly, D. P.; James, R. H.; Mills, R. A.

2017-04-01

Iron is a scarce but essential micronutrient in the oceans that limits primary productivity in many regions of the surface ocean. The mechanisms and rates of Fe supply to the ocean interior are still poorly understood and quantified. Iron isotope ratios of different Fe pools can potentially be used to trace sources and sinks of the global Fe biogeochemical cycle if these boundary fluxes have distinct signatures. Seafloor hydrothermal vents emit metal rich fluids from mid-ocean ridges into the deep ocean. Iron isotope ratios have the potential to be used to trace the input of hydrothermal dissolved iron to the oceans if the local controls on the fractionation of Fe isotopes during plume dispersal in the deep ocean are understood. In this study we assess the behaviour of Fe isotopes in a Southern Ocean hydrothermal plume using a sampling program of Total Dissolvable Fe (TDFe), and dissolved Fe (dFe). We demonstrate that δ56Fe values of dFe (δ56dFe) within the hydrothermal plume change dramatically during early plume dispersal, ranging from -2.39 ± 0.05‰ to -0.13 ± 0.06‰ (2 SD). The isotopic composition of TDFe (δ56TDFe) was consistently heavier than dFe values, ranging from -0.31 ± 0.03‰ to 0.78 ± 0.05‰, consistent with Fe oxyhydroxide precipitation as the plume samples age. The dFe present in the hydrothermal plume includes stabilised dFe species with potential to be transported to the deep ocean. We estimate that stable dFe exported from the plume will have a δ56Fe of -0.28 ± 0.17‰. Further, we show that the proportion of authigenic iron-sulfide and iron-oxyhydroxide minerals precipitating in the buoyant plume exert opposing controls on the resultant isotope composition of dissolved Fe passed into the neutrally buoyant plume. We show that such controls yield variable dissolved Fe isotope signatures under the authigenic conditions reported from modern vent sites elsewhere, and so ought to be considered during iron isotope reconstructions of past hydrothermalism from ocean sediment records.

Interplay of crystal fractionation, sulfide saturation and oxygen fugacity on the iron isotope composition of arc lavas: An example from the Marianas

NASA Astrophysics Data System (ADS)

Williams, H. M.; Prytulak, J.; Woodhead, J. D.; Kelley, K. A.; Brounce, M.; Plank, T.

2018-04-01

Subduction zone systems are central to a multitude of processes from the evolution of the continental crust to the concentration of metals into economically viable deposits. The interplay between oxygen fugacity, sulfur saturation, fluid exsolution and fractionating mineral assemblages that gives rise to typical arc magma chemical signatures is, however, still poorly understood and novel geochemical approaches are required to make further progress. Here we examine a well-characterized suite of arc lavas from the Marianas (W. Pacific) for their stable Fe isotope composition. In agreement with previous work and mass balance considerations, contributions from sediments and/or fluids are shown to have negligible effect on Fe isotopes. Instead, we focus on disentangling processes occurring during basalt through dacite differentiation using a sample suite from the island of Anatahan. Anatahan whole rock Fe isotope compositions (δ57Fe) range from -0.05 ± 0.05 to 0.17 ± 0.03 (2 S.D.)‰. A fractionation model is constructed, where three distinct stages of differentiation are required to satisfy the combined major and trace element and isotopic observations. In particular, the sequestration of isotopically heavy Fe into magnetite and isotopically light Fe into sulfide melts yields important constraints. The data require that lavas are first undersaturated with respect to crystalline or molten sulfide, followed by the crystallisation of magnetite, which then triggers late sulfide saturation. The model demonstrates that the final stage of removal of liquid or crystalline sulfide can effectively sequester Cu (and presumably other chalcophiles) and that late stage exsolution of magmatic fluids or brines may not be required to do this, although these processes are not mutually exclusive. Finally, the new Fe isotope data are combined with previous Tl-Mo-V stable isotope determinations on the same samples. Importantly, the multi-valent transition metal stable isotope systems of Fe and V are decoupled by sulfide saturation, thus providing a potential tool to constrain its somewhat intractable timing. The observed decoupling of notionally redox-sensitive tracers underlines the caution required in the application of transition metal isotopes as direct redox proxies.

Crystallization history of enriched shergottites from Fe and Mg isotope fractionation in olivine megacrysts

NASA Astrophysics Data System (ADS)

Collinet, Max; Charlier, Bernard; Namur, Olivier; Oeser, Martin; Médard, Etienne; Weyer, Stefan

2017-06-01

Martian meteorites are the only samples available from the surface of Mars. Among them, olivine-phyric shergottites are basalts containing large zoned olivine crystals with highly magnesian cores (Fo 70-85) and rims richer in Fe (Fo 45-60). The Northwest Africa 1068 meteorite is one of the most primitive "enriched" shergottites (high initial 87Sr/86Sr and low initial ε143Nd). It contains olivine crystals as magnesian as Fo 77 and is a major source of information to constrain the composition of the parental melt, the composition and depth of the mantle source, and the cooling and crystallization history of one of the younger magmatic events on Mars (∼180 Ma). In this study, Fe-Mg isotope profiles analyzed in situ by femtosecond-laser ablation MC-ICP-MS are combined with compositional profiles of major and trace elements in olivine megacrysts. The cores of olivine megacrysts are enriched in light Fe isotopes (δ56FeIRMM-14 = -0.6 to -0.9‰) and heavy Mg isotopes (δ26MgDSM-3 = 0-0.2‰) relative to megacryst rims and to the bulk martian isotopic composition (δ56Fe = 0 ± 0.05‰, δ26Mg = -0.27 ± 0.04‰). The flat forsterite profiles of megacryst cores associated with anti-correlated fractionation of Fe-Mg isotopes indicate that these elements have been rehomogenized by diffusion at high temperature. We present a 1-D model of simultaneous diffusion and crystal growth that reproduces the observed element and isotope profiles. The simulation results suggest that the cooling rate during megacryst core crystallization was slow (43 ± 21 °C/year), and consistent with pooling in a deep crustal magma chamber. The megacryst rims then crystallized 1-2 orders of magnitude faster during magma transport toward the shallower site of final emplacement. Megacryst cores had a forsterite content 3.2 ± 1.5 mol% higher than their current composition and some were in equilibrium with the whole-rock composition of NWA 1068 (Fo 80 ± 1.5). NWA 1068 composition is thus close to a primary melt (i.e. in equilibrium with the mantle) from which other enriched shergottites derived.

Thallium isotope evidence for a permanent increase in marine organic carbon export in the early Eocene

USGS Publications Warehouse

Nielsen, S.G.; Mar-Gerrison, S.; Gannoun, A.; LaRowe, D.; Klemm, V.; Halliday, A.N.; Burton, K.W.; Hein, J.R.

2009-01-01

The first high resolution thallium (Tl) isotope records in two ferromanganese crusts (Fe-Mn crusts), CD29 and D11 from the Pacific Ocean are presented. The crusts record pronounced but systematic changes in 205Tl/203Tl that are unlikely to reflect diagenetic overprinting or changes in isotope fractionation between seawater and Fe-Mn crusts. It appears more likely that the Fe-Mn crusts track the Tl isotope composition of seawater over time. The present-day oceanic residence time of Tl is estimated to be about 20,000??yr, such that the isotopic composition should reflect ocean-wide events. New and published Os isotope data are used to construct age models for these crusts that are consistent with each other and significantly different from previous age models. Application of these age models reveals that the Tl isotope composition of seawater changed systematically between ~ 55??Ma and ~ 45??Ma. Using a simple box model it is shown that the present day Tl isotope composition of seawater depends almost exclusively on the ratio between the two principal output fluxes of marine Tl. These fluxes are the rate of removal of Tl from seawater via scavenging by authigenic Fe-Mn oxyhydroxide precipitation and the uptake rate of Tl during low temperature alteration of oceanic crust. It is highly unlikely that the latter has changed greatly. Therefore, assuming that the marine Tl budget has also not changed significantly during the Cenozoic, the low 205Tl/203Tl during the Paleocene is best explained by a more than four-fold higher sequestration of Tl by Fe-Mn oxyhydroxides compared with at the present day. The calculated Cenozoic Tl isotopic seawater curve displays a striking similarity to that of S, providing evidence that both systems may have responded to the same change in the marine environment. A plausible explanation is a marked and permanent increase in organic carbon export from ~ 55??Ma to ~ 45??Ma, which led to higher pyrite burial rates and a significantly reduced flux of Fe-Mn oxide removal as a result of increased biological uptake of Fe and Mn. ?? 2008 Elsevier B.V. All rights reserved.

Experimental determination of iron isotope fractionations among Fe aq 2 + -FeSaq-Mackinawite at low temperatures: Implications for the rock record

NASA Astrophysics Data System (ADS)

Wu, Lingling; Druschel, Greg; Findlay, Alyssa; Beard, Brian L.; Johnson, Clark M.

2012-07-01

The Fe isotope fractionation factors among aqueous ferrous iron (Fe aq 2 +), aqueous FeS clusters (FeSaq), and nanoparticulate mackinawite under neutral and mildly acidic and alkaline pH conditions have been determined using the three-isotope method. Combined voltammetric analysis and geochemical modeling were used to determine the Fe speciation in the experimental systems. The equilibrium 56Fe/54Fe fractionation factor at 20 °C and pH 7 has been determined to be -0.32 ± 0.29 (2σ)‰ between Fe aq 2 + (minor FeSaq also present in the experiment) and mackinawite. This fractionation factor was essentially constant when pH was changed to 6 or 8. When equal molarity of HS- and Fe aq 2 + were added to the system, however, the isotopic fractionation at pH 7 changed to -0.64 ± 0.36 (2σ)‰, correlating with a significant increase in the proportion of FeHS+ and FeSaq. These results highlight a more important role of aqueous Fe-S speciation in the equilibrium Fe isotope fractionation factor than recognized in previous studies. The isotopic fractionation remained constant when temperature was increased from 20 °C to 35 °C for fractionation factors between Fe aq 2 + , and mackinawite and between dominantly FeHS+ and mackinawite. Synthesis experiments similar to those of Butler et al. (2005) and Guilbaud et al. (2010) at pH 4 show consistent results: over time, the aqueous Fe-mackinawite fractionation decreases but even after 38 days of aging the fractionation factor is far from the equilibrium value inferred using the three-isotope method. In contrast, at near-neutral pH the fractionation factor for the synthesis experiment reached the equilibrium value in 38 days. These differences are best explained by noting that at low pH the FeS mackinawite particles coarsen more rapidly via particle aggregation, which limits isotopic exchange, whereas at higher pH mackinawite aggregation is limited, and Fe isotope exchange occurs more rapidly, converging on the equilibrium value. These results suggest that mackinawite formed in natural environments at near-neutral or alkaline pH are unlikely to retain kinetic isotope fractionations, but are more likely to reflect equilibrium isotope compositions. This in turn has important implications for interpreting iron isotope compositions of Fe sulfides in natural systems.

Microbial production of isotopically light iron(II) in a modern chemically precipitated sediment and implications for isotopic variations in ancient rocks

USGS Publications Warehouse

Tangalos, G.E.; Beard, B.L.; Johnson, C.M.; Alpers, Charles N.; Shelobolina, E.S.; Xu, H.; Konishi, H.; Roden, E.E.

2012-01-01

The inventories and Fe isotope composition of aqueous Fe(II) and solid-phase Fe compounds were quantified in neutral-pH, chemically precipitated sediments downstream of the Iron Mountain acid mine drainage site in northern California, USA. The sediments contain high concentrations of amorphous Fe(III) oxyhydroxides [Fe(III)am] that allow dissimilatory iron reduction (DIR) to predominate over Fe–S interactions in Fe redox transformation, as indicated by the very low abundance of Cr(II)-extractable reduced inorganic sulfur compared with dilute HCl-extractable Fe. δ56Fe values for bulk HCl- and HF-extractable Fe were ≈ 0. These near-zero bulk δ56Fe values, together with the very low abundance of dissolved Fe in the overlying water column, suggest that the pyrite Fe source had near-zero δ56Fe values, and that complete oxidation of Fe(II) took place prior to deposition of the Fe(III) oxide-rich sediment. Sediment core analyses and incubation experiments demonstrated the production of millimolar quantities of isotopically light (δ56Fe ≈ -1.5 to -0.5‰) aqueous Fe(II) coupled to partial reduction of Fe(III)am by DIR. Trends in the Fe isotope composition of solid-associated Fe(II) and residual Fe(III)am are consistent with experiments with synthetic Fe(III) oxides, and collectively suggest an equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)am of approximately -2‰. These Fe(III) oxide-rich sediments provide a model for early diagenetic processes that are likely to have taken place in Archean and Paleoproterozoic marine sediments that served as precursors for banded iron formations. Our results suggest pathways whereby DIR could have led to the formation of large quantities of low-δ56Fe minerals during BIF genesis.

On the origin and composition of Theia: Constraints from new models of the Giant Impact

NASA Astrophysics Data System (ADS)

Meier, M. M. M.; Reufer, A.; Wieler, R.

2014-11-01

Knowing the isotopic composition of Theia, the proto-planet which collided with the Earth in the Giant Impact that formed the Moon, could provide interesting insights on the state of homogenization of the inner Solar System at the late stages of terrestrial planet formation. We use the known isotopic and modeled chemical compositions of the bulk silicate mantles of Earth and Moon and combine them with different Giant Impact models, to calculate the possible ranges of isotopic composition of Theia in O, Si, Ti, Cr, Zr and W in each model. We compare these ranges to the isotopic composition of carbonaceous chondrites, Mars, and other Solar System materials. In the absence of post-impact isotopic re-equilibration, the recently proposed high angular momentum models of the Giant Impact ("impact-fission", Cúk, M., Stewart, S.T. [2012]. Science 338, 1047; and "merger", Canup, R.M. [2012]. Science 338, 1052) allow - by a narrow margin - for a Theia similar to CI-chondrites, and Mars. The "hit-and-run" model (Reufer, A., Meier, M.M.M., Benz, W., Wieler, R. [2012]. Icarus 221, 296-299) allows for a Theia similar to enstatite-chondrites and other Earth-like materials. If the Earth and Moon inherited their different mantle FeO contents from the bulk mantles of the proto-Earth and Theia, the high angular momentum models cannot explain the observed difference. However, both the hit-and-run as well as the classical or "canonical" Giant Impact model naturally explain this difference as the consequence of a simple mixture of two mantles with different FeO. Therefore, the simplest way to reconcile the isotopic similarity, and FeO dissimilarity, of Earth and Moon is a Theia with an Earth-like isotopic composition and a higher (∼20%) mantle FeO content.

Tracing the secular evolution of the UCC using the iron isotope composition of ancient glacial diamictites

NASA Astrophysics Data System (ADS)

Liu, X. M.; Gaschnig, R. M.; Rudnick, R. L.; Hazen, R. M.; Shahar, A.

2014-12-01

Iron is the fourth most abundant element in the continental crust and influences global climate and biogeochemical cycles in the ocean1. Continental inputs, including river waters, sediments and atmospheric dust are dominant sources (>95%) of iron into the ocean2. Therefore, understanding how continental inputs may have changed through time is important in understanding the secular evolution of the marine Fe cycle. We analysed the Fe isotopic composition of twenty-four glacial diamictite composites, upper continental crust (UCC) proxies, with ages ranging from the Mesoarchean to the Paleozoic eras to characterize the secular evolution of the UCC. The diamictites all have elevated chemical index of alteration (CIA) and other characteristics of weathered regolith (e.g., strong depletion in soluble elements such as Sr), which they inherited from their upper crustal source region3. δ56Fe in the diamictite composites range from -0.59 to +0.23‰, however, most diamictites cluster with an average δ56Fe of 0.11± 0.20 (2s), overlapping juvenile continental material such as island arc basalts (IABs), which show a narrow range in δ56Fe from -0.04 to +0.14 ‰4. There is no obvious correlation between δ56Fe of the glacial diamictites and the CIA, except that the diamictite with the lowest δ56Fe at -0.59 ‰ also has the highest CIA = 89 (the Paleoproterozoic Makganyene Fm.). The data suggest that the Fe isotope compositions in the upper continental crust did not vary throughout Earth history. Interestingly, chemical weathering and sedimentary transport likely play only a minor role in producing Fe isotope variations in the upper continental crust. Anoxic weathering pre-GOE (Great Oxidation Event) does not seem to generate different Fe isotopic signatures from the post-GOE oxidative weathering environment in the upper continental crust. Therefore, large Fe isotopic fractionations observed in various marine sedimentary records are likely due to other processes occurring in the ocean (e.g., biological activity) instead of abiotic redox reactions on the continent. References: 1.Martin (1990) Paleoceanography. 2.Fantle and DePaolo (2004) EPSL. 3. Gaschnig et al. (2014) EPSL. 4. Dauphas et al. (2009) EPSL.

Tracing the secular evolution of the UCC using the iron isotope composition of ancient glacial diamictites

NASA Astrophysics Data System (ADS)

Liu, X. M.; Gaschnig, R. M.; Rudnick, R. L.; Hazen, R. M.; Shahar, A.

2015-12-01

Iron is the fourth most abundant element in the continental crust and influences global climate and biogeochemical cycles in the ocean1. Continental inputs, including river waters, sediments and atmospheric dust are dominant sources (>95%) of iron into the ocean2. Therefore, understanding how continental inputs may have changed through time is important in understanding the secular evolution of the marine Fe cycle. We analysed the Fe isotopic composition of twenty-four glacial diamictite composites, upper continental crust (UCC) proxies, with ages ranging from the Mesoarchean to the Paleozoic eras to characterize the secular evolution of the UCC. The diamictites all have elevated chemical index of alteration (CIA) and other characteristics of weathered regolith (e.g., strong depletion in soluble elements such as Sr), which they inherited from their upper crustal source region3. δ56Fe in the diamictite composites range from -0.59 to +0.23‰, however, most diamictites cluster with an average δ56Fe of 0.11± 0.20 (2s), overlapping juvenile continental material such as island arc basalts (IABs), which show a narrow range in δ56Fe from -0.04 to +0.14 ‰4. There is no obvious correlation between δ56Fe of the glacial diamictites and the CIA, except that the diamictite with the lowest δ56Fe at -0.59 ‰ also has the highest CIA = 89 (the Paleoproterozoic Makganyene Fm.). The data suggest that the Fe isotope compositions in the upper continental crust did not vary throughout Earth history. Interestingly, chemical weathering and sedimentary transport likely play only a minor role in producing Fe isotope variations in the upper continental crust. Anoxic weathering pre-GOE (Great Oxidation Event) does not seem to generate different Fe isotopic signatures from the post-GOE oxidative weathering environment in the upper continental crust. Therefore, large Fe isotopic fractionations observed in various marine sedimentary records are likely due to other processes occurring in the ocean (e.g., biological activity) instead of abiotic redox reactions on the continent. References: 1.Martin (1990) Paleoceanography. 2.Fantle and DePaolo (2004) EPSL. 3. Gaschnig et al. (2014) EPSL. 4. Dauphas et al. (2009) EPSL.

An assessment of the accuracy of stable Fe isotope ratio measurements on samples with organic and inorganic matrices by high-resolution multicollector ICP-MS

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; von Blanckenburg, Friedhelm

2005-04-01

Multicollector ICP-MS-based stable isotope procedures provide the capability to determine small variations in metal isotope composition of materials, but they are prone to substantial bias introduced by inadequate sample preparation. Such a "cryptic" bias is not necessarily identifiable from the measured isotope ratios. The analytical protocol for Fe isotope analyses of organic and inorganic materials described here identifies and avoids such pitfalls. In medium-mass resolution mode of the ThermoFinnigan Neptune MC-ICP-MS, a 1-ppm Fe solution with an uptake rate of 50-70 [mu]L min-1 yielded 3 × 10-11 A on 56Fe for the ThermoFinnigan stable introduction system and 1.2-1.8 × 10-10 A for the ESI Apex-Q uptake system. Sensitivity was increased again 3-5-fold when using Finnigan X-cones instead of the standard H-cones. The combination of the ESI Apex-Q apparatus and X-cones allowed the determination of the isotope composition on as little as 50 ng of Fe. Fe isotope compositions were corrected for mass bias with both the standard-sample bracketing (SSB) method, and by using the 65Cu/63Cu ratio of added synthetic copper (Cu-doping) as internal monitor of mass discrimination. Both methods provide identical results on high-purity Fe solutions of either synthetic or natural samples. We prefer the SSB method because of its shorter analysis time and more straightforward correction of instrumental mass bias compared to Cu-doping. Strong error correlations of the data are observed in three isotope diagrams. Thus, we suggest that the quality assessment in such diagrams should be performed with error ellipses rather than error bars. Reproducibility of [delta]56Fe, [delta]57Fe and [delta]58Fe values of natural samples alone is not a sufficient criterion for accuracy. A set of tests is lined out that identify cryptic matrix effects and ensure a reproducible level of quality control. Using these criteria and the SSB correction method, we determined the external reproducibilities for [delta]56Fe, [delta]57Fe and [delta]58Fe at the 95% confidence interval from 318 measurements of 95 natural samples to be 0.049, 0.071 and 0.28[per mille sign], respectively.

Persistence of deeply sourced iron in the Pacific Ocean.

PubMed

Horner, Tristan J; Williams, Helen M; Hein, James R; Saito, Mak A; Burton, Kevin W; Halliday, Alex N; Nielsen, Sune G

2015-02-03

Biological carbon fixation is limited by the supply of Fe in vast regions of the global ocean. Dissolved Fe in seawater is primarily sourced from continental mineral dust, submarine hydrothermalism, and sediment dissolution along continental margins. However, the relative contributions of these three sources to the Fe budget of the open ocean remains contentious. By exploiting the Fe stable isotopic fingerprints of these sources, it is possible to trace distinct Fe pools through marine environments, and through time using sedimentary records. We present a reconstruction of deep-sea Fe isotopic compositions from a Pacific Fe-Mn crust spanning the past 76 My. We find that there have been large and systematic changes in the Fe isotopic composition of seawater over the Cenozoic that reflect the influence of several, distinct Fe sources to the central Pacific Ocean. Given that deeply sourced Fe from hydrothermalism and marginal sediment dissolution exhibit the largest Fe isotopic variations in modern oceanic settings, the record requires that these deep Fe sources have exerted a major control over the Fe inventory of the Pacific for the past 76 My. The persistence of deeply sourced Fe in the Pacific Ocean illustrates that multiple sources contribute to the total Fe budget of the ocean and highlights the importance of oceanic circulation in determining if deeply sourced Fe is ever ventilated at the surface.

Persistence of deeply sourced iron in the Pacific Ocean

PubMed Central

Horner, Tristan J.; Williams, Helen M.; Hein, James R.; Saito, Mak A.; Burton, Kevin W.; Halliday, Alex N.; Nielsen, Sune G.

2015-01-01

Biological carbon fixation is limited by the supply of Fe in vast regions of the global ocean. Dissolved Fe in seawater is primarily sourced from continental mineral dust, submarine hydrothermalism, and sediment dissolution along continental margins. However, the relative contributions of these three sources to the Fe budget of the open ocean remains contentious. By exploiting the Fe stable isotopic fingerprints of these sources, it is possible to trace distinct Fe pools through marine environments, and through time using sedimentary records. We present a reconstruction of deep-sea Fe isotopic compositions from a Pacific Fe−Mn crust spanning the past 76 My. We find that there have been large and systematic changes in the Fe isotopic composition of seawater over the Cenozoic that reflect the influence of several, distinct Fe sources to the central Pacific Ocean. Given that deeply sourced Fe from hydrothermalism and marginal sediment dissolution exhibit the largest Fe isotopic variations in modern oceanic settings, the record requires that these deep Fe sources have exerted a major control over the Fe inventory of the Pacific for the past 76 My. The persistence of deeply sourced Fe in the Pacific Ocean illustrates that multiple sources contribute to the total Fe budget of the ocean and highlights the importance of oceanic circulation in determining if deeply sourced Fe is ever ventilated at the surface. PMID:25605900

Glacial influence on the geochemistry of riverine iron fluxes to the Gulf of Alaska and effects of deglaciation

USGS Publications Warehouse

Schroth, A.W.; Crusius, John; Chever, F.; Bostick, B.C.; Rouxel, O.J.

2011-01-01

Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.

Iron Isotopes in Meteorites

NASA Astrophysics Data System (ADS)

Kehm, K.; Alexander, C. M.; Hauri, E. H.

2001-12-01

The recent identification of naturally occurring isotopic mass fractionation of the transition met-als on the Earth has prompted a search for similar variability in meteorites. Studies of Cu, Zn, and Fe, for example, have revealed per-mil level and larger mass fractionations between different bulk meteorites. Such variations can result from temperature-sensitive isotope exchange reactions and kinetic processes, and therefore may reflect conditions in the solar nebula and on meteorite parent bodies. Recent advances in ICP-MS have permitted isotope studies of transition metals and other elements with similarly small isotopic mass dispersions. Among the transition metals, Fe is perhaps the most difficult to analyze by ICP-MS because plasma sources are copious producers of argide molecules that interfere with the measurement of iron isotopes. However, the stable isotope behavior of Fe is of special interest because it is a non-refractory major element in meteorites, present in a variety of mineral associations and redox states. Considerable effort has gone into overcoming the inherent analytical difficulties of measuring Fe using ICP-MS. We recently reported on a technique that achieves argide reduction by operating the plasma source in so-called 'cold' mode. In this presentation, we report results from this ongoing work. To date, analyses of nine different meteorites, and eight individual Tieschitz (H3) chondrules have been completed, along with a number of measurements of the Hawaiian basalt sample Kil1919. All of the bulk meteorite compositions, which include both chondrites and irons, have identical 56Fe/54Fe to within ~ 0.14 per mil (2 sigma), and are indistinguishable from the composition of the terrestrial basalt. The Tieschitz chondrules, on the other hand, tend to have isotopically light compositions. This could reflect formation from fractionated starting material. Alternatively, Fe condensation, under non-equilibrium conditions can enrich light isotopes. Future work will focus on determining the extent of Fe mass fractionation in chondrules from Tieschitz as well as other chondrites. This growing database will help us to understand the conditions in which chondrules formed, potentially placing stringent constraints on theories of their formation.

Iron isotope fingerprints of redox and biogeochemical cycling in the soil-water-rice plant system of a paddy field.

PubMed

Garnier, J; Garnier, J-M; Vieira, C L; Akerman, A; Chmeleff, J; Ruiz, R I; Poitrasson, F

2017-01-01

The iron isotope composition was used to investigate dissimilatory iron reduction (DIR) processes in an iron-rich waterlogged paddy soil, the iron uptake strategies of plants and its translocation in the different parts of the rice plant along its growth. Fe concentration and isotope composition (δ 56 Fe) in irrigation water, precipitates from irrigation water, soil, pore water solution at different depths under the surface water, iron plaque on rice roots, rice roots, stems, leaves and grains were measured. Over the 8.5-10cm of the vertical profiles investigated, the iron pore water concentration (0.01 to 24.3mg·l -1 ) and δ 56 Fe (-0.80 to -3.40‰) varied over a large range. The significant linear co-variation between Ln[Fe] and δ 56 Fe suggests an apparent Rayleigh-type behavior of the DIR processes. An average net fractionation factor between the pore water and the soil substrate of Δ 56 Fe≈-1.15‰ was obtained, taking the average of all the δ 56 Fe values weighted by the amount of Fe for each sample. These results provide a robust field study confirmation of the conceptual model of Crosby et al. (2005, 2007) for interpreting the iron isotope fractionation observed during DIR, established from a series of laboratories experiments. In addition, the strong enrichment of heavy Fe isotope measured in the root relative to the soil solution suggest that the iron uptake by roots is more likely supplied by iron from plaque and not from the plant-available iron in the pore water. Opposite to what was previously observed for plants following strategy II for iron uptake from soils, an iron isotope fractionation factor of -0.9‰ was found from the roots to the rice grains, pointing to isotope fractionation during rice plant growth. All these features highlight the insights iron isotope composition provides into the biogeochemical Fe cycling in the soil-water-rice plant systems studied in nature. Copyright © 2016 Elsevier B.V. All rights reserved.

Iron isotope evidence for the origin of the Moon through partial vaporisation

NASA Astrophysics Data System (ADS)

Poitrasson, F.; Halliday, A. N.; Lee, D. C.; Levasseur, S.; Teutsch, N.

2003-04-01

The currently favoured scenario of the origin of the Moon through a Giant Impact, in which a body approaching the size of Mars hit the proto-Earth and yielded ejecta leading to the Moon remains hypothetical. This theory predicts extremely high temperatures, sufficient to induce planetary-scale vaporisation. We have thus measured the Fe isotope composition of the Earth, Moon and meteorites thought to come from Mars and asteroid Vesta to see if this highly energetic process left an imprint. Our analytical method involves Fe purification through anionic exchange chromatography and iron isotope measurement by MC-ICP-MS. Repeat analyses of standards define 57Fe/54Fe reproducibility of 0.09 per mil (2SD). Meteorites from Mars and Vesta, give δ57Fe/54Fe values indistinguishable to the international IRMM-14 Fe isotopic standard. In contrast, ten lunar samples, spanning a large range in composition give a mean 0.2 per mil heavier than IRMM-14. Mantle-derived terrestrial samples yield a mean δ57Fe/54Fe intermediate between the Moon and Mars. Student's t-tests show that the terrestrial mean is significantly different from the averages of Mars, Vesta and the Moon at a confidence level of more than 99%. These new Fe isotope measurements, combined with previous oxygen isotope data rule out alternative theories of the origin of the Moon through co-accretion, capture or fission from the proto-Earth. In contrast, vaporisation of bodies in space can generate kinetic isotope fractionation, leaving residues with a relatively heavier isotope signature. Hence, the Earth, and especially the Moon, can represent such heavy residues having lost part of their light iron through vaporisation. Only the Giant Impact can account for the energy required to partially melt and vaporise major portion of the Earth and the impactor. Rayleigh kinetic isotope calculations suggest that the Moon lost up to 1% of its iron, whereas the Earth lost up to 0.5% during partial vaporisation.

The role of sedimentology, oceanography, and alteration on the δ56Fe value of the Sokoman Iron Formation, Labrador Trough, Canada

NASA Astrophysics Data System (ADS)

Raye, Urmidola; Pufahl, Peir K.; Kyser, T. Kurtis; Ricard, Estelle; Hiatt, Eric E.

2015-09-01

The Sokoman Formation is a ca. 100-m-thick succession of interbedded iron formation and fine-grained siliciclastics deposited at 1.88 Ga. Accumulation occurred on a dynamic paleoshelf where oxygen stratification, coastal upwelling of hydrothermally derived Fe and Si, microbial processes, tide and storm currents, diagenesis, and low-grade prehnite-pumpellyite metamorphism controlled lithofacies character and produced complex associations of multigenerational chert, hematite, magnetite, greenalite, stilpnomelane and Fe carbonate. Hematite-rich facies were deposited along suboxic segments of the coastline where photosynthetic oxygen oases impinged on the seafloor. Hematitic, cross-stratified grainstones were formed by winnowing and reworking of freshly precipitated Fe-(oxyhydr)oxide and opal-A by waves and currents into subaqueous dunes. Magnetite-rich facies contain varying proportions of greenalite and stilpnomelane and record deposition in anoxic middle shelf environments beneath an oxygen chemocline. Minor negative Ce anomalies in hematitic facies, but prominent positive Ce and Eu anomalies and high LREE/HREE ratios in magnetite-rich facies imply the existence of a weakly oxygenated surface ocean above anoxic bottom waters. The Fe isotopic composition of 31 whole rock (-0.46 ⩽ δ56Fe ⩽ 0.47‰) and 21 magnetite samples (-0.29 ⩽ δ56Fe ⩽ 0.22‰) from suboxic and anoxic lithofacies was controlled primarily by the physical oceanography of the paleoshelf. Despite low-grade metamorphism recorded by the δ18O values of paragenetically related quartz and magnetite, the Sokoman Formation preserves a robust primary Fe isotopic signal. Coastal upwelling is interpreted to have affected the isotopic equilibria between Fe2+aq and Fe-(oxyhydr)oxide in open marine versus coastal environments, which controlled the Fe isotopic composition of lithofacies. Unlike previous work that focuses on microbial and abiotic fractionation processes with little regard for paleoenvironment, our work demonstrates that depositional setting is paramount in governing the Fe isotopic composition of iron formations irrespective of what Fe-bearing minerals precipitated.

Fe isotope composition of the Quaternary Red Clay in Southeast China and its paleo-environmental implications

NASA Astrophysics Data System (ADS)

Hu, Xue-Feng; Xue, Yong

2015-04-01

Fe has four stable isotopes, 54Fe (5.84%), 56Fe (91.76%), 57Fe (2.12%) and 58Fe (0.28%). The occurrence of Fe isotopic fractionation during the weathering and pedogenic processes might have some significant paleo-environmental implications. The Quaternary Red Clay (QRC), widely distributed to the south of the Yangtze River, is regarded as a potential archive to record the paleoclimatic changes in subtropical China since the Middle Pleistocene. The composition of Fe isotopes in a profile of the QRC in Langxi County, Anhui Province, Southeast China, was analyzed by the MC-ICP-MS method in this study. The results were as follows: (1) δ56Fe of the Yellow-brown Earth (YBE), the uppermost layer of the profile, only slightly fluctuates between 0.10‰ ~ 0.12‰. That of the Uniform Red Clay (URC) was stable and 0.03‰ in content. That of the Reticulate Red Clay (RRC) in the lower part of the profile, however, was instable and fluctuates between -0.06‰ ~ 0.05‰. (2) The reticulate (net-like) pattern of the RRC was formed by the partial leaching of Fe in the red clay possibly due to long-term frequent fluctuations of groundwater table. The white veins of the RRC were deficiency in both total Fe (Fet) and free Fe (Fed), but the red ones were not. A significant difference of δ56Fe between the white and red veins of the RRC was found. δ56Fe of the white veins, 0.35‰ on average, was significantly higher than that of the red veins, -0.09‰ on average. This suggests that lighter Fe isotopes were preferentially removed during the formation of the reticulate pattern. (3) The content of free Fe oxides in soil is evaluated by the CBD-extracted method. δ56Fe of the CBD-extracted fraction of the red clay samples, -0.083‰ on average, is significantly lower than that of the residual fraction, 0.361‰ on average, suggesting that lighter Fe isotopes were preferentially released from primary minerals to form Fe oxides in the red clay. (4) δ56Fe of the entire profile was negatively significantly correlated with Fet and Fed contents (r2=0.3009 and 0.5105, respectively), which also suggests that Fe in the QRC becomes heavier after the preferential leaching of lighter Fe during the intensive weathering and reticulating processes. In short, the Fe isotopes were only weakly fractionated in the red clay formation under an aerobic condition. When the RRC was formed, however, a large amount of lighter Fe isotopes were preferentially removed under an anaerobic condition and heavier Fe were relatively accumulated in the residues. Therefore, heavier Fe in the red clay may imply a warm and humid climate and luxuriant vegetation during the Middle Pleistocene. The Fe isotope composition of soils or paleosols is a promising factor to interpret pedogenic processes and indicate paleo-environmental changes.

Contrasting Effects of Carbon and Sulfur on Fe-Isotope Fractionation between Metal and Silicate Melt during Planetary Core Formation

NASA Astrophysics Data System (ADS)

Elardo, S. M.; Shahar, A.

2015-12-01

There are numerous studies that show well-resolved Fe isotope fractionations in igneous materials from different planetary bodies. Potential explanations for these fractionations include a non-chondritic bulk planetary Fe isotopic composition, and equilibrium fractionation between Fe-alloys or minerals and silicate melts during planetary differentiation, mantle melting, or fractional crystallization. This is further complicated by the fact that these processes are not mutually exclusive, making the interpretation of Fe isotope data a complex task. Here we present new experimental results investigating the effect of C on Fe isotope fractionation between molten peridotite and an Fe-alloy. Experiments were conducted at 1 GPa and 1850° C for 0.5 - 3 hours on a mixture of an 54Fe-spiked peridotite and Fe-metal with and without Ni metal in an end-loaded piston cylinder at the Geophysical Laboratory. Carbon saturation was achieved with a graphite capsule, and resulted in C contents of the Fe-alloy in our experiments ranging from 3.8 - 4.9 wt. %. The metal and silicate phases from half of each experiment were separated manually and dissolved in concentrated acids. Iron was separated from matrix elements by anion exchange chromatagraphy. Iron-isotopic compositions were determined with the Nu Plasma II MC-ICP-MS at GL. The other half of each experiment was used for quantitative microbeam analysis. Equilibrium was assessed with a time series and the three-isotope exchange method. The Ni-free experiments resulted in no resolvable Fe isotope fractionation between the Fe-C-alloy and molten silicate. This is in contrast to the results of Shahar et al. (2015) which showed a fractionation for Δ57Fe of ~0.18 ‰ between a peridotite and an Fe-alloy with a similar S abundance to C in these experiments. The one experiment thus far that contained Ni (~4 wt. % in the alloy) showed a resolvable fractionation between the Fe-Ni-C alloy and silicate of ~0.10 ‰. Shahar et al. found a similar magnitude fractionation to our Ni bearing experiment in experiments with no C or S. The difference in temperature (1650° C in Shahar et al. vs. 1850° C here) may be partially responsible for these discrepancies. Ongoing experiments will further investigate the effects of C and other light elements on Fe isotope fractionation during core segregation.

Isotope pattern deconvolution as a tool to study iron metabolism in plants.

PubMed

Rodríguez-Castrillón, José Angel; Moldovan, Mariella; García Alonso, J Ignacio; Lucena, Juan José; García-Tomé, Maria Luisa; Hernández-Apaolaza, Lourdes

2008-01-01

Isotope pattern deconvolution is a mathematical technique for isolating distinct isotope signatures from mixtures of natural abundance and enriched tracers. In iron metabolism studies measurement of all four isotopes of the element by high-resolution multicollector or collision cell ICP-MS allows the determination of the tracer/tracee ratio with simultaneous internal mass bias correction and lower uncertainties. This technique was applied here for the first time to study iron uptake by cucumber plants using 57Fe-enriched iron chelates of the o,o and o,p isomers of ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA) and ethylenediamine tetraacetic acid (EDTA). Samples of root, stem, leaves, and xylem sap, after exposure of the cucumber plants to the mentioned 57Fe chelates, were collected, dried, and digested using nitric acid. The isotopic composition of iron in the samples was measured by ICP-MS using a high-resolution multicollector instrument. Mass bias correction was computed using both a natural abundance iron standard and by internal correction using isotope pattern deconvolution. It was observed that, for plants with low 57Fe enrichment, isotope pattern deconvolution provided lower tracer/tracee ratio uncertainties than the traditional method applying external mass bias correction. The total amount of the element in the plants was determined by isotope dilution analysis, using a collision cell quadrupole ICP-MS instrument, after addition of 57Fe or natural abundance Fe in a known amount which depended on the isotopic composition of the sample.

Iron isotope fractionation in marine invertebrates in near shore environments

NASA Astrophysics Data System (ADS)

Emmanuel, S.; Schuessler, J. A.; Vinther, J.; Matthews, A.; von Blanckenburg, F.

2014-04-01

Chitons (Mollusca) are marine invertebrates that produce radula (teeth or rasping tongue) containing high concentrations of biomineralized magnetite and other iron bearing minerals. As Fe isotope signatures are influenced by redox processes and biological fractionation, Fe isotopes in chiton radula might be expected to provide an effective tracer of ambient oceanic conditions and biogeochemical cycling. Here, in a pilot study to measure Fe isotopes in marine invertebrates, we examine Fe isotopes in modern marine chiton radula collected from different locations in the Atlantic and Pacific oceans to assess the range of isotopic values, and to test whether or not the isotopic signatures reflect seawater values. Furthermore, by comparing two species that have very different feeding habits but collected from the same location, we infer a possible link between diet and Fe isotopic signatures. Values of δ56Fe (relative to IRMM-014) in chiton teeth range from -1.90 to 0.00‰ (±0.05‰ (2σ) uncertainty in δ56Fe), probably reflecting a combination of geographical control and biological fractionation processes. Comparison with published local surface seawater Fe isotope data shows a consistent negative offset of chiton teeth Fe isotope compositions relative to seawater. Strikingly, two different species from the same locality in the North Pacific (Puget Sound, Washington, USA) have distinct isotopic signatures. Tonicella lineata, which feeds on red algae, has a mean δ56Fe of -0.65 ± 0.26‰ (2σ, 3 specimens), while Mopalia muscosa, which feeds primarily on green algae, shows lighter isotopic values with a mean δ56Fe of -1.47 ± 0.98‰ (2σ, 5 specimens). Although chitons are not simple recorders of the ambient seawater Fe isotopic signature, these preliminary results suggest that Fe isotopes provide information concerning Fe biogeochemical cycling in near shore environments, and might be used to probe sources of Fe in the diets of different organisms.

Iron isotope composition of particles produced by UV-femtosecond laser ablation of natural oxides, sulfides, and carbonates.

PubMed

d'Abzac, Francois-Xavier; Beard, Brian L; Czaja, Andrew D; Konishi, Hiromi; Schauer, James J; Johnson, Clark M

2013-12-17

The need for femtosecond laser ablation (fs-LA) systems coupled to MC-ICP-MS to accurately perform in situ stable isotope analyses remains an open question, because of the lack of knowledge concerning ablation-related isotopic fractionation in this regime. We report the first iron isotope analysis of size-resolved, laser-induced particles of natural magnetite, siderite, pyrrhotite, and pyrite, collected through cascade impaction, followed by analysis by solution nebulization MC-ICP-MS, as well as imaging using electron microscopy. Iron mass distributions are independent of mineralogy, and particle morphology includes both spheres and agglomerates for all ablated phases. X-ray spectroscopy shows elemental fractionation in siderite (C-rich agglomerates) and pyrrhotite/pyrite (S-rich spheres). We find an increase in (56)Fe/(54)Fe ratios of +2‰, +1.2‰, and +0.8‰ with increasing particle size for magnetite, siderite, and pyrrhotite, respectively. Fe isotope differences in size-sorted aerosols from pyrite ablation are not analytically resolvable. Experimental data are discussed using models of particles generation by Hergenröder and elemental/isotopic fractionation by Richter. We interpret the isotopic fractionation to be related to the iron condensation time scale, dependent on its saturation in the gas phase, as a function of mineral composition. Despite the isotopic variations across aerosol size fractions, total aerosol composition, as calculated from mass balance, confirms that fs-LA produces a stoichiometric sampling in terms of isotopic composition. Specifically, both elemental and isotopic fractionation are produced by particle generation processes and not by femtosecond laser-matter interactions. These results provide critical insights into the analytical requirements for laser-ablation-based stable isotope measurements of high-precision and accuracy in geological samples, including the importance of quantitative aerosol transport to the ICP.

High δ56Fe values in Samoan basalts

NASA Astrophysics Data System (ADS)

Konter, J. G.; Pietruszka, A. J.; Hanan, B. B.; Finlayson, V.

2014-12-01

Fe isotope fractionation spans ~0-0.4 permil in igneous systems, which cannot all be attributed to variable source compositions since peridotites barely overlap these compositions. Other processes may fractionate Fe isotopes such as variations in the degree of partial melting, magmatic differentiation, fluid addition related to the final stages of melt evolution, and kinetic fractionation related to diffusion. An important observation in igneous systems is the trend of increasing Fe isotope values against an index of magmatic fractionation (e.g. SiO2; [1]). The data strongly curve from δ56Fe >0.3 permil for SiO2 >70 wt% down to values around 0.09 permil from ~65 wt% down to 40 wt% SiO2 of basalts. However, ocean island basalts (OIBs) have a slightly larger δ56Fe variability than mid ocean ridge basalts (MORBs; [e.g. 2]). We present Fe isotope data on samples from the Samoan Islands (OIB) that have unusually high δ56Fe values for their SiO2 content. We rule out alteration by using fresh samples, and further test for the effects of magmatic processes on the δ56Fe values. In order to model the largest possible fractionation, unusually small degrees of melting with extreme fractionation factors are modeled with fractional crystallization of olivine alone, but such processing fails to fractionate the Fe isotopes to the observed values. Moreover, Samoan lavas likely also fractionated clinopyroxene, and its lower fractionation factor would limit the final δ56Fe value of the melt. We therefore suggest the mantle source of Samoan lavas must have had unusually high δ56Fe. However, there is no clear correlation with the highly radiogenic isotope signatures that reflect the unique source compositions of Samoa. Instead, increasing melt extraction correlates with lower δ56Fe values in peridotites assumed to be driven by the preference for the melt phase by heavy Fe3+, while high values may be related to metasomatism [3]. The latter would be in line with metasomatized xenoliths from Samoa [4]. [1] Heimann et al., 2008, doi:10.1016/j.gca.2008.06.009 [2] Teng et al., 2013, doi:10.1016/j.gca.2012.12.027 [3] Williams et al., 2004, doi: 10.1126/science.1095679 [4] Hauri et al., 1993, doi: 10.1038/365221a0

Discerning crystal growth from diffusion profiles in zoned olivine by in situ Mg–Fe isotopic analyses

USGS Publications Warehouse

Sio, Corliss Kin I.; Dauphas, Nicolas; Teng, Fang-Zhen; Chaussidon, Marc; Helz, Rosalind T.; Roskosz, Mathieu

2013-01-01

Mineral zoning is used in diffusion-based geospeedometry to determine magmatic timescales. Progress in this field has been hampered by the challenge to discern mineral zoning produced by diffusion from concentration gradients inherited from crystal growth. A zoned olivine phenocryst from Kilauea Iki lava lake (Hawaii) was selected for this study to evaluate the potential of Mg and Fe isotopes for distinguishing these two processes. Microdrilling of the phenocryst (∼300 μm drill holes) followed by MC-ICPMS analysis of the powders revealed negatively coupled Mg and Fe isotopic fractionations (δ26Mg from +0.1‰ to −0.2‰ and δ56Fe from −1.2‰ to −0.2‰ from core to rim), which can only be explained by Mg–Fe exchange between melt and olivine. The data can be explained with ratios of diffusivities of Mg and Fe isotopes in olivine scaling as D2/D1 = (m1/m2)β with βMg ∼0.16 and βFe ∼0.27. LA-MC-ICPMS and MC-SIMS Fe isotopic measurements are developed and are demonstrated to yield accurate δ56Fe measurements within precisions of ∼0.2‰ (1 SD) at spatial resolutions of ∼50 μm. δ56Fe and δ26Mg stay constant with Fo# in the rim (late-stage overgrowth), whereas in the core (original phenocryst) δ56Fe steeply trends toward lighter compositions and δ26Mg trends toward heavier compositions with higher Fo#. A plot of δ56Fe vs. Fo# immediately distinguishes growth-controlled from diffusion-controlled zoning in these two regions. The results are consistent with the idea that large isotopic fractionation accompanies chemical diffusion in crystals, whereas fractional crystallization induces little or no isotopic fractionation. The cooling timescale inferred from the chemical-isotope zoning profiles is consistent with the documented cooling history of the lava lake. In the absence of geologic context, in situ stable isotopic measurements may now be used to interpret the nature of mineral zoning. Stable isotope measurements by LA-MC-ICPMS and MC-SIMS can be used as standard petrologic tools to identify samples for diffusion-based geospeedometry.

Mass-dependent and -independent fractionation of Fe isotopes in magnetotactic bacteria

NASA Astrophysics Data System (ADS)

Amor, M.; Busigny, V.; Louvat, P.; Gelabert, A.; Cartigny, P.; Durand-Dubief, M.; Ona-Nguema, G.; Alphandéry, E.; Chebbi, I.; Guyot, F. J.

2016-12-01

Magnetotactic bacteria (MTB) perform biomineralization of intracellular magnetite (Fe3O4) nanoparticles. Although they may be among the oldest microorganisms capable of biomineralization on Earth, identification of their activity in the geological record remains poorly resolved because of the lack of reliable signatures. Here, we determined Fe isotope fractionation by the magnetotactic bacterium Magnetospirillum magneticum strain AMB-1 to better understand Fe cycling in MTB and provide new signatures of the contribution of MTB to iron geochemistry. AMB-1 strain was cultivated with either Fe(III)-quinate or Fe(II)-ascorbate as Fe sources. Iron isotope composition of Fe sources, bacterial growth media after AMB-1 cultures, bacterial lysates (corresponding to AMB-1 cells devoid of magnetite) and magnetite samples were analyzed by MC-ICP-MS after column chromatography. In the two culture conditions, growth media after AMB-1 cultures were enriched in light Fe isotopes relative to Fe sources. Two distinct bacterial Fe reservoirs were characterized in AMB-1: (1) magnetite enriched in the light Fe isotopes by 1.5 to 2.5‰ in δ56Fe relative to Fe sources, and (2) lysate enriched in the heavy Fe isotopes by 0.3 to 0.8‰ relative to Fe sources. More importantly, mass-independent fractionations in odd (57Fe) but not in even isotopes (54Fe, 56Fe and 58Fe) were observed for the first time, highlighting a magnetic isotope effect. Magnetite samples were significantly enriched in 57Fe by 0.23‰ relative to 54Fe, 56Fe and 58Fe. Based on our results, we propose a model for Fe cycling and magnetite biomineralization in AMB-1, and propose to use this specific mass-independent signature of Fe isotopes to evaluate the contribution of MTB to the iron biogeochemistry of recent and ancient environmental samples.

Iron Isotope Constraints on Planetesimal Core Formation

NASA Astrophysics Data System (ADS)

Jordan, M.; Young, E. D.

2016-12-01

The prevalence of iron in both planetary cores and silicate mantles renders the element a valuable tool for understanding core formation. Magmatic iron meteorites exhibit an enrichment in 57Fe/54Fe relative to chondrites and HED meteorites. This is suggestive of heavy Fe partitioning into the cores of differentiated bodies. If iron isotope fractionation accompanies core formation, we can elucidate details about the history of accretion for planetary bodies as well as their compositions and relative core sizes. The equilibrium 57Fe/54Fe between metal and silicate is necessary for understanding observed iron isotope compositions and placing constraints on core formation. We measure this fractionation in two Aubrite meteorites, Norton County and Mount Egerton, which have known temperatures of equilibration and equilibrated silicon isotopes. Iron was purified using ion-exchange chromatography. Data were collected on a ThermoFinnigan NeptuneTM multiple-collector inductively coupled plasma-source mass spectrometer (MC-ICP-MS) run in wet plasma mode. The measured fractionation Δ57Femetal-silicate is 0.08‰ ± 0.039 (2 SE) for Norton County and 0.09‰ ± 0.019 (2 SE) for Mount Egerton, indicating that the heavy isotopes of Fe partition into the metallic phase. These rocks are in isotopic equilibrium at a temperature of 1130 K and 1200 K ± 80 K, respectively. The concentration of the heavy isotopes of iron in the metallic phase is consistent with recent experimental studies. Using our measured metal-silicate Fe isotope fractionation and the resulting temperature calibration, while taking into account impurities in the metallic phase and temperatures of equilibration, determine that core formation could explain the observed difference between magmatic iron meteorites and chondrites if parent bodies have small cores. In order to verify that Rayleigh distillation during fractional crystallization was not a cause of iron isotope fractionation in iron meteorites, we measured iron isotope ratios in a suite of iron meteorites representing a large range of degrees of fractional crystallization. We find no clear variation in 57Fe/54Fe among these samples.

Magnesium isotopic evidence for chemical disequilibrium among cumulus minerals in layered mafic intrusion

NASA Astrophysics Data System (ADS)

Chen, Lie-Meng; Teng, Fang-Zhen; Song, Xie-Yan; Hu, Rui-Zhong; Yu, Song-Yue; Zhu, Dan; Kang, Jian

2018-04-01

Magnesium isotopic compositions of olivine, clinopyroxene, and ilmenite from the Baima intrusion, SW China, for the first time, are investigated to constrain the magnitude and mechanisms of Mg isotope fractionation among cumulus minerals in layered mafic intrusions and to evaluate their geological implications. Olivine and clinopyroxene have limited Mg isotope variations, with δ26Mg ranging from -0.33 to +0.05‰ and from -0.29 to -0.13‰, respectively, similar to those of mantle xenolithic peridotites. By contrast, ilmenites display extremely large Mg isotopic variation, with δ26Mg ranging from -0.50 to +1.90‰. The large inter-mineral fractionations of Mg isotopes between ilmenite and silicates may reflect both equilibrium and kinetic processes. A few ilmenites have lighter Mg isotopic compositions than coexisting silicates and contain high MgO contents without compositional zoning, indicating equilibrium fractionation. The implication is that the light Mg isotopic compositions of lunar high-Ti basalts may result from an isotopically light source enriched in cumulate ilmenites. On the other hand, most ilmenites have heavy Mg isotopic compositions, coupled with high MgO concentration and chemical zoning, which can be quantitatively modeled by kinetic Mg isotope fractionations induced by subsolidus Mg-Fe exchange between ilmenite and ferromagnesian silicates during the cooling of the Baima intrusion. The extensive occurrence of kinetic Mg isotope fractionation in ilmenites implies the possibility of widespread compositional disequilibrium among igneous minerals in magma chambers. Consequently, disequilibrium effects need to be considered in studies of basaltic magma evolution, magma chamber processes, and magmatic Fe-Ti oxide ore genesis.

Iron isotopes in ancient and modern komatiites: Evidence in support of an oxidised mantle from Archean to present

NASA Astrophysics Data System (ADS)

Hibbert, K. E. J.; Williams, H. M.; Kerr, A. C.; Puchtel, I. S.

2012-03-01

The mantle of the modern Earth is relatively oxidised compared to the initially reducing conditions inferred for core formation. The timing of the oxidation of the mantle is not conclusively resolved but has important implications for the timing of the development of the hydrosphere and atmosphere. In order to examine the timing of this oxidation event, we present iron isotope data from three exceptionally well preserved komatiite localities, Belingwe (2.7 Ga), Vetreny (2.4 Ga) and Gorgona (0.089 Ga). Measurements of Fe isotope compositions of whole-rock samples are complemented by the analysis of olivine, spinel and pyroxene separates. Bulk-rock and olivine Fe isotope compositions (δ57Fe) define clear linear correlations with indicators of magmatic differentiation (Mg#, Cr#). The mean Fe isotope compositions of the 2.7-2.4 Ga and 0.089 Ga samples are statistically distinct and this difference can be explained by greater extent of partial melting represented by the older samples and higher mantle ambient temperatures in the Archean and early Proterozoic relative to the present day. Significantly, samples of all ages define continuous positive linear correlations between bulk rock δ57Fe and V/Sc and δ57Fe and V, and between V/Sc and V with TiO2, providing evidence for the incompatible behaviour of V (relative to Sc) and of isotopically heavy Fe. Partial melting models calculated using partition coefficients for V at oxygen fugacities (fO2s) of 0 and + 1 relative to the fayalite-magnetite-quartz buffer (FMQ) best match the data arrays, which are defined by all samples, from late Archean to Tertiary. These data, therefore, provide evidence for komatiite generation under moderately oxidising conditions since the late Archean, and argue against a change in mantle fO2 concomitant with atmospheric oxygenation at ~ 2.4 Ga.

Iron isotopic systematics of pyroxenite xenoliths from North China Craton: implications for Melt-rock interaction in the sub-continental lithospheric mantle beneath eastern China

NASA Astrophysics Data System (ADS)

Zhao, X.; Cao, H.; Yu, H.; Huang, F.

2016-12-01

Iron isotope systems have become widely used tools in high temperature geochemistry and provide important constraints on mantle dynamics. Here, we report Fe isotopic data on a series of pyroxenite xenoliths from Hannuoba, North China Craton to further constrain the Fe isotopic composition of the mantle and investigate the behavior of Fe isotopes during mantle processes. These xenoliths range from Cr- pyroxenites, Al-pyroxenites to garnet pyroxenites, and are taken as physical evidence for different episodes of melt injection events. Our results show that both Cr- pyroxenites and Al-pyroxenites have a narrow range of Fe isotopes (δ57Fe=-0.01 to 0.09), similar to that reported typical mantle peridotites and they show equilibrium inter-mineral Fe isotope fractionation between coexisting mantle minerals. In contract, the garnet pyroxenites, which are products of reaction between a silicate melt and peridotite, exhibit larger Fe isotopic variations, with δ57Fe ranging from 0.08 to 0.30. The δ57Fe values of minerals in these garnet pyroxenites also vary widely from -0.25 to -0.03 in olivines, from -0.04 to 0.14 in orthopyroxenes, from -0.07 to 0.31 in clinopyroxenes, from 0.07 to 0.26 in spinels and from 0.30 to 0.39 in garnets. These observed data stand in marked contrast to the calculated equilibrium Fe isotope fractionation between coexisting mantle minerals at mantle temperature from theory, indicating disequilibrium isotope fractionation. The disequilibrium isotope fractionations between coexisting mantle minerals in garnet pyroxenites most likely reflect kinetic isotope fractionation during melt-peridotite interaction. In addition, the phlogopite clinopyroxenite with an apparent metasomatic overprint has the heaviest δ57Fe (as high as 1.00) but lightest δ26Mg (as low as -1.50) values of the investigated samples. Our study shows that mantle metasomatism plays an important role in producing Fe isotopic heterogeneity of the subcontinental mantle.

Controls on the iron isotopic composition of global arc magmas

NASA Astrophysics Data System (ADS)

Foden, John; Sossi, Paolo A.; Nebel, Oliver

2018-07-01

We determined the iron isotope composition of 130 mafic lavas from 15 arcs worldwide with the hypothesis that the results would reflect the relatively high oxidation state of arc magmas. Although this expectation was not realized, this Fe isotope data set reveals important insights into the geodynamic controls and style of the melting regimes in the sub-arc mantle. Samples are from oceanic arcs from the circum-Pacific, the Indonesian Sunda-Banda islands, Scotia and the Lesser Antilles as well as from the eastern Pacific Cascades. Their mean δ57Fe value is +0.075 ± 0.05‰, significantly lighter than MORB (+0.15 ± 0.03‰). Western Pacific arcs extend to very light δ57Fe (Kamchatka = -0.11 ± 0.04‰). This is contrary to expectation, because Fe isotope fractionation factors (Sossi et al., 2016, 2012) and the incompatibility of ferric versus ferrous iron during mantle melting, predict that melts of more oxidized sources will be enriched in heavy Fe isotopes. Subducted oxidation capacity flux may correlate with hydrous fluid release from the slab. If so, a positive correlation between each arc's thermal parameter (ϕ) and δ57Fe is predicted. On the contrary, the sampled arcs mostly contribute to a negative array with the ϕ value. High ϕ arcs, largely in the western Pacific, have primary magmas with lower δ57Fe values than the low ϕ, eastern Pacific arcs. Arcs with MORB-like Sr-, Nd- and Pb-isotopes, show a large range of δ57Fe from heavy MORB-like values (Scotia or the Cascades) to very light values (Kamchatka, Tonga). Although all basalts with light δ57Fe values have MORB-like Pb-, Nd- and Sr-isotope ratios some, particularly those from eastern Indonesia, have heavier δ57Fe and higher Pb- and Sr- and lower Nd-isotope ratios reflecting sediment contamination of the mantle wedge. Because basalts with MORB-like radiogenic isotopes range all the way from heavy to light δ57Fe values this trend is process-, not source composition-driven. Neither the slab-derived influx of fluids with light iron or sediment-derived melts with heavier iron can drive the iron isotopic shifts. The trend to light iron isotopes is partly the result of repeated, hydrous flux-driven, fO2-buffered, melting of initially normal-DMM-like mantle. However the most negative δ57Fe must also reflect re-melting of sources that have experienced prior diffusive (disequilibrium) stripping of heavy Fe isotopes due to rapid melt extraction and metasomatism. Data from intra-arc to back-arc rifts in the western Pacific show that these arc signatures are rapidly dispersed by influx of DMM or OIB mantle once intra- and back-arc rifting and slab rollback gains momentum. We suggest that the characteristic light arc signatures only form when the source is lodged under arcs where sub-arc mantle undergoes corner flow forming an isolated roll. This process of heavy iron depletion is most efficient in the high ϕ arcs of the western Pacific and least prevalent in the low ϕ arcs of the eastern Pacific where δ57Fe values are MORB-like. This implies that there is a fundamental change in character of sub-arc mantle melting between east and west Pacific, percolative and fluid fluxed in the west and diapiric and decompressional in the east.

Spatially controlled Fe and Si isotope variations: an alternative view on the formation of the Torres del Paine pluton

NASA Astrophysics Data System (ADS)

Gajos, Norbert A.; Lundstrom, Craig C.; Taylor, Alexander H.

2016-11-01

We present new Fe and Si isotope ratio data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of an approximately 1 km vertical exposure of homogenous granite overlying a contemporaneous 250-m-thick mafic gabbro suite. This first-of-its-kind spatially dependent Fe and Si isotope investigation of a convergent margin-related pluton aims to understand the nature of granite and silicic igneous rock formation. Results collected by MC-ICP-MS show a trend of increasing δ56Fe and δ30Si with increasing silica content as well as a systematic increase in δ56Fe away from the mafic base of the pluton. The marginal Torres del Paine granites have heavier Fe isotope signatures (δ56Fe = +0.25 ± 0.02 2se) compared to granites found in the interior pluton (δ56Fe = +0.17 ± 0.02 2se). Cerro Toro country rock values are isotopically light in both Fe and Si isotopic systems (δ56Fe = +0.05 ± 0.02 ‰; δ30Si = -0.38 ± 0.07 ‰). The variations in the Fe and Si isotopic data cannot be accounted for by local assimilation of the wall rocks, in situ fractional crystallization, late-stage fluid exsolution or some combination of these processes. Instead, we conclude that thermal diffusion or source magma variation is the most likely process producing Fe isotope ratio variations in the Torres del Paine pluton.

Experimental investigation on V isotope equilibrium fractionation factor between metal and silicate melt

NASA Astrophysics Data System (ADS)

Zhang, S.; Zhang, H.; Huang, F.

2017-12-01

Equilibrium fractionation factors of stable isotopes between metal and silicate melt are of vital importance for understanding the isotope variations within meteorites and planetary bodies. The V isotope composition (reported as δ51V = 1000 × [(51V/50Vsample/51V/50VAA)-1] ) of the bulk silicate Earth (BSE) has been estimated as δ51V = -0.7 ± 0.2‰ (2sd) [1], which is significantly heavier than most meteorites by 1‰ [2]. Such isotopic offset may provide insights for the core formation and core-mantle segregation. Therefore, it is important to understand V isotope equilibrium fractionation factor between silicate melt and metal. Nielsen et al. (2014) [2] had performed 3 experiments using starting materials of pure Fe metal and An50Di28Fo22 composition, revealing no resolvable V isotope fractionation. However, it is not clear whether chemical compositions in the melts can affect V isotope fractionations. Therefore, we experimentally calibrated equilibrium V isotope fractionation between Fe metallic and basaltic melt, with particular focus on the effect of Ni and other light elements. Experiments were performed at 1 GPa and 1600 oC using a 3/4″ end-loaded piston cylinder. The starting materials consisted of 1:1 mixture of pure Fe metal and basaltic composition [3]. The isotope equilibrium was assessed using time series experiments combined with the reverse reaction method. Carbon saturation and C-free experiments were achieved by using graphite and silica capsules, respectively. The Ni series experiments were doped with 6 wt% Ni into the starting Fe metal. The metal and silicate phases of samples were mechanically separated, V was purified using a chromatographic technique, and V isotope ratios were measured using MC-ICP-MS [4]. Carbon saturation, C-free experiments and Ni series experiment all show non-resolvable V isotope fractionation between metal and basaltic melt, which indicates that the presence of C and Ni could not affect V isotope fractionation during core formation. More experiments will be performed to explore the effect of Si and S in the metal on V isotope fractionation between metal and silicate melt.References: [1] Prytulak et al. (2013) EPSL 365, 177-189 [2] Nielsen et al. (2014) EPSL 389, 167-175 [3] Cottrell et al. (2009) CG 268, 167-179 [4] Wu et al. (2016) CG 421, 17-25

Experimental evidence for the absence of iron isotope fractionation between metal and silicate liquids at 1 GPa and 1250-1300 °C and its cosmochemical consequences

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Schmidt, Max W.; Bourdon, Bernard

2012-09-01

Iron isotope fractionation during metal-silicate differentiation has been proposed as a cause for differences in iron isotope compositions of chondrites, iron meteorites and the bulk silicate Earth. Stable isotope fractionation, however, rapidly decreases with increasing temperature. We have thus performed liquid metal-liquid silicate equilibration experiments at 1250-1300 °C and 1 GPa to address whether Fe isotope fractionation is resolvable at the lowest possible temperatures for magmatic metal-silicate differentiation. A centrifuging piston cylinder apparatus enabled quantitative metal-silicate segregation. Elemental tin or sulphur was used in the synthetic metal-oxide mixtures to lower the melting temperature of the metal. The analyses demonstrate that eight of the 10 experimental systems equilibrated in a closed isotopic system, as was assessed by varying run durations and starting Fe isotope compositions. Statistically significant iron isotope fractionation between quenched metals and silicates was absent in nine of the 10 experiments and all 10 experiments yield an average metal-silicate fractionation factor of 0.01 ± 0.04‰, independent of whether graphite or silica glass capsules were used. This implies that Fe isotopes do not fractionate during low pressure metal-silicate segregation under magmatic conditions. In large bodies such as the Earth, fractionation between metal and high pressure (>20 GPa) silicate phases may still be a possible process for equilibrium fractionation during metal-silicate differentiation. However, the 0.07 ± 0.02‰ heavier composition of bulk magmatic iron meteorites relative to the average of bulk ordinary/carbonaceous chondrites cannot result from equilibrium Fe isotope fractionation during core segregation. The up to 0.5‰ lighter sulphide than metal fraction in iron meteorites and in one ordinary chondrite can only be explained by fractionation during subsolidus processes.

Constraints on Galactic Cosmic-Ray Origins from Elemental and Isotopic Composition Measurements

NASA Technical Reports Server (NTRS)

Binns, W. R.; Christian, E. R.; Cummings, A. C.; deNolfo, G. A.; Israel, M. H.; Leske, R. A.; Mewaldt, R. A,; Stone, E. C.; vonRosevinge, T. T.; Wiedenbeck, M. E.

2013-01-01

The most recent measurements by the Cosmic Ray Isotope Spectrometer (CRIS) aboard the Advanced Composition Explorer (ACE) satellite of ultra-heavy cosmic ray isotopic and elemental abundances will be presented. A range of isotope and element ratios, most importantly Ne-22/Ne-20, Fe-58/Fe-56, and Ga-31/Ge -32 show that the composition is consistent with source material that is a mix of approx 80% ISM (with Solar System abundances) and 20% outflow/ejecta from massive stars. In addition, our data show that the ordering of refractory and volatile elements with atomic mass is greatly improved when compared to an approx 80%/20% mix rather than pure ISM, that the refractory and volatile elements have similar slopes, and that refractory elements are preferentially accelerated by a factor of approx 4. We conclude that these data are consistent with an OB association origin of GCRs.

Ge and Fe Isotope Fractionation in Metabasites during Subduction-Zone Metamorphism

NASA Astrophysics Data System (ADS)

Luais, B.; El Korh, A. M. T.; Boiron, M. C.; Deloule, E.; Cividini, D.

2016-12-01

Non-traditional stable isotope fractionation during subduction of oceanic crust provides a powerful but challenging tool for understanding geochemical processes in the sub-arc mantle. Iron and germanium are strongly sensitive to low-temperature (T) hydrothermal processes (< 350°C), but can also fractionate at high-T (>700°C) [1-4]. We measured Fe and Ge isotopes in high-pressure metabasites of hydrothermally altered MORB (1.7-2.3 GPa; 550-600°C [5]) from the Ile de Groix (France) to study their behaviour during subduction and fluid-rock interactions. Eclogites and blueschists have δ74GeNIST3120a values (+0.42-0.65‰) similar to those of tholeiitic basalts (+0.55-0.57‰ [2]), indicating a negligible effect of hydrothermal alteration on δ74Ge values. Weak decreases in δ74Ge values occur during dehydration from blueschist to eclogite facies, and in greenschists showing evidence of restricted fluid-rock interaction, but remain close to the HP range (+0.39-0.49‰). This near constancy is attributed to stability of garnet, the main Ge host. By contrast, albite and calcite-bearing greenschists that suffer garnet breakdown show evidence of Ge isotope fractionation (δ74Ge = +0.84-0.98‰) during intensive fluid interaction in a reduced context (Fe2+/Fetot= 0.77-0.80). The metabasites have δ56FeIRMM-014 values (+0.16-0.33‰) heavier than MORBs-OIBs (+0.07-0.18‰ [3]). Unlike Ge isotopes, Fe isotopes correlate with HFSE and mainly reflect protolith heterogeneity. The increase in δ56Fe compared to igneous basic rocks results from open-system hydrothermal alteration prior to subduction. Small correlated variations in Fe elemental (Fe2+/Fetot) and isotopic compositions between blueschists, eclogites and greenschists suggest that Fe isotope fractionation was buffered by the iron of the basic protoliths during subduction and exhumation. Thus metasomatism related to fluids derived from subducted hydrothermally altered metabasites might have little effect on mantle Ge and Fe isotope compositions under subsolidus conditions. [1] Rouxel et al 2003, Chem Geol 202, 155-182. [2] Luais 2012. Chem Geol 334, 295-311. [3] Teng et al, 2013, GCA 107, 12-26. [4] Escoube et al 2015. GCA 167, 93-112. [5] El Korh et al 2009, J Petrol 50, 1107-1148.

Lithium contents and isotopic compositions of ferromanganese deposits from the global ocean

USGS Publications Warehouse

Chan, L.-H.; Hein, J.R.

2007-01-01

To test the feasibility of using lithium isotopes in marine ferromanganese deposits as an indicator of paleoceanographic conditions and seawater composition, we analyzed samples from a variety of tectonic environments in the global ocean. Hydrogenetic, hydrothermal, mixed hydrogenetic–hydrothermal, and hydrogenetic–diagenetic samples were subjected to a two-step leaching and dissolution procedure to extract first the loosely bound Li and then the more tightly bound Li in the Mn oxide and Fe oxyhydroxide. Total leachable Li contents vary from 2 by coulombic force. Hence, the abundant Li in hydrothermal deposits is mainly associated with the dominant phase, MnO2. The surface of amorphous FeOOH holds a slightly positive charge and attracts little Li, as demonstrated by data for hydrothermal Fe oxyhydroxide. Loosely sorbed Li in both hydrogenetic crusts and hydrothermal deposits exhibit Li isotopic compositions that resemble that of modern seawater. We infer that the hydrothermally derived Li scavenged onto the surface of MnO2 freely exchanged with ambient seawater, thereby losing its original isotopic signature. Li in the tightly bound sites is always isotopically lighter than that in the loosely bound fraction, suggesting that the isotopic fractionation occurred during formation of chemical bonds in the oxide and oxyhydroxide structures. Sr isotopes also show evidence of re-equilibration with seawater after deposition. Because of their mobility, Li and Sr in the ferromanganese crusts do not faithfully record secular variations in the isotopic compositions of seawater. However, Li content can be a useful proxy for the hydrothermal history of ocean basins. Based on the Li concentrations of the globally distributed hydrogenetic and hydrothermal samples, we estimate a scavenging flux of Li that is insignificant compared to the hydrothermal flux and river input to the ocean.

Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

2014-06-01

The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during uptake. However, Cu in Fe-Mn crusts is isotopically light (at ∼0.3 to 0.5‰) compared to the dissolved phase in seawater (at ∼0.9‰). We suggest that this is because dissolved Cu in the oceans is overwhelmingly complexed to strong organic ligands, which are better competitors for the heavy isotope.

Does a Heavy Fe-Isotope Composition of Akilia Quartz-Amphibole-Pyroxene Rocks Necessitate a BIF Origin?

PubMed

Whitehouse, M J; Schoenberg, R; Fedo, C M; Kamber, B S

2015-10-01

The age and origin of the quartz-amphibole-pyroxene (qap) gneiss from the island of Akilia, southern West Greenland, have been the subject of intense debate since the light C-isotope composition of graphite inclusions in apatite was interpreted to indicate the presence of Earth's earliest biological activity. Although this claim for biogenic relicts has been vigorously challenged, the possibility that the rocks might represent some of Earth's earliest water-lain sediments and, hence, a suitable repository for life remains an open question. While some workers have suggested that the entire sequence represents an originally mafic-ultramafic igneous precursor subsequently modified by metasomatism, quartz injection, high-grade metamorphism, and extreme ductile deformation, others maintain that at least a small part of the sequence retains geochemical characteristics indicative of a chemical sedimentary origin. Fractionated Fe isotopes with δ(56)Fe values similar to those observed in Isua BIF have been reported from high-SiO2 units of qap and used to support a chemical sedimentary protolith for the qap unit. Here, we present new Fe isotope data from all lithologic variants in the qap gneiss on Akilia, including layers of undisputed ultramafic igneous origin. Since the latter require introduction of fractionated Fe into at least part of the qap unit, we argue that Fe isotopes must therefore be treated with considerable caution when used to infer BIF for part or all of the qap protolith.

Osmium isotope variations in the oceans recorded by Fe-Mn crusts

USGS Publications Warehouse

Burton, K.W.; Bourdon, B.; Birck, J.-L.; Allegre, C.J.; Hein, J.R.

1999-01-01

This study presents osmium (Os) isotope data for recent growth surfaces of hydrogenetic ferromanganese (Fe-Mn) crusts from the Pacific, Atlantic and Indian Oceans. In general, these data indicate a relatively uniform Os isotopic composition for modern seawater, but suggest that North Atlantic seawater is slightly more radiogenic than that of the Pacific and Indian Oceans. The systematic difference in the Os isotopic composition between the major oceans probably reflects a greater input of old continental material with a high Re/Os ratio in the North Atlantic Ocean, consistent with the distribution of Nd and Pb isotopes. This spatial variation in the Os isotope composition in seawater is consistent with a residence time for Os of between 2 and 60 kyr. Indian Ocean samples show no evidence of a local source of radiogenic Os, which suggests that the present-day riverine input from the Himalaya-Tibet region is not a major source for Os. Recently formed Fe-Mn crusts from the TAG hydrothermal field in the North Atlantic yield an Os isotopic composition close to that of modern seawater, which indicates that, in this area, the input of unradiogenic Os from the hydrothermal alteration of oceanic crust is small. However, some samples from the deep Pacific (???4 km) possess a remarkably unradiogenic Os isotope composition (187Os/186Os ratios as low as 4.3). The compositional control of Os incorporation into the crusts and mixing relationships suggest that this unradiogenic composition is most likely due to the direct incorporation of micrometeoritic or abyssal peridotite particles, rather than indicating the presence of an unradiogenic deep-water mass. Moreover, this unradiogenic signal appears to be temporary, and local, and has had little apparent effect on the overall evolution of seawater. These results confirm that input of continental material through erosion is the dominant source of Os in seawater, but it is not clear whether global Os variations are due to the input of mantle or meteoritic material, or simply indicate that the continental source itself is not uniform.

The behavior of iron and zinc stable isotopes accompanying the subduction of mafic oceanic crust: A case study from Western Alpine ophiolites

NASA Astrophysics Data System (ADS)

Inglis, Edward C.; Debret, Baptiste; Burton, Kevin W.; Millet, Marc-Alban; Pons, Marie-Laure; Dale, Christopher W.; Bouilhol, Pierre; Cooper, Matthew; Nowell, Geoff M.; McCoy-West, Alex J.; Williams, Helen M.

2017-07-01

Arc lavas display elevated Fe3+/ΣFe ratios relative to MORB. One mechanism to explain this is the mobilization and transfer of oxidized or oxidizing components from the subducting slab to the mantle wedge. Here we use iron and zinc isotopes, which are fractionated upon complexation by sulfide, chloride, and carbonate ligands, to remark on the chemistry and oxidation state of fluids released during prograde metamorphism of subducted oceanic crust. We present data for metagabbros and metabasalts from the Chenaillet massif, Queyras complex, and the Zermatt-Saas ophiolite (Western European Alps), which have been metamorphosed at typical subduction zone P-T conditions and preserve their prograde metamorphic history. There is no systematic, detectable fractionation of either Fe or Zn isotopes across metamorphic facies, rather the isotope composition of the eclogites overlaps with published data for MORB. The lack of resolvable Fe isotope fractionation with increasing prograde metamorphism likely reflects the mass balance of the system, and in this scenario Fe mobility is not traceable with Fe isotopes. Given that Zn isotopes are fractionated by S-bearing and C-bearing fluids, this suggests that relatively small amounts of Zn are mobilized from the mafic lithologies in within these types of dehydration fluids. Conversely, metagabbros from the Queyras that are in proximity to metasediments display a significant Fe isotope fractionation. The covariation of δ56Fe of these samples with selected fluid mobile elements suggests the infiltration of sediment derived fluids with an isotopically light signature during subduction.

A model for osmium isotopic evolution of metallic solids at the core-mantle boundary

NASA Astrophysics Data System (ADS)

Humayun, Munir

2011-03-01

Some plumes are thought to originate at the core-mantle boundary, but geochemical evidence of core-mantle interaction is limited to Os isotopes in samples from Hawaii, Gorgona (89 Ma), and Kostomuksha (2.7 Ga). The Os isotopes have been explained by physical entrainment of Earth's liquid outer core into mantle plumes. This model has come into conflict with geophysical estimates of the timing of core formation, high-pressure experimental determinations of the solid metal-liquid metal partition coefficients (D), and the absence of expected 182W anomalies. A new model is proposed where metallic liquid from the outer core is partially trapped in a compacting cumulate pile of Fe-rich nonmetallic precipitates (FeO, FeS, Fe3Si, etc.) at the top of the core and undergoes fractional crystallization precipitating solid metal grains, followed by expulsion of the residual metallic liquid back to the outer core. The Os isotopic composition of the solids and liquids in the cumulate pile is modeled as a function of the residual liquid remaining and the emplacement age using 1 bar D values, with variable amounts of oxygen (0-10 wt %) as the light element. The precipitated solids evolve Os isotope compositions that match the trends for Hawaii (at an emplacement age of 3.5-4.5 Ga; 5%-10% oxygen) and Gorgona (emplacement age < 1.5 Ga; 0%-5% oxygen). The Fe-rich matrix of the cumulate pile dilutes the precipitated solid metal decoupling the Fe/Mn ratio from Os and W isotopes. The advantages to using precipitated solid metal as the Os host include a lower platinum group element and Ni content to the mantle source region relative to excess iron, miniscule anomalies in 182W (<0.1 ɛ), and no effects for Pb isotopes, etc. A gradual thermomechanical erosion of the cumulate pile results in incorporation of this material into the base of the mantle, where mantle plumes subsequently entrain it. Fractional crystallization of metallic liquids within the CMB provides a consistent explanation of both Os isotope correlations, Os-W isotope systematics, and Fe/Mn evidence for core-mantle interaction over the entire Hawaiian source.

Iron uptake and magnetite biomineralization in the magnetotactic bacterium Magnetospirillum magneticum strain AMB-1: An iron isotope study

NASA Astrophysics Data System (ADS)

Amor, Matthieu; Busigny, Vincent; Louvat, Pascale; Tharaud, Mickaël; Gélabert, Alexandre; Cartigny, Pierre; Carlut, Julie; Isambert, Aude; Durand-Dubief, Mickaël; Ona-Nguema, Georges; Alphandéry, Edouard; Chebbi, Imène; Guyot, François

2018-07-01

Magnetotactic bacteria (MTB) produce intracellular, membrane-bounded magnetite [Fe(II)Fe(III)2O4] crystals in a genetically controlled way. They are ubiquitous in aquatic environments, and have been proposed to represent some of the most ancient biomineralizing organisms on Earth. Although tremendous advances have been made in constraining the mechanisms of magnetite formation in MTB, the precise biomineralization pathways are still a matter of debate. To further constrain the processes of Fe uptake and magnetite precipitation in MTB, Fe stable isotope measurements were carried out with the magnetotactic strain AMB-1 cultivated with Fe(III), Fe(II) or mixed Fe(III)/Fe(II) species in the growth media. The Fe isotope compositions of growth media before and after AMB-1 cultures, bacterial lysates (i.e. cells devoid of magnetite) and magnetite samples were measured. Single valence Fe(III) or Fe(II) growth media after AMB-1 cultures showed depletion in heavy Fe isotopes by 0.2 to 1.5‰ (δ56Fe), relative to the initial Fe source. Contrastingly, heavy Fe isotopes accumulated in the growth media supplemented with mixed Fe(III)/Fe(II) sources, with enrichment up to 0.25‰. These results support a preferential bacterial uptake of Fe(II) when both Fe(III) and Fe(II) are bioavailable. Bacterial lysates contained at least 50% of the total cellular Fe; thus, magnetite was not the main Fe reservoir in AMB-1 under the experimental conditions investigated in this study. In all cultures, bacterial lysates δ56Fe were 0.4 to 0.8‰ higher than the initial Fe sources, while magnetite δ56Fe were 1.2 to 2.5‰ lower. This depletion in heavy Fe isotopes of magnetite can be explained by partial reduction of Fe(III) to Fe(II) within the cell and subsequent magnetite precipitation. The data also show mass-independent fractionations (MIF) in odd (57Fe) but not in even (54Fe, 56Fe, 58Fe) isotopes, expressed mainly in magnetite crystals, and supporting a magnetic isotope effect on 57Fe. Bacterial Fe uptake and MIF patterns suggest that Fe(II) species can freely exchange between the intracellular and external media. Based on these observations, an integrative biogeochemical model for Fe uptake, cellular trafficking, and magnetite precipitation in AMB-1 is presented.

The Effect of Nickel on Iron Isotope Fractionation and Implications for the Earth's Core

NASA Astrophysics Data System (ADS)

Reagan, M. M.; Shahar, A.; Elardo, S. M.; Liu, J.; Xiao, Y.; Mao, W. L.

2017-12-01

The Earth's core is thought to be composed mainly of an iron-rich iron nickel (FeNi) alloy. Therefore, determining the behavior of these alloys at core conditions is crucial for interpreting and constraining geophysical and geochemical models. Understanding the effect of nickel on iron isotope fractionation can shed light on planetary core formation. We collected a series of phonon excitation spectra using nuclear resonant inelastic x-ray scattering (NRIXS) on 57Fe-enriched FeNi alloys with varying (Fe0.9Ni0.1, Fe0.8Ni0.2, Fe0.7Ni0.3) nickel content in a diamond anvil cell at pressures up to 50 GPa. All three alloys studied exhibited differences from pure Fe, indicating that increasing nickel content could have an effect on iron isotope fractionation which would have implications for planetary core formation and provide constraints the bulk composition for terrestrial planets.

Study of the dynamics of Zn, Fe, and Cu in the soil-plant system during leaf litter decomposition using isotopic compositions

NASA Astrophysics Data System (ADS)

Pichat, S.; Fekiacova, Z.

2013-12-01

Litter decomposition is a key process in the cycle of the elements in the soil-plant system. We have investigated the dynamics of three essential micronutrients (Zn, Fe, and Cu) in the vegetal cover, litter, organic horizons, and upper soil horizon (0-2 and 5-10 cm) using both element concentrations and isotopic compositions. The study was conducted on the O3HP (Oak Observatory at the Haute-Provence Observatory) experimental field site in southern France. O3HP is located far from pollution sources. It has been a fallow land for 70 years with the tree cover represented mainly by oak trees (Quercus pubescens). The soil is a thin layer of Calcisol developed under Mediterranean climate. The area has been subdivided in four zones as a function of plant cover. The results for two of these zones, dominated by respectively Poaceae and Genista hispanica, are reported here. We found that the concentrations of the three elements increase from the Ol to the Of horizon. Copper concentration in the Of horizon is close to that of the soil, whereas it is lower for Fe and Zn. For isotopic compositions, the behavior of the three elements is, however, different, which suggests different processes of redistribution for these elements. An enrichment in light Fe isotopes was observed from the Ol to the Of horizon, the latter having an isotopic composition similar to that of the soil. Zinc isotopic compositions are also similar in the Of horizon and the soil but they are isotopically heavier than in the Ol horizon. For Cu, the O horizons are isotopically heavier than the soil, with Of being the heaviest horizon. In addition, for Cu and Zn, the profiles in the O-horizons in the Poaceae-dominated and Genista hispanica-dominated areas are similar but their values are offset, suggesting an influence of the vegetal cover. The increase in concentration for Cu, Zn and Fe with age/depth in the O horizons is in agreement with what is commonly observed in litter-bag experiments, e.g. 1,2. Two mechanisms have been invoked to explain this phenomenon: 1) addition of metals by aerial dust and wet deposition or 2) absorption of metals from the soil by organisms that develop on the litter. Our vertical profiles of isotopic compositions in the O horizons show that the first hypothesis is unlikely. Instead, they suggest a downward transfer of isotopically light metals from the fresh litter to the base of the O horizon. In addition, the assumption of an upward transfer of isopically heavy Cu and Zn from the upper soil horizon to the Of horizon is needed to fully explain the profiles we observed. 1 Lomander and Johansson (2001) Water, Air, and Soil Pollut. 132, 165-184 2 Scheid et al. (2009) Eur. J. Soil Sci. 60, 613-621

Lead isotopes in iron and manganese oxide coatings and their use as an exploration guide for concealed mineralization

USGS Publications Warehouse

Gulson, B.L.; Church, S.E.; Mizon, K.J.; Meier, A.L.

1992-01-01

Lead isotopes from Fe and Mn oxides that coat stream pebbles from around the Mount Emmons porphyry molybdenum deposit in Colorado were studied to assess the feasibility of using Pb isotopes to detect concealed mineral deposits. The Fe/Mn oxide coatings were analyzed to determine their elemental concentrations using ICP-AES. The Pb isotope compositions of solutions from a selected suite of samples were measured, using both thermal ionization and ICP mass spectrometry, to compare results determined by the two analytical methods. Heavy mineral concentrates from the same sites were also analyzed to compare the Pb isotope compositions of the Fe/Mn coatings with those found in panned concentrates. The Fe/Mn and 206Pb/204Pb ratios of the oxide coatings are related to the lithology of the host rocks; Fe/Mn oxide coatings on pebbles of black shale have higher Fe/Mn values than do the coatings on either sandstone or igneous rocks. The shale host rocks have a more radiogenic signature (e.g. higher 206Pb/ 204Pb) than the sandstone or igneous host rocks. The Pb isotope data from sandstone and igneous hosts can detect concealed mineralized rock on both a regional and local scale, even though there are contributions from: (1) metals from the main-stage molybdenite ore deposit; (2) metals from the phyllic alteration zone which has a more radiogenic Pb isotope signature reflecting hydrothermal leaching of Pb from the Mancos Shale; (3) Pb-rich base metal veins with a highly variable Pb isotope signature; and (4) sedimentary country rocks which have a more radiogenic Pb isotope signature. An investigation of within-stream variation shows that the Pb isotope signature of the molybdenite ore zone is retained in the Fe/Mn oxide coatings and is not camouflaged by contributions from Pb-rich base-metal veins that crop out upstream. In another traverse, the Pb isotope data from Fe/Mn oxide coatings reflect a complex mixing of Pb from the molybdenite ore zone and its hornfels margin, Pb-rich base-metal veins, and sedimentary country rocks. Stream-sediment anomalies detected using oxalic acid leaches can be evaluated using Pb isotope analysesof selected geochemical anomalies. Such an evaluation procedure, given regional target Pb isotope signatures for concealed mineralization, can greatly reduce the cost of exploration for undiscovered ore deposits concealed beneath barren overburden. Lead isotope measurements on aliquots of the same solutions showed that ICP-MS determinations are of low precision and vary non-systematically when compared with the Pb isotope values of the higher precision thermal ionization method. These variations and lower precision of the ICP-MS measurements are attributed to matrix effects. ?? 1992.

Selenium isotope fractionation during reduction by Fe(II)-Fe(III) hydroxide-sulfate (green rust)

USGS Publications Warehouse

Johnson, T.M.; Bullen, T.D.

2003-01-01

We have determined the extent of Se isotope fractionation induced by reduction of selenate by sulfate interlayered green rust (GRSO4), a Fe(II)-Fe(III) hydroxide-sulfate. This compound is known to reduce selenate to Se(0), and it is the only naturally relevant abiotic selenate reduction pathway documented to date. Se reduction reactions, when they occur in nature, greatly reduce Se mobility and bioavailability. Se stable isotope analysis shows promise as an indicator of Se reduction, and Se isotope fractionation by various Se reactions must be known in order to refine this tool. We measured the increase in the 80Se/76Se ratio of dissolved selenate as lighter isotopes were preferentially consumed during reduction by GRSO4. Six different experiments that used GRSO4 made by two methods, with varying solution compositions and pH, yielded identical isotopic fractionations. Regression of all the data yielded an instantaneous isotope fractionation of 7.36 ?? 0.24???. Selenate reduction by GRSO4 induces much greater isotopic fractionation than does bacterial selenate reduction. If selenate reduction by GRSO4 occurs in nature, it may be identifiable on the basis of its relatively large isotopic fractionation. ?? 2003 Elsevier Science Ltd.

Iron isotope composition of depleted MORB

NASA Astrophysics Data System (ADS)

Labidi, J.; Sio, C. K. I.; Shahar, A.

2015-12-01

In terrestrial basalts, iron isotope ratios are observed to weakly fractionate as a function of olivine and pyroxene crystallization. However, a ~0.1‰ difference between chondrites and MORB had been reported (Dauphas et al. 2009, Teng et al. 2013 and ref. therein). This observation could illustrate an isotope fractionation occurring during partial melting, as a function of the Fe valence in melt versus crystals. Here, we present high-precision Fe isotopic data measured by MC-ICP-MS on well-characterized samples from the Pacific-Antarctic Ridge (PAR, n=9) and from the Garrett Transform Fault (n=8). These samples allow exploring the Fe isotope fractionation between melt and magnetite, and the role of partial melting on Fe isotope fractionation. Our average δ56Fe value is +0.095±0.013‰ (95% confidence, n=17), indistinguishable from a previous estimate of +0.105±0.006‰ (95% confidence, n=43, see ref. 2). Our δ56Fe values correlate weakly with MgO contents, and correlate positively with K/Ti ratios. PAC1 DR10 shows the largest Ti and Fe depletion after titanomagnetite fractionation, with a δ56Fe value of +0.076±0.036‰. This is ~0.05‰ below other samples at a given MgO. This may illustrate a significant Fe isotope fractionation between the melt and titanomagnetite, in agreement with experimental determination (Shahar et al. 2008). GN09-02, the most incompatible-element depleted sample, has a δ56Fe value of 0.037±0.020‰. This is the lowest high-precision δ56Fe value recorded for a MORB worldwide. This basalt displays an incompatible-element depletion consistent with re-melting beneath the transform fault of mantle source that was depleted during a first melting event, beneath the ridge axis (Wendt et al. 1999). The Fe isotope observation could indicate that its mantle source underwent 56Fe depletion after a first melting event. It could alternatively indicate a lower Fe isotope fractionation during re-melting, if the source was depleted of its Fe3+, likely producing a relatively reduced melt. These hypotheses are testable, and will be discussed in detail at the conference.

Preservation of Fe Isotope Proxies in the Rock Record

NASA Astrophysics Data System (ADS)

Johnson, C.; Beard, B.; Valley, J.; Valaas, E.

2005-12-01

Iron isotope variations provide powerful constraints on redox conditions and pathways involved during biogeochemical cycling of Fe in surface and near-surface environments. The relative isotopic homogeneity of igneous rocks and most bulk weathering products contrasts with the significant isotopic variations (4 per mil in 56Fe/54Fe) that accompany oxidation of Fe(II)aq, precipitation of sulfides, and reduction by bacteria. These isotopic variations often reflect intrinsic (equilibrium) Fe isotope fractionations between minerals and aqueous species whose interactions may be directly or indirectly catalyzed by bacteria. In addition, Fe isotope exchange may be limited between reactive Fe pools in low-temperature aqueous-sediment environments, fundamentally reflecting disequilibrium effects. In the absence of significant sulfide, dissimilatory Fe(III) reduction by bacteria produces relatively low 56Fe/54Fe ratios for Fe(II)aq and associated biogenic minerals such as magnetite and siderite. In contrast, Fe(II)aq that exchanges with Fe sulfides (FeS and pyrite) is relatively enriched in 56Fe/54Fe ratios. In modern and ancient environments, anoxic diagenesis tends to produce products that have low 56Fe/54Fe ratios, whereas oxidation of Fe(II)aq from hydrothermal sources tends to produce ferric Fe products that have high 56Fe/54Fe ratios. Redox cycling by bacteria tends to produce reactive ferric Fe reservoirs that have low 56Fe/54Fe ratios. Application of Fe isotopes as a proxy for redox conditions in the ancient rock record depends upon the preservation potential during metamorphism, given the fact that most Archean sedimentary sequences have been subjected to regional greenschist- to granulite-facies metamorphism. The 1.9 Ga banded iron formations (BIFs) of the Lake Superior region that are intruded by large ~1 Ga intrusions (e.g., Duluth gabbro) provide a test of the preservation potential for primary, low-temperature Fe isotope variations in sedimentary rocks. 56Fe/54Fe ratios for re-crystallized magnetite from BIFs of the Biwabik iron formation that have apparent oxygen-isotope (quartz-magnetite) temperatures between 270 and 800 oC span a significant portion of the range measured in lower-grade BIFs from South Africa and Australia. d56Fe values for Biwabik magnetite vary from -0.2 to +0.7 per mil, whereas magnetite from the Dales Gorge member of the Brockman iron formation and the Kuruman iron formation has d56Fe values that lie between -1.2 and +1.3 per mil. Iron isotope fractionations between magnetite and Fe silicates (greenalite, hedenbergite, and fayalite) in the Biwabik iron formation regularly decrease with increasing oxygen-isotope temperatures, approaching the zero fractionation expected at igneous temperatures; apparent magnetite-Fe silicate fractionations range from +0.2 per mil at 650 oC to +0.5 per mil at 300 oC, lying close to those predicted using the revised beta factors of Polyakov et al. (2005, Goldschmidt). During closed-system Fe isotope exchange during metamorphism, the overall range in d56Fe values for magnetite will remain relatively constant, although it may shift to higher d56Fe values relative to primary (low-temperature) magnetite due to the non-zero magnetite-Fe silicate fractionation factor at moderate temperature ranges. If the mineral parageneis is known, and some assumptions regarding primary mineralogy can be made, these small corrections may be made to successfully infer the original Fe isotope compositions of sedimentary minerals and rocks that have been subjected to metamorphism.

Iron Stable Isotopes, Magmatic Differentiation and the Oxidation State of Mariana Arc Magmas

NASA Astrophysics Data System (ADS)

Williams, H. M.; Prytulak, J.; Plank, T. A.; Kelley, K. A.

2014-12-01

Arc magmas are widely considered to be oxidized, with elevated ferric iron contents (Fe3+/ΣFe) relative to mid-ocean ridge lavas (1, 2). However, it is unclear whether the oxidized nature of arc basalts is a primary feature, inherited from the sub-arc mantle, or the product of magmatic differentiation and/or post eruptive alteration processes (3). Iron stable isotopes can be used to trace the distribution of Fe during melting and magmatic differentiation processes (4, 5). Here we present Fe isotope data for well-characterized samples (6-8) from islands of the Central Volcanic Zone (CVZ) of the intra-oceanic Mariana Arc to explore the effect of magmatic differentiation processes on Fe isotope systematics. The overall variation in the Fe isotope compositions (δ57Fe) of samples from the CVZ islands ranges from -0.10 ±0.04 to 0.29 ± 0.01 ‰. Lavas from Anatahan are displaced to lower overall δ57Fe values (range -0.10 ±0.04 to 0.18 ±0.01 ‰) relative to other CVZ samples. Fe isotopes in the Anatahan suite (range -0.10 ±0.04 to 0.18 ±0.01 ‰) are positively correlated with SiO2 and negatively correlated with Ca, Fe2O3(t), Cr and V and are displaced to lower overall δ57Fe values relative to other CVZ samples. These correlations can be interpreted in terms of clinopyroxene and magnetite fractionation, with magnetite saturation throughout the differentiation sequence. Magnetite saturation is further supported by negative correlations between V, Fe2O3(t), Cr and MgO (for MgO <3.5 wt%). The early saturation of magnetite in the Anatahan and CVZ lavas is likely to be a function of high melt water content (9, 10) and potentially elevated melt oxidation state. Future work will focus on determining the relationships between mineral Fe isotope partitioning effects and melt composition and oxidation state. 1. R. Arculus, Lithos (1994). 2. K. A. Kelley et al., Science (2009). 3. C.-T. A. Lee et al., J. Pet. (2005). 4. N. Dauphas et al., EPSL (2014). 5. P. A. Sossi et al., CMP (2012). 6. T. Elliott et al., JGR (1997). 7. J. A. Wade et al.. JVGR (2005). 8. J. Woodhead, Chem. Geol. (1989). 9. K. A. Kelley et al., J. Pet. (2010). 10. T. Sisson et al., CMP (1993).

Oxygen isotope geochemistry of the amphiboles: isotope effects of cation substitutions in minerals

NASA Astrophysics Data System (ADS)

Kohn, Matthew J.; Valley, John W.

1998-06-01

The occurrence of coexisting amphiboles in rocks and the likelihood of concurrent isotope closure allows equilibrium oxygen isotope fractionations among the amphiboles to be recovered from natural samples. Oxygen isotope analyses of mineral separates using laser fluorination show that coexisting amphiboles increasingly partition 18O in the order: hornblende ≪ gedrite < cummingtonite ≤ anthophyllite. The observed fractionations at ˜575°C are: Δ(Ged-Hbl) = 0.8‰, Δ(Cum-Hbl) = 0.9, Δ(Cum-Ged) = 0.2, Δ(Ath-Ged) = 0.3, and Δ(Ath-Hbl) > 0.9. Previously published data for hornblende, actinolite, glaucophane, and garnet show that Δ(Act-Hbl) ˜ 0.2, Δ(Gln-Grt) ≫ 1, and Δ(Hbl-Grt) ˜ 0. Thus, glaucophane strongly partitions 18O relative to the calcic amphiboles. The fractionation between two amphiboles of arbitrary composition can be predicted from the known fractionations for mica endmembers, pyroxene endmembers, and exchange components such as CaAl(NaSi) -1, NaAl(CaMg) -1, CaMg -1, MgFe -1, FeMn -1, KNa -1, KAl( Si) -1, and Fe 3+Al -1. Applications of the exchange component method reproduce measured amphibole fractionations to within ±0.1 to ±0.2‰, whereas other predictive methods cause misfit for typical metamorphic hornblende of ≥0.5‰ at 575°C. Although the isotope effects of cation exchanges may be small at high-T, they magnify dramatically for minerals formed in surficial, diagenetic, and low-T metamorphic environments. Different composition clays are predicted to have equilibrium δ 18O differences of 2-9‰. If the isotope fractionation can be determined for one mineral endmember, then calibrated exchanges allow accurate prediction of the isotope fractionations for intermediate compositions of most ortho-, ring-, chain-, and sheet-silicates.

Geochemistry and mineralogy of kimberlites from the Arkhangelsk Region, NW Russia: evidence for transitional kimberlite magma types

NASA Astrophysics Data System (ADS)

Beard, A. D.; Downes, H.; Hegner, E.; Sablukov, S. M.

2000-03-01

The Arkhangelsk kimberlite province (AKP) is situated in the north of the Baltic Shield within the buried southeastern portion of the Kola-Kuloi craton. It forms part of the extensive Devonian magmatic event of the northern Baltic Shield and Kola Peninsula. Two main groups of kimberlites can be distinguished within the province: (1) kimberlites from the diamondiferous Zolotitsa field that have geochemical and isotopic affinities with Group 2 kimberlites and lamproites; (2) diamond-poor Ti-Fe-rich kimberlites from other Arkhangelsk fields that have geochemical and isotopic affinities with Group 1 kimberlites. However, the Zolotitsa and Ti-Fe-rich kimberlites have mineralogical characteristics that are not typical for their respective assigned kimberlite group classifications. Both groups of Arkhangelsk kimberlites are apparently transitional to Group 1 kimberlites, Group 2 kimberlites and lamproites as they are defined elsewhere in the world. An associated kimberlite from the Mela Sill Complex has strong affinities with carbonatites. The low Al 2O 3, high Ni and Cr contents, and high Mg# in both groups of kimberlites indicate strongly depleted lherzolitic-harzburgitic mantle sources. Trace element patterns show a variable enrichment of incompatible elements and strong LREE enrichment. However, kimberlites from the Zolotitsa field have overall lower trace element abundances and less steep REE patterns, suggesting a higher degree of partial melt and/or a less enriched source compared to that of the Ti-Fe-rich kimberlites. A calciocarbonatite of the Mela Sill Complex has trace element and REE patterns typical of other carbonatites closely associated with kimberlites. 87Sr/ 86Sri and 143Nd/ 144Ndi isotope compositions of the Arkhangelsk kimberlites and carbonatite reveal that at least two mantle sources are required to explain the isotopic variation: (1) most of the Zolotitsa and Mela kimberlites and the Mela carbonatite are derived from an ancient enriched lithospheric source (EMI); (2) the Ti-Fe-rich kimberlites are derived from a plume-related asthenospheric mantle source with an isotopic composition close to Bulk Earth. Present-day Pb isotope compositions reveal that the Zolotitsa kimberlites have values close to Group 1 kimberlites. However, the Ti-Fe-rich kimberlites generally have slightly more radiogenic Pb isotope values.

Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

USGS Publications Warehouse

Balci, N.; Bullen, T.D.; Witte-Lien, K.; Shanks, Wayne C.; Motelica, M.; Mandernack, K.W.

2006-01-01

Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42- and Cl- salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor ??Fe(III)aq-Fe(II)aq???1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (???1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (???1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9??? (??Fe(III)aq-Fe(II)aq ???1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments revealed that 56Fe/54Fe ratios of Fe(III)aq were generally equal to or greater than those of Fe(III)ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record. ?? 2005 Elsevier Inc. All rights reserved.

Searching for signatures of life on Mars: an Fe-isotope perspective.

PubMed

Anand, M; Russell, S S; Blackhurst, R L; Grady, M M

2006-10-29

Recent spacecraft and lander missions to Mars have reinforced previous interpretations that Mars was a wet and warm planet in the geological past. The role of liquid water in shaping many of the surface features on Mars has long been recognized. Since the presence of liquid water is essential for survival of life, conditions on early Mars might have been more favourable for the emergence and evolution of life. Until a sample return mission to Mars, one of the ways of studying the past environmental conditions on Mars is through chemical and isotopic studies of Martian meteorites. Over 35 individual meteorite samples, believed to have originated on Mars, are now available for lab-based studies. Fe is a key element that is present in both primary and secondary minerals in the Martian meteorites. Fe-isotope ratios can be fractionated by low-temperature processes which includes biological activity. Experimental investigations of Fe reduction and oxidation by bacteria have produced large fractionation in Fe-isotope ratios. Hence, it is considered likely that if there is/were any form of life present on Mars then it might be possible to detect its signature by Fe-isotope studies of Martian meteorites. In the present study, we have analysed a number of Martian meteorites for their bulk-Fe-isotope composition. In addition, a set of terrestrial analogue material has also been analysed to compare the results and draw inferences. So far, our studies have not found any measurable Fe-isotopic fractionation in bulk Martian meteorites that can be ascribed to any low-temperature process operative on Mars.

Searching for signatures of life on Mars: an Fe-isotope perspective

PubMed Central

Anand, M; Russell, S.S; Blackhurst, R.L; Grady, M.M

2006-01-01

Recent spacecraft and lander missions to Mars have reinforced previous interpretations that Mars was a wet and warm planet in the geological past. The role of liquid water in shaping many of the surface features on Mars has long been recognized. Since the presence of liquid water is essential for survival of life, conditions on early Mars might have been more favourable for the emergence and evolution of life. Until a sample return mission to Mars, one of the ways of studying the past environmental conditions on Mars is through chemical and isotopic studies of Martian meteorites. Over 35 individual meteorite samples, believed to have originated on Mars, are now available for lab-based studies. Fe is a key element that is present in both primary and secondary minerals in the Martian meteorites. Fe-isotope ratios can be fractionated by low-temperature processes which includes biological activity. Experimental investigations of Fe reduction and oxidation by bacteria have produced large fractionation in Fe-isotope ratios. Hence, it is considered likely that if there is/were any form of life present on Mars then it might be possible to detect its signature by Fe-isotope studies of Martian meteorites. In the present study, we have analysed a number of Martian meteorites for their bulk-Fe-isotope composition. In addition, a set of terrestrial analogue material has also been analysed to compare the results and draw inferences. So far, our studies have not found any measurable Fe-isotopic fractionation in bulk Martian meteorites that can be ascribed to any low-temperature process operative on Mars. PMID:17008212

Iron isotope signatures within chondrules from Allende and Chainpur as indicators of thermal history.

NASA Astrophysics Data System (ADS)

Mullane, E.; Russell, S. S.; Gounelle, M.; Mason, T. F. D.

2003-04-01

Introduction: We have studied the petrography and Fe-isotope composition of seven chondrules, four from Allende (CV3) and three from Chainpur (LL3.4). A range of textural-chemical chondrule types are represented, allowing us to examine the Fe-isotope signature in material with different thermal histories, with a view to constraing the chondrule forming process and elucidating the nature of chondrule precursor material. Analytical procedures are detailed elsewhere [1,2,3] Fe-isotope Fractionation: The overall variation in δ56Fe is 1.98 ppm and in δ57Fe is 2.87 ppm. EM-1 (non-porphyritic) is most isotopically heavy and EM-3 (porphyritic) is most isotopically light, with all other chondrules falling in a mass fractionation line between these two end-members. This line is defined by the equation δ57Fe = (1.450±0.050)δ56Fe - (0.009±0.016) (R^2 = 0.9995). Discussion: The Fe-fractionation exhibited here is less than would be expected during open system evaporation. This suggests that Rayleigh conditions were not fulfilled during chondrule melting. Chainpur chondrules exhibit less fractionation than Allende chondrules, a total of 0.46 ppm (δ56Fe) in contrast to 1.98 ppm (δ56Fe), respectively, suggesting that Chainpur may be more equilibrated than Allende. Chainpur Fe-isotopes may have been increasingly homogenised by later addition of Fe, either from the nebular reservoir or parent body alteration. Porphyritic and nonporphyritic chondrules have differing thermal histories. The former are a product of incomplete melting, whereas the latter derive from almost total/complete melting of precursor material. However, Fe-isotope fractionation does not appear to vary systematically with texture. We conclude that chondrule Fe-isotopic signatures represent that of the precursor material, with later equilibration of the Chainpur chondrules. Melting history may also influence the Fe-isotopic signature. The isotopically heaviest chondrules (e.g. EM-1 &EC-3) may derive from a melt which attained liquidus temperatures more than once. The precursor to EM-2 (isotopically lightest), may not have been subject to as many aggressive heating events. References: [1] Mullane et al. (2001) LPS XXXII, Abs. #1545. [2] Mullane et al. (2002) In: Plasma Source Mass Spec. Royal Soc. Chem. (in press). [3] Mullane et al. (2002) Met. Plan. Sci. 37, 105 Abs. [4] Alexander C.M.O'D. &Wang J. (2001) Met. Plan. Sci. 36, 419--428.

Diffusion-driven magnesium and iron isotope fractionation at a gabbro-granite boundary

NASA Astrophysics Data System (ADS)

Wu, Hongjie; He, Yongsheng; Teng, Fang-Zhen; Ke, Shan; Hou, Zhenhui; Li, Shuguang

2018-02-01

Significant magnesium and iron isotope fractionations were observed in an adjacent gabbro and granite profile from the Dabie Orogen, China. Chilled margin and granitic veins at the gabbro side and gabbro xenoliths in the granite indicate the two intrusions were emplaced simultaneously. The δ26Mg decreases from -0.28 ± 0.04‰ to -0.63 ± 0.08‰ and δ56Fe increases from -0.07 ± 0.03‰ to +0.25 ± 0.03‰ along a ∼16 cm traverse from the contact to the granite. Concentrations of major elements such as Al, Na, Ti and most trace elements also systematically change with distance to the contact. All the observations suggest that weathering, magma mixing, fluid exsolution, fractional crystallization and thermal diffusion are not the major processes responsible for the observed elemental and isotopic variations. Rather, the negatively correlated Mg and Fe isotopic compositions as well as co-variations of Mg and Fe isotopes with Mg# reflect Mg-Fe inter-diffusion driven isotope fractionation, with Mg diffusing from the chilled gabbro into the granitic melt and Fe oppositely. The diffusion modeling yields a characteristic diffusive transport distance of ∼6 cm. Consequently, the diffusion duration, during which the granite may have maintained a molten state, can be constrained to ∼2 My. The cooling rate of the granite is calculated to be 52-107 °C/My. Our study suggests diffusion profiles can be a powerful geospeedometry. The observed isotope fractionations also indicate that Mg-Fe inter-diffusion can produce large stable isotope fractionations at least on a decimeter scale, with implications for Mg and Fe isotope study of mantle xenoliths, mafic dikes, and inter-bedded lavas.

Neodymium isotopic study of rare earth element sources and mobility in hydrothermal Fe-oxide (Fe-P-REE) systems

NASA Astrophysics Data System (ADS)

Gleason, James D.; Marikos, Mark A.; Barton, Mark D.; Johnson, David A.

2000-03-01

Rare earth element (REE)-enriched, igneous-related hydrothermal Fe-oxide hosted (Fe-P-REE) systems from four areas in North America have been analyzed for their neodymium isotopic composition to constrain REE sources and mobility in these systems. The Nd isotopic results evidence a common pattern of REE concentration from igneous sources despite large differences in age (Proterozoic to Tertiary), tectonic setting (subduction vs. intraplate), and magmatic style (mafic vs. felsic). In the Middle Proterozoic St. Francois Mountains terrane of southeastern Missouri, ɛ Nd for Fe-P-REE (apatite, monazite, xenotime) deposits ranges from +3.5 to +5.1, similar to associated felsic to intermediate igneous rocks of the same age (ɛ Nd = +2.6 to +6.2). At the mid-Jurassic Humboldt mafic complex in western Nevada, ɛ Nd for Fe-P-REE (apatite) mineralization varies between +1.1 and +2.4, similar to associated mafic igneous rocks (-1.0 to +3.5). In the nearby Cortez Mountains in central Nevada, mid-Jurassic felsic volcanic and plutonic rocks (ɛ Nd = -2.0 to -4.4) are associated with Fe-P-REE (apatite-monazite) mineralization having similar ɛ Nd (-1.7 to -2.4). At Cerro de Mercado, Durango, Mexico, all assemblages analyzed in this Tertiary rhyolite-hosted Fe oxide deposit have identical isotopic compositions with ɛ Nd = -2.5. These data are consistent with coeval igneous host rocks being the primary source of REE in all four regions, and are inconsistent with a significant contribution of REE from other sources. Interpretations of the origin of these hydrothermal systems and their concomitant REE mobility must account for nonspecialized igneous sources and varied tectonic settings.

A counter-intuitive approach to calculating non-exchangeable 2H isotopic composition of hair: treating the molar exchange fraction fE as a process-related rather than compound-specific variable

USGS Publications Warehouse

Landwehr, J.M.; Meier-Augenstein, W.; Kemp, H.F.

2011-01-01

Hair is a keratinous tissue that incorporates hydrogen from material that an animal consumes but it is metabolically inert following synthesis. The stable hydrogen isotope composition of hair has been used in ecological studies to track migrations of mammals as well as for forensic and archaeological purposes to determine the provenance of human remains or the recent geographic life trajectory of living people. Measurement of the total hydrogen isotopic composition of a hair sample yields a composite value comprised of both metabolically informative, non-exchangeable hydrogen and exchangeable hydrogen, with the latter reflecting ambient or sample preparation conditions. Neither of these attributes is directly measurable, and the non-exchangeable hydrogen composition is obtained by estimation using a commonly applied mathematical expression incorporating sample measurements obtained from two distinct equilibration procedures. This commonly used approach treats the fraction of exchangeable hydrogen as a mixing ratio, with a minimal procedural fractionation factor assumed to be close or equal to 1. Instead, we propose to use full molar ratios to derive an expression for the non-exchangeable hydrogen composition explicitly as a function of both the procedural fractionation factor α and the molar hydrogen exchange fraction fE. We apply these derivations in a longitudinal study of a hair sample and demonstrate that the molar hydrogen exchange fraction fE should, like the procedural fractionation factor α, be treated as a process-dependent parameter, i.e. a reaction-specific constant. This is a counter-intuitive notion given that maximum theoretical values for the molar hydrogen exchange fraction fE can be calculated that are arguably protein-type specific and, as such, fE could be regarded as a compound-specific constant. We also make some additional suggestions for future approaches to determine the non-exchangeable hydrogen composition of hair and the use of standards.

Stable Fe isotope fractionation during anaerobic microbial dissimilatory iron reduction at low pH

NASA Astrophysics Data System (ADS)

Chanda, P.; Amenabar, M. J.; Boyd, E. S.; Beard, B. L.; Johnson, C.

2017-12-01

In low-temperature anaerobic environments microbial dissimilatory iron reduction (DIR) plays an important role in Fe cycling. At neutral pH, sorption of aqueous Fe(II) (Fe(II)aq, produced by DIR) catalyzes isotopic exchange between Fe(II) and solid Fe(III), producing 56Fe/54Fe fractionations on the order of 3‰ during DIR[1,2,3]. At low pH, however, the absence of sorbed Fe(II) produces only limited abiologic isotopic exchange[4]. Here we investigated the scope of isotopic exchange between Fe(II)aq and ferric (hydr)oxides (ferrihydrite and goethite) and the associated stable Fe isotope fractionation during DIR by Acidianus strain DS80 at pH 3.0 and 80°C[5]. Over 19 days, 13% reduction of both minerals via microbial DIR was observed. The δ56Fe values of the fluid varied from -2.31 to -1.63‰ (ferrihydrite) and -0.45 to 0.02‰ (goethite). Partial leaching of bulk solid from each reactor with dilute HCl showed no sorption of Fe(II), and the surface layers of the solids were composed of Fe(III) with high δ56Fe values (ferrihydrite: 0.20 to 0.48‰ and goethite: 1.20 to 1.30‰). These results contrast with the lack of Fe isotope exchange in abiologic low-pH systems and indicate a key role for biology in catalyzing Fe isotope exchange between Fe(II)aq and Fe(III) solids, despite the absence of sorbed Fe(II). The estimated fractionation factor (ΔFeFe(III) -Fe(II)aq 2.6‰) from leaching of ferrihydrite is similar to the abiologic equilibrium fractionation factor ( 3.0‰)[3]. The fractionation factor (ΔFeFe(III) -Fe(II)aq 2.0‰) for goethite is higher than the abiologic fractionation factor ( 1.05‰)[2], but is consistent with the previously proposed "distorted surface layer" of goethite produced during the exchange with Fe(II)aq at neutral pH[1]. This study indicates that significant variations in Fe isotope compositions may be produced in low-pH environments where biological cycling of Fe occurs, in contrast to the expected lack of isotopic fractionation in low-pH abiologic systems, and such results bear on the search for biosignatures in Mars and Mars-analog settings. [1] Crosby et al., 2007 Geobiol. 5, 169-189 [2] Beard et al., 2010 Earth Planet. Sci. Lett. 295, 241-250 [3] Wu et al., 2011 Environ. Sci. Technol. 45, 1847-1852 [4] Reddy et al., 2015 Chem. Geol. 397, 118-127 [5] Amenabar et al., 2017 Nat. Geosci. In press

Experimentally determined isotope effect during Mg-Fe interdiffusion in olivine

NASA Astrophysics Data System (ADS)

Sio, C. K. I.; Roskosz, M.; Dauphas, N.; Bennett, N.; Mock, T. D.; Shahar, A.

2017-12-01

Isotopic fractionation provides the most direct means to investigate the nature of chemical zoning in minerals, which can be produced by either diffusive transport or crystal growth. Misinterpreting the nature of chemical zoning can result in erroneous conclusions regarding magmatic cooling rates and diffusion timescales. Isotopes are useful in this regard because the light isotopes diffuse faster than their heavier counterparts. As a result, isotopic fractionations should be associated with chemical zoning profiles if they are diffusion-driven. In contrast, little isotopic fractionation is associated with crystal growth during slow cooling at magmatic temperatures. The isotope effect for diffusion is described by β and is related to the mass (m) and diffusivity (D) of isotopes i and j of an element via: Di/Dj = (mj/mi)β. To model isotopic profiles, knowledge of β is required. Several estimates of β for Mg and Fe diffusion in olivine have been reported using natural samples but these estimates are uncertain because they depend on the choice of modeling parameters (Sio et al., 2013; Oeser et al., 2015; Collinet et al., 2017). We have experimentally determined β for Fe (βFe) in olivine as a function of crystallographic orientation, composition, and temperature. Thirty experiments have been conducted by juxtaposing crystallographically oriented olivine crystals to make Fo83.4-Fo88.8 and Fo88.8-Fo100 diffusion couples. These diffusion couples were annealed in a 1 atm gas mixing furnace at 1200 °C, 1300 °C or 1400 °C at QFM - 1.5 for up to 15 days. Chemical profiles were characterized using an electron microprobe and isotopic analyses were done using laser ablation MC-ICPMS. We found a crystallographic dependence of βFe for the Fo88.8-Fo100 couple where βFe [100] ≈ βFe [010] > βFe [001]. For the Fo83.4-Fo88.8 couple, βFe is 0.16 ± 0.09 (2σ) for all 3 major crystallographic axes. A temperature dependence of βFe could not be resolved. These experimentally determined β-values can be used in conjunction with the Mg-Fe diffusivities given in Dohmen and Chakraborty (2007) to simultaneously model the chemical-isotopic profiles of olivine to retrieve cooling and crystallization histories of magmatic rocks.

New bulk and in situ isotopic and elemental geochemistry of shallow drill core from Atlantis Massif: insights into the sources and paths of fluids and clasts

NASA Astrophysics Data System (ADS)

Bilenker, L.; Weis, D.; Scoates, J. S.

2017-12-01

We present stable Fe and radiogenic isotope and complementary trace element data for samples from Atlantis Massif. This oceanic core complex is located at 30°N where the Atlantis Transform Fault intersects the Mid-Atlantic Ridge (MAR) and is associated with the Lost City Hydrothermal Field (LCHF). It is a unique place to investigate the abiotic and biotic geochemical processes that play a role in the alteration of both crustal and mantle seafloor rocks. The samples analyzed represent a shallow (<15 m) survey of five drill sites (IODP Expedition 357) within Atlantis Massif, varying in distance from the LCHF and MAR. Analyses were performed on a sample set spanning a wide range in degree of alteration and lithology. Bulk measurements involved dissolving whole rock powders, whereas in situ analyses were performed on digested microdrilled samples or by laser ablation. Bulk rock Fe isotope values (n = 34) are correlated with loss-on-ignition (LOI) by sample lithology and location relative to LCHF. Using LOI as a proxy for degree of alteration, this observation indicates that the Fe isotope systematics of seafloor crustal and mantle rocks preserve indicators of fluid flow and source. The Hf and Nd isotope compositions for various lithologies form all analyzed sites are homogeneous, indicating minimal alteration of these isotopic systems. Bulk Sr values provide insight into elemental exchange between seawater and the surface of Atlantis Massif and bulk Pb isotopes allow for fingerprinting of the source of basalt breccias through comparison with published Pb isotope values of MAR basalts. The new results cluster around the Pb, Hf, Nd isotopic composition of mid-ocean ridge basalt from 30.68°N and do not match samples north or south of that location. In situ Fe isotope data within three altered samples reflect varying degrees of hydrothermal and seawater interaction, where the Fe isotope ratios within each sample are likely correlated with extent of exchange or redox. Laser trace element and Pb isotope data in progress will allow us to investigate this further. This study contributes to our understanding of element mobility and mass transfer during chemical reactions within the seafloor, provides insight into the source of the lithological units and fluid flow, and allows for quantification of alteration processes.

Fractionation of iron isotopes during leaching of natural particles by acidic and circumneutral leaches and development of an optimal leach for marine particulate iron isotopes

NASA Astrophysics Data System (ADS)

Revels, Brandi N.; Zhang, Ruifeng; Adkins, Jess F.; John, Seth G.

2015-10-01

Iron (Fe) is an essential nutrient for life on land and in the oceans. Iron stable isotope ratios (δ56Fe) can be used to study the biogeochemical cycling of Fe between particulate and dissolved phases in terrestrial and marine environments. We have investigated the dissolution of Fe from natural particles both to understand the mechanisms of Fe dissolution, and to choose a leach appropriate for extracting labile Fe phases of marine particles. With a goal of finding leaches which would be appropriate for studying dissolved-particle interactions in an oxic water column, three particle types were chosen including oxic seafloor sediments (MESS-3), terrestrial dust (Arizona Test Dust - A2 Fine), and ocean sediment trap material from the Cariaco basin. Four leaches were tested, including three acidic leaches similar to leaches previously applied to marine particles and sediments (25% acetic acid, 0.01 N HCl, and 0.5 N HCl) and a pH 8 oxalate-EDTA leach meant to mimic the dissolution of particles by organic complexation, as occurs in natural seawater. Each leach was applied for three different times (10 min, 2 h, 24 h) at three different temperatures (25 °C, 60 °C, 90 °C). MESS-3 was also leached under various redox conditions (0.02 M hydroxylamine hydrochloride or 0.02 M hydrogen peroxide). For all three sample types tested, we find a consistent relationship between the amount of Fe leached and leachate δ56Fe for all of the acidic leaches, and a different relationship between the amount of Fe leached and leachate δ56Fe for the oxalate-EDTA leach, suggesting that Fe was released through proton-promoted dissolution for all acidic leaches and by ligand-promoted dissolution for the oxalate-EDTA leach. Fe isotope fractionations of up to 2‰ were observed during acidic leaching of MESS-3 and Cariaco sediment trap material, but not for Arizona Test Dust, suggesting that sample composition influences fractionation, perhaps because Fe isotopes are greatly fractionated during leaching of silicates and clays but only minimally fractionated during dissolution of Fe oxyhydroxides. Two different analytical models were developed to explain the relationship between amount of Fe leached and δ56Fe, one of which assumes mixing between two Fe phases with different δ56Fe and different dissolution rates, and the other of which assumes dissolution of a single phase with a kinetic isotope effect. We apply both models to fit results from the acidic leaches of MESS-3 and find that the fit for both models is very similar, suggesting that isotope data will never be sufficient to distinguish between these two processes for natural materials. Next, we utilize our data to choose an optimal leach for application to marine particles. The oxalate-EDTA leach is well-suited to this purpose because it does not greatly fractionate Fe isotopes for a diversity of particle types over a wide variety of leaching conditions, and because it approximates the conditions by which particulate Fe dissolves in the oceans. We recommend a 2 h leach at 90 °C with 0.1 M oxalate and 0.05 M EDTA at pH 8 to measure labile ;ligand-leachable; particulate δ56Fe on natural marine materials with a range of compositions.

2015 Progress Report/July 2016: Iron Oxide Redox Transformation Pathways: The Bulk Electrical Conduction Mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherer, Michelle M.; Rosso, Kevin M.

Despite decades of research on the reactivity and stable isotope properties of Fe oxides, the ability to describe the redox behavior of Fe oxides in the environment is still quite limited. This is due, in large part, to the analytical and spatial complexities associated with studying microscopic processes at the Fe oxide-water interface. This project had the long-term vision of filling this gap by developing a detailed understanding of the relationship between interfacial ET processes, surface structure and charge, and mineral semiconducting properties. We focused on the Fe(III)-oxides and oxyhydroxides because of their geochemical preponderance, versatility in synthesis of compositionally,more » structurally, and morphologically tailored phases, and because they are amenable to a wide range of surface and bulk properties characterization. In particular, reductive transformation of phases such as hematite (α-Fe 2O 3) and goethite (α-FeOOH) in aqueous solution can serve as excellent model systems for studies of electron conduction processes, as well as provide valuable insights into effect of nanoscale conductive materials on contaminant fate at DOE sites. More specifically, the goal of the Iowa component of this project was to use stable Fe isotope measurements to simultaneously measure isotope specific oxidation states and concentrations of Fe at the hematite-water and goethite-water interface. This work builds on our previous work where we used an innovative combination of 57Fe Mössbauer spectroscopy and high precision isotope ratio measurements (MC-ICP-MS) to probe the dynamics of the reaction of aqueous Fe(II) with goethite. Mössbauer spectroscopy detects 57Fe only among all other Fe isotopes and we have capitalized on this to spectroscopically demonstrate Fe(II)-Fe(III) electron transfer between sorbed Fe(II) and Fe(III) oxides (Handler, et al., 2009; Gorski, et al. 2010; Rosso et al., 2010). By combining the Mössbauer spectroscopy and stable isotopes measurements, we have been able to simultaneously track the oxidation state and isotope concentration of the bulk Fe oxide and aqueous Fe. One of our most compelling findings is that despite the apparent stability of the Fe(II)-goethite system, there is actually a tremendous amount of Fe atom cycling occurring between the aqueous phase and the bulk goethite as indicated by the isotopic composition of both phases approaching the mass balance average (Handler et al., 2009). How such extensive re-crystallization and Fe atom exchange can occur with no significant morphological change is a fascinating question. Based on previous work from PI Rosso’s group showing that a potential gradient across hematite crystal faces leads to conduction through hematite and growth and dissolution at separate crystal faces we proposed that a redox-driven recrystallization could be occurring that would explain the extensive mixing observed with the isotope data. From our previous studies utilizing Mössbauer spectroscopy, we know that sorption of Fe(II) onto goethite results in electron transfer between the sorbed Fe(II) and the structural Fe(III) in goethite. Oxidation of the sorbed Fe(II) produces growth of goethite on goethite (i.e., homoepitaxy), as well as injection of an electron into goethite. It is possible that electron transfer from sorbed Fe(II) occurs across a potential gradient, and that Fe(II) atoms are dissolved at a different location on the goethite surface. These newly-reduced Fe(II) atoms could then dissolve into the aqueous phase, exposing fresh Fe(III) goethite to the aqueous phase. Through a repeated series of these five steps of sorption–electron transfer–crystal growth–conduction– dissolution, a redox-driven conveyor belt, could be established that would allow all of the goethite to be eventually exposed to the aqueous phase and exchanged. This surface-mediated recrystallization process would result in similar Fe isotope distributions in the aqueous phase and goethite particle, as we have observed here. It would also result in a stable aqueous Fe(II) concentration, if there were equal rates of goethite growth and dissolution.« less

Precise measurement of Fe isotopes in marine samples by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS).

PubMed

de Jong, Jeroen; Schoemann, Véronique; Tison, Jean-Louis; Becquevort, Sylvie; Masson, Florence; Lannuzel, Delphine; Petit, Jérôme; Chou, Lei; Weis, Dominique; Mattielli, Nadine

2007-04-18

A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)(2), and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is +/-0.07 per thousand on delta(56)Fe and +/-0.09 per thousand on delta(57)Fe while typical internal precision of a measurement (1S.E.) is +/-0.03 per thousand on delta(56)Fe and +/-0.04 per thousand on delta(57)Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of approximately 2 nmol L(-1) for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L(-1) Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. delta(56)Fe varies between -3.5 per thousand and +1.5 per thousand. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.

Iron and silicon isotope behaviour accompanying weathering in Icelandic soils, and the implications for iron export from peatlands

NASA Astrophysics Data System (ADS)

Opfergelt, S.; Williams, H. M.; Cornelis, J. T.; Guicharnaud, R. A.; Georg, R. B.; Siebert, C.; Gislason, S. R.; Halliday, A. N.; Burton, K. W.

2017-11-01

Incipient warming of peatlands at high latitudes is expected to modify soil drainage and hence the redox conditions, which has implications for Fe export from soils. This study uses Fe isotopes to assess the processes controlling Fe export in a range of Icelandic soils including peat soils derived from the same parent basalt, where Fe isotope variations principally reflect differences in weathering and drainage. In poorly weathered, well-drained soils (non-peat soils), the limited Fe isotope fractionation in soil solutions relative to the bulk soil (Δ57Fesolution-soil = -0.11 ± 0.12‰) is attributed to proton-promoted mineral dissolution. In the more weathered poorly drained soils (peat soils), the soil solutions are usually lighter than the bulk soil (Δ57Fesolution-soil = -0.41 ± 0.32‰), which indicates that Fe has been mobilised by reductive mineral dissolution and/or ligand-controlled dissolution. The results highlight the presence of Fe-organic complexes in solution in anoxic conditions. An additional constraint on soil weathering is provided by Si isotopes. The Si isotope composition of the soil solutions relative to the soil (Δ30Sisolution-soil = 0.92 ± 0.26‰) generally reflects the incorporation of light Si isotopes in secondary aluminosilicates. Under anoxic conditions in peat soils, the largest Si isotope fractionation in soil solutions relative to the bulk soil is observed (Δ30Sisolution-soil = 1.63 ± 0.40‰) and attributed to the cumulative contribution of secondary clay minerals and amorphous silica precipitation. Si supersaturation in solution with respect to amorphous silica is reached upon freezing when Al availability to form aluminosilicates is limited by the affinity of Al for metal-organic complexes. Therefore, the precipitation of amorphous silica in peat soils indirectly supports the formation of metal-organic complexes in poorly drained soils. These observations highlight that in a scenario of decreasing soil drainage with warming high latitude peatlands, Fe export from soils as Fe-organic complexes will increase, which in turn has implications for Fe transport in rivers, and ultimately the delivery of Fe to the oceans.

Origins of GEMS Grains

NASA Technical Reports Server (NTRS)

Messenger, S.; Walker, R. M.

2012-01-01

Interplanetary dust particles (IDPs) collected in the Earth s stratosphere contain high abundances of submicrometer amorphous silicates known as GEMS grains. From their birth as condensates in the outflows of oxygen-rich evolved stars, processing in interstellar space, and incorporation into disks around new stars, amorphous silicates predominate in most astrophysical environments. Amorphous silicates were a major building block of our Solar System and are prominent in infrared spectra of comets. Anhydrous interplanetary dust particles (IDPs) thought to derive from comets contain abundant amorphous silicates known as GEMS (glass with embedded metal and sulfides) grains. GEMS grains have been proposed to be isotopically and chemically homogenized interstellar amorphous silicate dust. We evaluated this hypothesis through coordinated chemical and isotopic analyses of GEMS grains in a suite of IDPs to constrain their origins. GEMS grains show order of magnitude variations in Mg, Fe, Ca, and S abundances. GEMS grains do not match the average element abundances inferred for ISM dust containing on average, too little Mg, Fe, and Ca, and too much S. GEMS grains have complementary compositions to the crystalline components in IDPs suggesting that they formed from the same reservoir. We did not observe any unequivocal microstructural or chemical evidence that GEMS grains experienced prolonged exposure to radiation. We identified four GEMS grains having O isotopic compositions that point to origins in red giant branch or asymptotic giant branch stars and supernovae. Based on their O isotopic compositions, we estimate that 1-6% of GEMS grains are surviving circumstellar grains. The remaining 94-99% of GEMS grains have O isotopic compositions that are indistinguishable from terrestrial materials and carbonaceous chondrites. These isotopically solar GEMS grains either formed in the Solar System or were completely homogenized in the interstellar medium (ISM). However, the chemical compositions of GEMS grains are extremely heterogeneous and seem to rule out this possibility. Based on their solar isotopic compositions and their non-solar elemental compositions we propose that most GEMS grains formed in the nebula as late-stage non-equilibrium condensates.

Investigation of Cu-, Zn- and Fe-containing human brain proteins using isotopic-enriched tracers by LA-ICP-MS and MALDI-FT-ICR-MS

NASA Astrophysics Data System (ADS)

Becker, J. Susanne; Zoriy, Miroslav; Pickhardt, Carola; Przybylski, Michael; Becker, J. Sabine

2005-04-01

Identification of metal-containing proteins and determination of Cu, Fe, Zn concentration in very small protein volumes is of increasing importance in protein research. Proteins containing metal ions were analyzed directly and simultaneously in separated protein spots in two-dimensional gels (2D gels) by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as an element mass spectrometric technique. In order to study the formation of proteins containing Cu, Zn and Fe in a human brain sample, isotopic-enriched tracers (54Fe, 65Cu and 67Zn) were doped to two-dimensional gels of separated Alzheimer-diseased brain proteins after two-dimensional (2D) gel electrophoresis. The protein spots were screened systematically by LA-ICP-MS with respect to these metal ion intensities. 54Fe/56Fe, 65Cu/63Cu and 67Zn/64Zn isotope ratios in metal-containing proteins were measured directly by LA-ICP-MS. The isotope ratio measurements obtained by LA-ICP-MS indicate certain protein spots with a natural isotope composition of Cu, Zn and/or Fe. These proteins already contained the metal investigated in the original proteins and are stable enough to survive the reducing conditions during gel electrophoresis. On the other hand, proteins with a changed isotope ratio of metals in comparison to the isotope ratio in nature demonstrate the accumulation of tracers within the protein complexes during the tracer experiments in 2D gels. The identification of singular protein spots from Alzheimer-diseased brain separated by 2D gel electrophoresis was attempted by biopolymer mass spectrometry using MALDI-FTICR-MS after excision from the 2D gel and tryptic digestion.

Investigating Changes in Iron Solubility and Isotopic Composition of Mineral Dust and Industrial Ash during Simulated Atmospheric Processing

NASA Astrophysics Data System (ADS)

Maters, E. C.; Flament, P.; de Jong, J.; Mattielli, N. D. C.; Deboudt, K.

2017-12-01

Iron (Fe) is a key element in ocean biogeochemistry and hence the carbon cycle. Its low concentration in seawater limits primary production in >30% of the surface ocean, and thus strong interest lies in constraining Fe inputs to the ocean on different spatial and temporal scales. During Earth's past, large fluctuations in atmospheric deposition fluxes of continental particles including mineral dust and volcanic ash to the ocean may have played a role in climate change events. At present, anthropogenic particles from metal working, biomass burning, and fossil fuel combustion are increasingly recognised to deliver Fe to the ocean as well. To assess the relative importance of these particulate Fe sources, knowledge of their deposition flux (overall dominated by natural dusts) and their Fe solubility (a proxy for Fe bioavailability, and typically higher in anthropogenic materials) is needed, although large uncertainties remain in these parameters. A potential tool for tracing atmospheric inputs to the ocean is the Fe isotope composition (δ56Fe), previously reported to be distinct for natural versus anthropogenic particles. However, it remains unknown if and how the δ56Fe is influenced by various physicochemical processes (e.g. acidification, photochemistry) shown to enhance Fe solubility in airborne particles. Iron isotopic fractionation has been observed during ligand-controlled and photo-reductive dissolution of goethite at low pH,[1] and similar effects may apply to more complex materials during atmospheric transport. Specifically, isotopic enrichment in partially dissolved particles may result from initial preferential release of 54Fe over 56Fe from the solid surface. To test these hypotheses, we subjected natural and anthropogenic specimens, including mineral dust from the Sahara desert and industrial ash from an Fe-Mn alloy factory, to simulated atmospheric processing in pH 2 solution in the presence/absence of oxalic acid and solar radiation. The Fe solubility and δ56Fe/IRMM-014 values of the solid samples were measured to determine the extents of fractionation relative to unprocessed particles. The results of these experiments and the implications for tracing atmospheric Fe inputs to the ocean will be presented. [1] Wiederhold, J. G. et. al. (2006) Environ. Sci. Technol., 40, 3787-3793.

A balloon measurement of the isotopic composition of galactic cosmic ray iron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grove, J.E.

1989-01-01

The isotopic composition of galactic cosmic ray iron in the energy interval of approximately 1550 to 2200 MeV/nucleon was measured using a balloon-borne mass spectrometer. The instrument was flown from Palestine, Texas, in May 1984 for greater than 35 hours at an atmospheric depth of approximately 6 g/sq cm. Masses were derived by the Cerenkov-Energy technique. The Cerenkov counter employed a silica aerogel radiator with an index of refraction n = 1.1. Particle energies were measured in a stack of NaI(Tl) scintillators, which also provided particle trajectories. A detailed discussion of the sources of mass uncertainty is presented, including anmore » analytic model of the contribution from fluctuations in the Cerenkov yield from knock-on electrons. The achieved mass resolution is approximately 0.65 amu, which is consistent with the theoretical estimate. An Fe-54/Fe-56 abundance ratio of 0.14(sup +0.18)(sub -0.11) and an 84 percent confidence upper limit of Fe-58/Fe-56 is less than or = to 0.07 at the top of the atmosphere is reported. Combining the data with those of precious measurements of the composition of iron at lower energies, and using a model of the galactic propagation, cosmic-ray source abundance ratios of Fe-54/Fe-56 = 0.064(sup +0.032)(sub -0.027) and Fe-58/F3-56 is less than or = to 0.062 were derived. These values are consistent with the composition of solar system iron and place restrictions on the conditions under which cosmic-ray iron is synthesized.« less

Paleoceanographic conditions on the São Paulo Ridge, SW Atlantic Ocean, for the past 30 million years inferred from Os and Pb isotopes of a hydrogenous ferromanganese crust

NASA Astrophysics Data System (ADS)

Goto, Kosuke T.; Nozaki, Tatsuo; Toyofuku, Takashi; Augustin, Adolpho H.; Shimoda, Gen; Chang, Qing; Kimura, Jun-Ichi; Kameo, Koji; Kitazato, Hiroshi; Suzuki, Katsuhiko

2017-12-01

Hydrogenous ferromanganese (Fe-Mn) crusts can provide records of long-term environmental changes during the Cenozoic. To understand the paleoceanographic conditions in the southwestern Atlantic Ocean, we investigated depth profiles of major- and trace-element concentrations as well as Os and Pb isotopic compositions in a Fe-Mn crust collected from the southern flank of the São Paulo Ridge in the southwestern Atlantic. Major and trace element data plotted on ternary Mn-Fe-10×(Ni+Co+Cu) and rare-earth element plus yttrium (REY) discrimination diagrams indicate that the analyzed sample is a typical hydrogenous Fe-Mn crust. The obtained 187Os/188Os data were matched to the Cenozoic seawater Os isotope evolution curve reconstructed from pelagic sediments. The result suggests that the Fe-Mn crust has accreted over 30 Myr with growth rates of 0.5-3 mm/Myr, although the sample likely grew in two directions during the early stage of its growth. We found no evidence of growth hiatus in the sample, which may contrast with the growth histories of many Pacific Fe-Mn crusts. Hence, the conditions favorable for the accretion of hydrogenous Fe-Mn crusts were likely to have developed on the São Paulo Ridge over the past 30 Myr. The Pb isotopic compositions show very limited ranges (e.g., 206Pb/204Pb=18.80-18.85), and are similar to those of pre-anthropogenic seawater in the Southern Ocean. As the São Paulo Ridge is located near the Vema Channel, which is presently a major path of Antarctic Bottom Water, we suggest that a strong northward bottom current has continuously swept detrital and biogenic sediments from the ridge, and played a vital role in the Fe-Mn crust formation since 30 Ma.

Hydrogenetic Ferromanganese Crusts of the California Continental Margin

NASA Astrophysics Data System (ADS)

Conrad, Tracey A.

Hydrogenetic Ferromanganese (Fe-Mn) crusts grow from seawater and in doing so sequester elements of economic interest and serve as archives of past seawater chemistry. Ferromanganese crusts have been extensively studied in open-ocean environments. However, few studies have examined continent-proximal Fe-Mn crusts especially from the northeast Pacific. This thesis addresses Fe-Mn crusts within the northeast Pacific California continental margin (CCM), which is a dynamic geological and oceanographic environment. In the first of three studies, I analyzed the chemical and mineralogical composition of Fe-Mn crusts and show that continental-proximal processes greatly influence the chemistry and mineralogy of CCM Fe-Mn crusts. When compared to global open-ocean Fe-Mn crusts, CCM crusts have higher concentrations of iron, silica, and thorium with lower concentrations of many elements of economic interest including manganese, cobalt, and tellurium, among other elements. The mineralogy of CCM Fe-Mn crusts is also unique with more birnessite and todorokite present than found in open-ocean samples. Unlike open-ocean Fe-Mn crusts, carbonate-fluorapatite is not present in CCM crusts. This lack of phosphatization makes CCM Fe-Mn crusts excellent candidates for robust paleoceanography records. The second and third studies in this thesis use isotope geochemistry on select CCM Fe-Mn crusts from four seamounts in the CCM to study past terrestrial inputs into the CCM and sources and behavior of Pb and Nd isotopes over the past 7 million years along the northeast Pacific margin. The second study focuses on riverine inputs into the Monterey Submarine Canyon System and sources of the continental material. Osmium isotopes in the crusts are compared to the Cenozoic Os seawater curve to develop an age model for the samples that show the crusts range in age of initiation of crust growth from approximately 20 to 6 Myr. Lead and neodymium isotopes measured in select Fe-Mn crusts show that large amounts of terrestrial material entered the CCM via the Monterey Canyon from prior to 6.8+/-0.5 until 4.5 +/-0.5 Myr ago. These data combined with reconstructions of the paleo-coastline indicate that incision of the modern Monterey Canyon started around 7 Myr ago. Isotope plots of potential source regions indicate that the source of the material is the border of the southern Sierra Nevada and western Basin and Range. This answers a long-standing and fundamental question about the timing and formation of the Monterey Canyon, the dominant feature of the Monterey Bay. The third study presented here uses the differences in lead and neodymium isotopic values in CCM Fe-Mn crusts over time compared to open-ocean Pacific, North Pacific, and Arctic Ocean Fe-Mn crusts to identify regional time-series trends and sources for these important oceanographic tracers. I found that sediment fluxes and inputs of terrestrial material from North American rivers effects the lead and neodymium isotope composition of regional seawater.

Isotopic composition of zinc, copper, and iron in lunar samples

NASA Astrophysics Data System (ADS)

Moynier, F.; Albarède, F.; Herzog, G. F.

2006-12-01

We determined by ICP-MS the concentrations and isotopic ratios of Fe, Cu, and Zn in the Ti-rich lunar basalt 74275, in the lunar orange glass 74220, and in up to 10 lunar soils, namely, 14163, 15231, 64501, 66041, 68841, 69941, 70011, 72501, 75081, and 76501. Two analyses of zinc in lunar basalt 74275 give δ 66Zn = 0.17‰ and 0.75‰, values within the range of those measured in terrestrial basalts; copper in lunar basalt 74275 has δ 65Cu ˜ +1.4‰, which is isotopically heavier than values observed in terrestrial basalts. In the orange glass, we measured δ 56Fe = -0.24‰, δ 65Cu = -0.42‰, and δ 66Zn ˜ -3.6‰. These values of δ are more negative than those obtained for 74275 and for typical lunar basalts, but for Cu, comparable to those observed in terrestrial sulfides and meteorites. In lunar soils we found 0.11‰ ⩽ δ 56Fe ⩽ 0.51‰, 2.6‰ ⩽ δ 65Cu ⩽ 4.5‰, and 2.2‰ ⩽ δ 66Zn ⩽ 6.4‰. Insofar as we can generalize from a small sample set, S, Fe, Cu, Zn, and Cd show similar trends in isotopic fractionation on the Moon. Lunar basalts have nearly terrestrial isotopic ratios. Relative to the lunar basalt 74275, the pyroclastic glass 74220 is enriched in the lighter isotopes of Fe, Cu, and Zn, and the soils are enriched in the heavier isotopes of Fe, Cu, and Zn. The patterns in the basalts are likely inherited from the source material; the light-isotope enrichments seen in the orange glass originated during lava fountaining or, less probably, during partial condensation of vapor; and the heavy-isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering. In the orange glass, the light-isotope enrichments (relative to lunar basalts) of Zn are larger than those of Cu. If these enrichments reflect accurately the isotopic composition of the gas, they suggest that Cu is more volatile than Zn in the liquid from which the gas derived. A simple model built on the known flux of micrometeorites to the lunar surface and a published estimate that micrometeorites generate 10 times their own mass of vapor, predicts heavy-isotope enrichments comparable to those observed in soils but only if the regolith gardening rate is set at about one twentieth of the generally accepted value of 1 cm/My. This discrepancy may reflect the difference in the time constants for micrometeorite milling and decimeter-scale gardening, or the importance of sputtering.

Iron and oxygen isotope fractionation during iron UV photo-oxidation: Implications for early Earth and Mars

NASA Astrophysics Data System (ADS)

Nie, Nicole X.; Dauphas, Nicolas; Greenwood, Richard C.

2017-01-01

Banded iron formations (BIFs) contain appreciable amounts of ferric iron (Fe3+). The mechanism by which ferrous iron (Fe2+) was oxidized into Fe3+ in an atmosphere that was globally anoxic is highly debated. Of the three scenarios that have been proposed to explain BIF formation, photo-oxidation by UV photons is the only one that does not involve life (the other two are oxidation by O2 produced by photosynthesis, and anoxygenic photosynthesis whereby Fe2+ is directly used as electron donor in place of water). We experimentally investigated iron and oxygen isotope fractionation imparted by iron photo-oxidation at a pH of 7.3. The iron isotope fractionation between precipitated Fe3+-bearing lepidocrocite and dissolved Fe2+ follows a Rayleigh distillation with an instantaneous 56Fe/54Fe fractionation factor of + 1.2 ‰. Such enrichment in the heavy isotopes of iron is consistent with the values measured in BIFs. We also investigated the nature of the mass-fractionation law that governs iron isotope fractionation in the photo-oxidation experiments (i.e., the slope of the δ56Fe-δ57Fe relationship). The experimental run products follow a mass-dependent law corresponding to the high-T equilibrium limit. The fact that a ∼3.8 Gyr old BIF sample (IF-G) from Isua (Greenland) falls on the same fractionation line confirms that iron photo-oxidation in the surface layers of the oceans was a viable pathway to BIF formation in the Archean, when the atmosphere was largely transparent to UV photons. Our experiments allow us to estimate the quantum yield of the photo-oxidation process (∼0.07 iron atom oxidized per photon absorbed). This yield is used to model iron oxidation on early Mars. As the photo-oxidation proceeds, the aqueous medium becomes more acidic, which slows down the reaction by changing the speciation of iron to species that are less efficient at absorbing UV-photons. Iron photo-oxidation in centimeter to meter-deep water ponds would take months to years to complete. Oxidation by O2 in acidic conditions would be slower. Iron photo-oxidation is thus likely responsible for the formation of jarosite-hematite deposits on Mars, provided that shallow standing water bodies could persist for extended periods of time. The oxygen isotopic composition of lepidocrocite precipitated from the photo-oxidation experiment was measured and it is related to the composition of water by mass-dependent fractionation. The precipitate-fluid 18O/16O isotope fractionation of ∼ + 6 ‰ is consistent with previous determinations of oxygen equilibrium fraction factors between iron oxyhydroxides and water.

Platinum stable isotopes in ferromanganese crust and nodules

NASA Astrophysics Data System (ADS)

Corcoran, Loretta; Seward, Terry; Handler, Monica R.

2015-04-01

Hydrogenetic ferromanganese (Fe-Mn) crust and nodules are slow-growing chemical sediments that form by direct precipitation from seawater, resulting in a record of changing seawater chemistry. These sediments are the primary sink for platinum in the modern oxic marine environment, hosting well-documented enrichments over other platinum-group elements (PGEs): the Pt anomaly [1]. Platinum is a non-bio-essential, highly siderophile, transition metal with six stable isotopes (190Pt, 192Pt, 194Pt, 195Pt, 196Pt, and 198Pt) with several oxidation states (Pt0, Pt2+ and Pt4+). Platinum is generally considered to exist in the hydrosphere as Pt2+ although its behaviour in the marine environment is poorly constrained, and Pt4+may also be present. Variations in ocean redox state, together with changes in source fluxes to the oceans, may therefore lead to small variations (< ±1) in the stable isotopic composition of marine platinum, raising the potential of adding platinum to the growing arsenal of paleoceanographic tracers. A method has been developed to measure the platinum isotopic composition using double spike MC-ICPMS analysis [2]and applied to a global suite of modern Fe-Mn crust and nodules. Combining synchrotron XAFS analyses of platinum adsorbed onto Fe-Mn oxide and oxyhydroxide surfaces to determine oxidation state and bonding environment, with platinum stable isotopic measurements allowing us to evaluate both platinum incorporation onto these sediments and the associated degree of platinum isotopic fractionation. Leaching experiments conducted on platinum rich terrestrial materials underwent platinum stable isotopic measurement as an analogue for the Pt isotopic fractionation associated with continental weathering. [1] Hodge, V.F. et al. (1985) Earth and Planetary Science Letters, 72, 158-162. [2] Creech, J. et al. (2013) Journal of Analytical Atomic Spectrometry, 28. 853-865.

Biogeochemistry Science and Education Part One: Using Non-Traditional Stable Isotopes as Environmental Tracers Part Two: Identifying and Measuring Undergraduate Misconceptions in Biogeochemistry

NASA Astrophysics Data System (ADS)

Mead, Chris

This dissertation is presented in two sections. First, I explore two methods of using stable isotope analysis to trace environmental and biogeochemical processes. Second, I present two related studies investigating student understanding of the biogeochemical concepts that underlie part one. Fe and Hg are each biogeochemically important elements in their own way. Fe is a critical nutrient for phytoplankton, while Hg is detrimental to nearly all forms of life. Fe is often a limiting factor in marine phytoplankton growth. The largest source, by mass, of Fe to the open ocean is windblown mineral dust, but other more soluble sources are more bioavailable. To look for evidence of these non-soil dust sources of Fe to the open ocean, I measured the isotopic composition of aerosol samples collected on Bermuda. I found clear evidence in the fine size fraction of a non-soil dust Fe source, which I conclude is most likely from biomass burning. Widespread adoption of compact fluorescent lamps (CFL) has increased their importance as a source of environmental Hg. Isotope analysis would be a useful tool in quantifying this impact if the isotopic composition of Hg from CFL were known. My measurements show that CFL-Hg is isotopically fractionated, in a unique pattern, during normal operation. This fractionation is large and has a distinctive, mass-independent signature, such that CFL Hg can be uniquely identified from other sources. Misconceptions research in geology has been a very active area of research, but student thinking regarding the related field of biogeochemistry has not yet been studied in detail. From interviews with 40 undergraduates, I identified over 150 specific misconceptions. I also designed a multiple-choice survey (concept inventory) to measure understanding of these same biogeochemistry concepts. I present statistical evidence, based on the Rasch model, for the reliability and validity of this instrument. This instrument will allow teachers and researchers to easily quantify learning outcomes in biogeochemistry and will complement existing concept inventories in geology, chemistry, and biology.

Simultaneous iron and nickel isotopic analyses of presolar silicon carbide grains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trappitsch, Reto; Stephan, Thomas; Savina, Michael R.

Aside from recording stellar nucleosynthesis, a few elements in presolar grains can also provide insights into the galactic chemical evolution (GCE) of nuclides. We have studied the carbon, silicon, iron, and nickel isotopic compositions of presolar silicon carbide (SiC) grains from asymptotic giant branch (AGB) stars to better understand GCE. Since only the neutron-rich nuclides in these grains have been heavily in uenced by the parent star, the neutron-poor nuclides serve as GCE proxies. Using CHILI, a new resonance ionization mass spectrometry (RIMS) instrument, we measured 74 presolar SiC grains for all iron and nickel isotopes. With the CHARISMA instrument,more » 13 presolar SiC grains were analyzed for iron isotopes. All grains were also measured by NanoSIMS for their carbon and silicon isotopic compositions. A comparison of the measured neutron-rich isotopes with models for AGB star nucleosynthesis shows that our measurements are consistent with AGB star predictions for low-mass stars between half-solar and solar metallicity. Furthermore, our measurements give an indication on the 22Ne( ,n) 25Mg reaction rate. In terms of GCE, we nd that the GCE-dominated iron and nickel isotope ratios, 54Fe/56Fe and 60Ni/ 58Ni, correlate with their GCE-dominated counterpart in silicon, 29Si/ 28Si. The measured GCE trends include the Solar System composition, showing that the Solar System is not a special case. However, as seen in silicon and titanium, many presolar SiC grains are more evolved for iron and nickel than the Solar System. This con rms prior ndings and agrees with observations of large stellar samples that a simple age-metallicity relationship for GCE cannot explain the composition of the solar neighborhood.« less

Simultaneous iron and nickel isotopic analyses of presolar silicon carbide grains

DOE PAGES

Trappitsch, Reto; Stephan, Thomas; Savina, Michael R.; ...

2018-01-01

Aside from recording stellar nucleosynthesis, a few elements in presolar grains can also provide insights into the galactic chemical evolution (GCE) of nuclides. We have studied the carbon, silicon, iron, and nickel isotopic compositions of presolar silicon carbide (SiC) grains from asymptotic giant branch (AGB) stars to better understand GCE. Since only the neutron-rich nuclides in these grains have been heavily in uenced by the parent star, the neutron-poor nuclides serve as GCE proxies. Using CHILI, a new resonance ionization mass spectrometry (RIMS) instrument, we measured 74 presolar SiC grains for all iron and nickel isotopes. With the CHARISMA instrument,more » 13 presolar SiC grains were analyzed for iron isotopes. All grains were also measured by NanoSIMS for their carbon and silicon isotopic compositions. A comparison of the measured neutron-rich isotopes with models for AGB star nucleosynthesis shows that our measurements are consistent with AGB star predictions for low-mass stars between half-solar and solar metallicity. Furthermore, our measurements give an indication on the 22Ne( ,n) 25Mg reaction rate. In terms of GCE, we nd that the GCE-dominated iron and nickel isotope ratios, 54Fe/56Fe and 60Ni/ 58Ni, correlate with their GCE-dominated counterpart in silicon, 29Si/ 28Si. The measured GCE trends include the Solar System composition, showing that the Solar System is not a special case. However, as seen in silicon and titanium, many presolar SiC grains are more evolved for iron and nickel than the Solar System. This con rms prior ndings and agrees with observations of large stellar samples that a simple age-metallicity relationship for GCE cannot explain the composition of the solar neighborhood.« less

Fractionation of silver isotopes in native silver explained by redox reactions

NASA Astrophysics Data System (ADS)

Mathur, Ryan; Arribas, Antonio; Megaw, Peter; Wilson, Marc; Stroup, Steven; Meyer-Arrivillaga, Danilo; Arribas, Isabel

2018-03-01

Scant data exist on the silver isotope composition of native silver specimens because of the relative newness of the technique. This study increases the published dataset by an order of magnitude and presents 80 silver new isotope analyses from native silver originating from a diverse set of worldwide deposits (8 deposit types, 33 mining districts in five continents). The measured isotopic range (defined as δ109Ag/107Ag in per mil units compared to NIST 978 Ag isotope standard) is +2.1 to -0.86‰ (2σ errors less than 0.015); with no apparent systematic correlations to date with deposit type or even within districts. Importantly, the data centering on 0‰ all come from high temperature hypogene/primary deposits whereas flanking and overlapping data represent secondary supergene deposits. To investigate the causes for the more fractionated values, several laboratory experiments involving oxidation of silver from natural specimens of Ag-rich sulfides and precipitation and adsorption of silver onto reagent grade MnO2 and FeOOH were conducted. Simple leach experiments demonstrate little Ag isotope fractionation occurred through oxidation of Ag from native Ag (Δsolution-native109Ag = 0.12‰). In contrast, significant fractionation occurred through precipitation of native Ag onto MnO2 (up to Δsolution-MnO2109Ag = 0.68‰, or 0.3amu). Adsorption of silver onto the MnO2 and FeOOH did not produce as large fractionation as precipitation (mean value of Δsolution-MnO2109Ag = 0.10‰). The most likely cause for the isotopic variations seen relates to redox effects such as the reduction of silver from Ag (I) to Ag° that occurs during precipitation onto the mineral surface. Since many Ag deposits have halos dominated by MnO2 and FeOOH phases, potential may exist for the silver isotope composition of ores and surrounding geochemical haloes to be used to better understand ore genesis and potential exploration applications. Aside from the Mn oxides, surface fluid silver isotope compositions might provide information about geochemical reactions relevant to both environmental and hydrometallurgical applications.

Iron isotope fractionation during magmatic differentiation in Kilauea Iki lava lake.

PubMed

Teng, Fang-Zhen; Dauphas, Nicolas; Helz, Rosalind T

2008-06-20

Magmatic differentiation helps produce the chemical and petrographic diversity of terrestrial rocks. The extent to which magmatic differentiation fractionates nonradiogenic isotopes is uncertain for some elements. We report analyses of iron isotopes in basalts from Kilauea Iki lava lake, Hawaii. The iron isotopic compositions (56Fe/54Fe) of late-stagemeltveins are 0.2 permil (per thousand) greater than values for olivine cumulates. Olivine phenocrysts are up to 1.2 per thousand lighter than those of whole rocks. These results demonstrate that iron isotopes fractionate during magmatic differentiation at both whole-rock and crystal scales. This characteristic of iron relative to the characteristics of magnesium and lithium, for which no fractionation has been found, may be related to its complex redox chemistry in magmatic systems and makes iron a potential tool for studying planetary differentiation.

Iron isotope fractionation during magmatic differentiation in Kilauea Iki lava lake

USGS Publications Warehouse

Teng, F.-Z.; Dauphas, N.; Helz, R.T.

2008-01-01

Magmatic differentiation helps produce the chemical and petrographic diversity of terrestrial rocks. The extent to which magmatic differentiation fractionates nonradiogenic isotopes is uncertain for some elements. We report analyses of iron isotopes in basalts from Kilauea Iki lava lake, Hawaii. The iron isotopic compositions (56Fe/54Fe) of late-stage melt veins are 0.2 per mil (???) greater than values for olivine cumulates. Olivine phenocrysts are up to 1.2??? lighter than those of whole rocks. These results demonstrate that iron isotopes fractionate during magmatic differentiation at both whole-rock and crystal scales. This characteristic of iron relative to the characteristics of magnesium and lithium, for which no fractionation has been found, may be related to its complex redox chemistry in magmatic systems and makes iron a potential tool for studying planetary differentiation.

Stable isotope fractionation of tungsten during adsorption on Fe and Mn (oxyhydr)oxides

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Kubo, Sayuri; Tanaka, Masato; Senda, Ryoko; Iizuka, Tsuyoshi; Tanimizu, Masaharu; Takahashi, Yoshio

2017-05-01

The similar, but not identical chemical properties of W compared with Mo suggest that the stable isotope system of W could be a novel proxy to explore the modern and ancient ocean as is the case in the well-established utility of Mo isotopes. We experimentally investigated the isotopic fractionation of W during adsorption on Fe and Mn (oxyhydr)oxides (ferrihydrite and δ-MnO2), a key process in the global ocean budget of this element. Our adsorption experiments confirmed that W isotopes fractionate substantially on both ferrihydrite and δ-MnO2: lighter W isotopes are preferentially adsorbed on both oxides as a result of equilibrium isotopic exchange between dissolved and adsorbed species, and the obtained values of Δ186/183Wliquid-solid (= δ186Wdissolved - δ186Wadsorbed) are 0.76 ± 0.09‰ for ferrihydrite and 0.88 ± 0.21‰ for δ-MnO2 (2σ, n = 6). Compared with the case of Mo isotopes, fractionation of W isotopes is (i) of comparable magnitude between ferrihydrite and δ-MnO2, and (ii) much smaller than that of Mo on δ-MnO2. Our previous XAFS observations and newly-performed DFT calculations both indicate that the observed W isotopic fractionations are caused by the symmetry change from Td (tetrahedral) WO42- to distorted Oh (octahedral) monomeric W species via formation of inner-sphere complexes on both ferrihydrite and δ-MnO2. The similar isotopic fractionations between the two oxides relate to the strong tendency for W to form inner-sphere complexes, which causes the symmetry change, in contrast to the outer-sphere complex of Mo on ferrihydrite. The smaller isotopic fractionation of W compared with Mo on δ-MnO2 despite their similar molecular symmetry seems to be due to their different degrees of distortion of Oh species. Our findings imply that the isotopic composition of W in modern oxic seawater is likely to become heavier relative to the input by removal of lighter W isotopes via adsorption on ferromanganese oxides in analogy with the Mo isotope budget. In contrast, the isotopic composition of W in ancient seawater should have evolved in response to the extent of deposition of both Fe and Mn oxides; this is likely to be different compared with that of the Mo isotopes, which is strongly associated with the occurrence of Mn oxides relative to Fe oxides.

Mg-Fe Isotope Systems of Mantle Xenoliths: Constrains on the Evolution of Siberian Craton

NASA Astrophysics Data System (ADS)

An, Y.; Kiseeva, E. S.; Sobolev, N. V.; Zhang, Z.

2017-12-01

Mantle xenoliths bring to the surface a variety of lithologies (dunites, lherzolites, harzburgites, wehrlites, eclogites, pyroxenites, and websterites) and represent snapshots of the geochemical processes that occur deep within the Earth. Recent improvements in the precision of the MC-ICP-MS measurements have allowed us to expand the amount of data on Mg and Fe isotopes for mantle-derived samples. For instance, to constrain the isotopic composition of the Earth based on the study of spinel and garnet peridotites (An et al., 2017; Teng et al., 2010), to trace the origin and to investigate the isotopic fractionation mechanism during metamorphic process using cratonic or orogenic eclogites (Li et al., 2011; Wang et al., 2012) and to reveal the metasomatism-induced mantle heterogeneity by pyroxenites (Hu et al., 2016). Numerous multi-stage modification events and mantle layering are detected in the subcontinental lithospheric mantle under the Siberian craton (Ashchepkov et al., 2008a; Sobolev et al., 1975, etc). Combined analyses of Mg and Fe isotopic systems could provide new constraints on the formation and evolution of the ancient cratonic mantle. In order to better constrain the magnitude and mechanism of inter-mineral Mg and Fe isotopic fractionations at high temperatures, systematic studies of mantle xenoliths are needed. For example, theoretical calculations and natural samples measurements have shown that large equilibrium Mg isotope fractionations controlled by the difference in coordination number of Mg among minerals could exist (Huang et al., 2013; Li et al., 2011). Thus, the Mg isotope geothermometer could help us trace the evolution history of ancient cratons. In this study we present Mg and Fe isotopic data for whole rocks and separated minerals (clinopyroxene (cpx) and garnet (grt)) from different types of mantle xenoliths (garnet pyroxenites, eclogites, grospydites and garnet peridotites) from a number of kimberlite pipes in Siberian craton (Udachnaya, Obnazhennaya, Mir, and Zagadochnaya). The large Mg and Fe isotope fractionations between clinopyroxene and garnet for various mantle rocks (Δ26Mg cpx-gnt= 0.360‰ 0.888‰, Δ56Fe cpx-gnt= 0.018‰ 0.348‰) indicate that the Siberian cratonic lithosphetic mantle has undergone multiple complex metasomatic and re-equilibration events.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swanner, E. D.; Bayer, T.; Wu, W.

In this study, we couple iron isotope analysis to microscopic and mineralogical investigation of iron speciation during circumneutral Fe(II) oxidation and Fe(III) precipitation with photosynthetically produced oxygen. In the presence of the cyanobacterium Synechococcus PCC 7002, aqueous Fe(II) (Fe(II) aq) is oxidized and precipitated as amorphous Fe(III) oxyhydroxide minerals (iron precipitates, Fe ppt), with distinct isotopic fractionation (ε 56Fe) values determined from fitting the δ 56Fe(II) aq (1.79‰ and 2.15‰) and the δ 56Fe ppt (2.44‰ and 2.98‰) data trends from two replicate experiments. Additional Fe(II) and Fe(III) phases were detected using microscopy and chemical extractions and likely represent Fe(II)more » and Fe(III) sorbed to minerals and cells. The iron desorbed with sodium acetate (FeNaAc) yielded heavier δ 56Fe compositions than Fe(II) aq. Modeling of the fractionation during Fe(III) sorption to cells and Fe(II) sorption to Feppt, combined with equilibration of sorbed iron and with Fe(II) aq using published fractionation factors, is consistent with our resulting δ 56FeNaAc. The δ 56Fe ppt data trend is inconsistent with complete equilibrium exchange with Fe(II)aq. Because of this and our detection of microbially excreted organics (e.g., exopolysaccharides) coating Feppt in our microscopic analysis, we suggest that electron and atom exchange is partially suppressed in this system by biologically produced organics. These results indicate that cyanobacteria influence the fate and composition of iron in sunlit environments via their role in Fe(II) oxidation through O 2 production, the capacity of their cell surfaces to sorb iron, and the interaction of secreted organics with Fe(III) minerals.« less

Neodymium isotopic study of rare earth element sources and mobility in hydrothermal Fe oxide (Fe-P-REE) systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gleason, J.D.; Marikos, M.A.; Barton, M.D.

2000-03-01

Rare earth element (REE)-enriched, igneous-related hydrothermal Fe-oxide hosted (Fe-P-REE) systems from four areas in North America have been analyzed for their neodymium iosotopic composition to constrain REE sources and mobility in these systems. The Nd isotopic results evidence a common pattern of REE concentration from igneous sources despite large differences in age (Proterozoic to Tertiary), tectonic setting (subduction vs. intraplate), and magmatic style (mafic vs. felsic). In the Middle Proterozoic St. Francois Mountains terrane of southeastern Missouri, {epsilon}{sub Nd} for Fe-P-REE (apatite, monazite, xenotime) deposits ranges from +3.5 to +5.1, similar to associated felsic to intermediate igneous rocks of themore » same age ({epsilon}{sub Nd} = +2.6 to +6.2). At the mid-Jurassic Humboldt mafic complex in western Nevada, {epsilon}{sub Nd} for Fe-P-REE (apatite) mineralization varies between +1.1 and +2.4, similar to associated mafic igneous rocks ({minus}1.0 to +3.5). In the nearby Cortez Mountains in central Nevada, mid-Jurassic felsic volcanic and plutonic rocks ({epsilon}{sub Nd} = {minus}2.0 to {minus}4.4) are associated with Fe-P-REE (apatite-monazite) mineralization having similar {epsilon}{sub Nd}({minus}1.7 to {minus}2.4). At Cerro de Mercado, Durango, Mexico, all assemblages analyzed in this Tertiary rhyolite-hosted Fe oxide deposit have identical isotopic compositions with {epsilon}{sub Nd} = {minus}2.5. These data are consistent with coeval igneous host rocks being the primary source of REE in all four regions, and are inconsistent with a significant contribution of REE from other sources. Interpretations of the origin of these hydrothermal systems and their concomitant REE mobility must account for nonspecialized igneous sources and varied tectonic settings.« less

A Cerenkov-Range analysis of the isotopic composition of cosmic rays with Z from 6 to 26

NASA Technical Reports Server (NTRS)

Fisher, A. J.; Hagen, F. A.; Maehl, R.; Ormes, J. F.

1975-01-01

High-altitude balloon data on the isotopic composition of heavy cosmic rays are reported. The experiment used a Cerenkov detector, arrays of scintillators, and a digitized wire spark chamber. Peaks assigned to the mono-isotopic elements F and Na indicate that an absolute mass scale can be derived from the data. Even-Z elements in the Z range from 12 through 16 are represented mainly by alpha-particle nuclei. Neutron-rich components dominate in the case of neon present. Mass histograms are plotted for C, O, N, Ne, Mg, and Fe.

The effect of fusion-relevant helium levels on the mechanical properties of isotopically tailored ferritic alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hankin, G.L.; Hamilton, M.L.; Gelles, D.S.

1997-04-01

The yield and maximum strengths of an irradiated series of isotopically tailored ferritic alloys were evaluated using the shear punch test. The composition of three of the alloys was Fe-12Cr-1.5Ni. Different balances of nickel isotopes were used in each alloy in order to produce different helium levels. A fourth alloy, which contained no nickel, was also irradiated. The addition of nickel at any isotopic balance to the Fe-12Cr base alloy significantly increased the shear yield and maximum strengths of the alloys, and as expected, the strength of the alloys decreased with increasing irradiation temperature. Helium itself, up to 75 appmmore » over 7 dpa appears to have little effect on the mechanical properties of the alloys.« less

Large Calcium Isotopic Variation in Peridotitic Xenoliths from North China Craton

NASA Astrophysics Data System (ADS)

Huang, S.; Zhao, X.; Zhang, Z.

2016-12-01

Calcium is the fifth most abundant element in the Earth. The Ca isotopic composition of the Earth is important in many aspects, ranging from tracing the Ca cycle on the Earth to comparing the Earth to other terrestrial planets. There is large mass-dependent Ca isotopic variation, measured as δ44/40Ca relative to a standard sample, in terrestrial igneous rocks: about 2 per mil in silicate rocks, compared to 3 per mil in carbonates. Therefore, a good understanding of the Ca isotopic variation in igneous rocks is necessary. Here we report Ca isotopic data on a series of peridotitic xenoliths from North China Craton (NCC). There is about 1 per mil δ44/40Ca variation in these NCC peridotites: The highest δ44/40Ca is close to typical mantle values, and the lowest δ44/40Ca is found in an Fe-rich peridotite, -1.13 relative to normal mantle (or -0.08 on the SRM 915a scale). This represents the lowest δ44/40Ca value ever reported for igneous rocks. Combined with published Fe isotopic data on the same samples, our data show a positive linear correlation between δ44/40Ca and δ57/54Fe in NCC peridotites. This trend is inconsistent with mixing a low-δ44/40Ca and -δ57/54Fe sedimentary component with a normal mantle component. Rather, it is best explained as the result of kinetic isotopic effect caused by melt-peridotite reaction on a time scale of several hundreds of years. In detail, basaltic melt reacts with peridotite, replaces orthopyroxene with clinopyroxene, and increases the Fo number of olivine. Consistent with this interpretation, our on-going Mg isotopic study shows that low-δ44/40Ca and -δ57/54Fe NCC peridotites also have heavier Mg isotopes compared to normal mantle. Our study shows that mantle metasomatism plays an important role generating stable isotopic variations within the Earth's mantle.

Magnesium isotope evidence that accretional vapour loss shapes planetary compositions

PubMed Central

Hin, Remco C.; Coath, Christopher D.; Carter, Philip J.; Nimmo, Francis; Lai, Yi-Jen; Pogge von Strandmann, Philip A.E.; Willbold, Matthias; Leinhardt, Zoë M.; Walter, Michael J.; Elliott, Tim

2017-01-01

It has long been recognised that Earth and other differentiated planetary bodies are chemically fractionated compared to primitive, chondritic meteorites and by inference the primordial disk from which they formed. An important question has been whether the notable volatile depletions of planetary bodies are a consequence of accretion1, or inherited from prior nebular fractionation2. The isotopic compositions of the main constituents of planetary bodies can contribute to this debate3–6. Using a new analytical approach to address key issues of accuracy inherent in conventional methods, we show that all differentiated bodies have isotopically heavier magnesium compositions than chondritic meteorites. We argue that possible magnesium isotope fractionation during condensation of the solar nebula, core formation and silicate differentiation cannot explain these observations. However, isotopic fractionation between liquid and vapour followed by vapour escape during accretionary growth of planetesimals generates appropriate residual compositions. Our modelling implies that the isotopic compositions of Mg, Si and Fe and the relative abundances of the major elements of Earth, and other planetary bodies, are a natural consequence of substantial (~40% by mass) vapour loss from growing planetesimals by this mechanism. PMID:28959965

Iron isotope constraints on arsenic release from Mekong Delta sediments, Cambodia

NASA Astrophysics Data System (ADS)

Matsumoto, T.; Yamaguchi, K. E.; Hirata, T.; Yamagata, Y.; Yamaguchi, A.; Abe, G.

2017-12-01

Arsenic-contaminated groundwater is a world-wide environmental problem and threatens more than 100 million people living in delta areas of South, SE and East Asia. It is typically associated with reducing aquifers with organic-rich alluvial sediments, little thermal gradients, low sulfate concentrations, and slow flushing rates. Such conditions are typical for low-lying countries in Asian deltas; however, compared to Bangladesh, Cambodia has received far less attention. Upon reductive dissolution of Fe-(oxyhydr)oxides that adsorbed As, Fe and As are released into solution as dissolved Fe2+ and arsenate, respectively. Following the oxidation of dissolved Fe2+, newly-formed Fe-(oxyhydr)oxides adsorb As again. Thus, in anoxic waters, concentrations of As correlate with those of dissolved Fe2+. Fluctuating redox conditions in the aquifer are control As release, although inhibition of adsorption of arsenate and arsenite onto the Fe-(oxyhydr)oxides occurs when the concentrations of phosphate, bicarbonate, silicate, and/or organic matter become sufficiently high. Biogeochemical redox reactions of Fe result in significant isotope fractionation (e.g., Johnson et al., 2008). We hypothesized that magnitude of isotope fractionation of Fe in the aquifer sediments, reflecting repeated (incomplete) redox reactions of Fe, may be proportional to the amount of total As release. We aim to calibrate the As release from aquifer sediment by Fe isotope analysis. As a preliminary study, series of sediment samples were collected from the Mekong Delta, Cambodia, in September 2016. Based on measurements by XRF, ICP-AES and ICP-MS, concentrations of As varied significantly covering the range from 4.5 to 15.5 µg/g with a median value of 11 µg/g (higher than the average crustal value of 5 µg/g), and those of Fe is from 2.6 to 9.7 wt.% with a median value of 7.1 wt.%. Concentrations of As and Fe show positive correlation (R2 = 0.72), indicating an effective redox cycling of Fe and As as stated above. Sediment incubation experiment to explore various pathways of As release would show time-series correlated changes in the Fe isotope compositions and As concentrations. The data obtained here are essential in investigating the mechanism of As release.

Elemental and isotopic (C, O, Sr, Nd) compositions of Late Paleozoic carbonated eclogite and marble from the SW Tianshan UHP belt, NW China: Implications for deep carbon cycle

NASA Astrophysics Data System (ADS)

Zhu, Jianjiang; Zhang, Lifei; Lü, Zeng; Bader, Thomas

2018-03-01

Subduction zones are important for understanding of the global carbon cycle from the surface to deep part of the mantle. The processes involved the metamorphism of carbonate-bearing rocks largely control the fate of carbon and contribute to local carbon isotopic heterogeneities of the mantle. In this study, we present petrological and geochemical results for marbles and carbonated eclogites in the Southwestern Tianshan UHP belt, NW China. Marbles are interlayered with coesite-bearing pelitic schists, and have Sr-Nd isotopic values (εNd (T=320Ma) = -3.7 to -8.9, 87Sr/86Sr (i) = 0.7084-0.7089), typical of marine carbonates. The marbles have dispersed low δ18OVSMOW values (ranging from 14 to 29‰) and unaffected carbon isotope (δ13CVPDB = -0.2-3.6‰), possibly due to infiltration of external H2O-rich fluids. Recycling of these marbles into mantle may play a key role in the carbon budget and contributed to the mantle carbon isotope heterogeneity. The carbonated eclogites have high Sr isotopic compositions (87Sr/86Sr (i) = 0.7077-0.7082) and positive εNd (T = 320 Ma) values (from 7.6 to 8.2), indicative of strong seafloor alteration of their protolith. The carbonates in the carbonated eclogites are mainly dolomite (Fe# = 12-43, Fe# = Fe2+/(Fe2+ + Mg)) that were added into oceanic basalts during seafloor alteration and experienced calcite - dolomite - magnesite transformation during the subduction metamorphic process. The uniformly low δ18O values (∼11.44‰) of carbonates in the carbontaed eclogites can be explained by closed-system equilibrium between carbonate and silicate minerals. The low δ13C values (from -3.3 to -7.7‰) of the carbonated eclogites most likely reflect contribution from organic carbon. Recycling of these carbonated eclogites with C isotope similar to typical mantle reservoirs into mantle may have little effect on the mantle carbon isotope heterogeneity.

Mechanisms of iron-silica aqueous interaction and the genesis of Precambrian iron formation

NASA Astrophysics Data System (ADS)

Chemtob, S. M.; Catalano, J. G.; Moynier, F.; Pringle, E. A.

2015-12-01

Iron formations (IFs), Fe- and Si-rich chemical sediments common in Precambrian successions, preserve key information about the compositional, biological, and oxidative evolution of the Precambrian ocean. Stable Si isotopes (δ30Si) of IF have been used to infer paleo-oceanic composition, and secular variations in δ30Si may reflect ancient biogeochemical cycles. The δ30Si of primary Fe-Si precipitates that formed IF depends not only on the δ30Si of aqueous silica but also on the precipitation mechanism. Multiple formation mechanisms for these primary precipitates are plausible. Aqueous Si may have adsorbed on newly precipitated iron oxyhydroxide surfaces; alternatively, Fe and Si may have coprecipitated as a single phase. Here we explore variations in the Si isotope fractionation factor (ɛ) with Fe-Si aqueous interaction mechanism (adsorption vs. coprecipitation). In adsorption experiments, sodium silicate solutions (pH 8.1, 125-2000 µM Si) were reacted with iron oxide particles (hematite, ferrihydrite, goethite, and magnetite) for 24 to 72 hours. Resultant solutions had δ30Si between 0 and +6‰. Calculated ɛ varied significantly with oxide mineralogy and morphology. For ferrihydrite, ɛ = -1.7‰; for hematite, ɛ = -2 to -5‰, depending on particle morphology. Apparent ɛ decreased upon surface site saturation, implying a smaller isotope effect for polymeric Si adsorption than monomeric adsorption. In coprecipitation experiments, solutions of Na-silicate and Fe(II) chloride (0.4-10 mM) were prepared anaerobically, then air-oxidized for 3 days to induce precipitation. At low Si concentrations, magnetite formed; near silica saturation, lepidocrocite and ferrihydrite formed. The Si isotope fractionation factor for coprecipitation was within the range of ɛ observed for adsorption (ɛ = -2.3 ± 1.0‰). These results indicate that the mechanism of Fe-Si interaction affects ɛ, presumably due to varying silicate coordination environments. These isotopic analyses will be paired with Si K-edge and Fe K-edge X-ray absorption spectra of the solids to illustrate how Si bonding environment affects ɛ. Effective reconstruction of paleo-oceanic δ30Si may require additional constraints on the relative importance of Si adsorption and Fe-Si coprecipitation in the production of IF primary precipitates.

Hydrogen-isotope permeation barrier

DOEpatents

Maroni, Victor A.; Van Deventer, Erven H.

1977-01-01

A composite including a plurality of metal layers has a Cu-Al-Fe bronze layer and at least one outer layer of a heat and corrosion resistant metal alloy. The bronze layer is ordinarily intermediate two outer layers of metal such as austenitic stainless steel, nickel alloys or alloys of the refractory metals. The composite provides a barrier to hydrogen isotopes, particularly tritium that can reduce permeation by at least about 30 fold and possibly more below permeation through equal thicknesses of the outer layer material.

Bonanza: An extremely large dust grain from a supernova

NASA Astrophysics Data System (ADS)

Gyngard, Frank; Jadhav, Manavi; Nittler, Larry R.; Stroud, Rhonda M.; Zinner, Ernst

2018-01-01

We report the morphology, microstructure, and isotopic composition of the largest SiC stardust grain known to have condensed from a supernova. The 25-μm diameter grain, termed Bonanza, was found in an acid-resistant residue of the Murchison meteorite. Grains of such large size have neither been observed around supernovae nor predicted to form in stellar environments. The large size of Bonanza has allowed the measurement of the isotopic composition of more elements in it than any other previous presolar grain, including: Li, B, C, N, Mg, Al, Si, S, Ca, Ti, Fe, and Ni. Bonanza exhibits large isotopic anomalies in the elements C, N, Mg, Si, Ca, Ti, Fe, and Ni typical of an astrophysical origin in ejecta of a Type II core-collapse supernova and comparable to those previously observed for other presolar SiC grains of type X. Additionally, we extracted multiple focused ion beam lift-out sections from different regions of the grain. Our transmission electron microscopy demonstrates that the crystalline order varies at the micrometer scale, and includes rare, higher order polytype domains (e.g., 15 R). Analyses with STEM-EDS show Bonanza contains a heterogeneous distribution of subgrains with sizes ranging from <10 nm to >100 nm of Ti(N, C); Fe, Ni-rich grains with variable Fe:Ni; and (Al, Mg)N. Bonanza also has the highest ever inferred initial 26Al/27Al ratio, consistent with its supernova origin. This unique grain affords us the largest expanse of data, both microstructurally and isotopically, to compare with detailed calculations of nucleosynthesis and dust condensation in supernovae.

Constraining the role of iron in environmental nitrogen transformations. Dual stable isotope systematics of abiotic NO 2- reduction by Fe(II) and its production of N 2O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnston, David; Wankel, Scott David; Buchwald, Carolyn

Redox reactions involving nitrogen and iron have been shown to have important implications for mobilization of priority contaminants. Thus, an understanding of the linkages between their biogeochemical cycling is critical for predicting subsurface mobilization of radionuclides such as uranium. Despite mounting evidence for biogeochemical interactions between iron and nitrogen, our understanding of their environmental importance remains limited. Here we present an investigation of abiotic nitrite (NO 2 -) reduction by Fe(II) or ‘chemodenitrification,’ and its relevance to the production of nitrous oxide (N 2O), specifically focusing on dual (N and O) isotope systematics under a variety of environmentally relevant conditions.more » We observe a range of kinetic isotope effects that are regulated by reaction rates, with faster rates at higher pH (~8), higher concentrations of Fe(II) and in the presence of mineral surfaces. A clear non-linear relationship between rate constant and kinetic isotope effects of NO 2 - reduction was evident (with larger isotope effects at slower rates) and is interpreted as reflecting the dynamics of Fe(II)-N reaction intermediates. N and O isotopic composition of product N 2O also suggests a complex network of parallel and/or competing pathways. Our findings suggest that NO 2 - reduction by Fe(II) may represent an important abiotic source of environmental N 2O, especially in iron-rich environments experiencing dynamic redox variations. This study provides a multi-compound, multi-isotope framework for evaluating the environmental occurrence of abiotic NO 2 - reduction and N 2O formation, helping future studies constrain the relative roles of abiotic and biological N 2O production pathways.« less

COORDINATED ANALYSES OF PRESOLAR GRAINS IN THE ALLAN HILLS 77307 AND QUEEN ELIZABETH RANGE 99177 METEORITES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Ann N.; Nittler, Larry R.; Alexander, Conel M. O'D.

2010-08-10

We report the identification of presolar silicates ({approx}177 ppm), presolar oxides ({approx}11 ppm), and one presolar SiO{sub 2} grain in the Allan Hills (ALHA) 77307 chondrite. Three grains having Si-isotopic compositions similar to SiC X and Z grains were also identified, though the mineral phases are unconfirmed. Similar abundances of presolar silicates ({approx}152 ppm) and oxides ({approx}8 ppm) were also uncovered in the primitive CR chondrite Queen Elizabeth Range (QUE) 99177, along with 13 presolar SiC grains and one presolar silicon nitride. The O-isotopic compositions of the presolar silicates and oxides indicate that most of the grains condensed in low-massmore » red giant and asymptotic giant branch stars. Interestingly, unlike presolar oxides, few presolar silicate grains have isotopic compositions pointing to low-metallicity, low-mass stars (Group 3). The {sup 18}O-rich (Group 4) silicates, along with the few Group 3 silicates that were identified, likely have origins in supernova outflows. This is supported by their O- and Si-isotopic compositions. Elemental compositions for 74 presolar silicate grains were determined by scanning Auger spectroscopy. Most of the grains have non-stoichiometric elemental compositions inconsistent with pyroxene or olivine, the phases commonly used to fit astronomical spectra, and have comparable Mg and Fe contents. Non-equilibrium condensation and/or secondary alteration could produce the high Fe contents. Transmission electron microscopic analysis of three silicate grains also reveals non-stoichiometric compositions, attributable to non-equilibrium or multistep condensation, and very fine scale elemental heterogeneity, possibly due to subsequent annealing. The mineralogies of presolar silicates identified in meteorites thus far seem to differ from those in interplanetary dust particles.« less

Fe isotopes and the contrasting petrogenesis of A-, I- and S-type granite

NASA Astrophysics Data System (ADS)

Foden, John; Sossi, Paolo A.; Wawryk, Christine M.

2015-01-01

We present new Fe isotope data of 42 S-, I- and A-type (ferroan) granites from the Cambrian Delamerian orogen in South Australia, the Palaeozoic Lachlan Fold Belt and Western USA. Interpretation of these data, together with modelling suggests that magmatic processes do result in quite complex Fe-isotopic differentiation trends and can lead to granites with isotopically heavy iron with δ57Fe > 0.35‰. By comparison Mid-Ocean Ridge Basalts (MORBs) have δ57Fe = 0.15‰ (Teng et al., 2013). These variations are similar to those previously reported (Poitrasson and Freydier, 2005; Heimann et al., 2008; Telus et al., 2012), but, contrary to some interpretations (Beard and Johnson, 2006; Heimann et al., 2008), heavy values are not necessarily the product of late-stage hydrothermal fluid loss, though this process is undoubtedly also an important factor in some circumstances. A-type (ferroan) granites reach very heavy δ57Fe values (0.4-0.5‰) whereas I-types are systematically lighter (δ57Fe = 0.2‰). S-type granites show a range of intermediate values, but also tend to be isotopically heavy (δ57Fe ≈ 0.2-0.4‰). Our results show that the iron isotopic values and trends are signatures that reflect granite generation processes. A modelling using the Rhyolite-MELTS software suggests that contrasting trajectories and end-points in Fe isotope evolution towards granite depend on: oxidation state of the evolving magma and, whether or not the system is oxygen-buffered. Iron isotopic evolution supports an origin of ferroan A-type granite from protracted, closed magma chamber fractionation of moderately reduced mafic magmas. In these systems magnetite saturation is delayed and the ferric iron budget is finite. I-type systems originate with the supply of relatively oxidised, hydrous, subduction-related magmas from the mantle wedge to the upper plate crust. These then experience oxygen-buffered open-system AFC processes in lower crustal hot-zones. S-type magmas are crustal melts that crystallise under reduced conditions initially imposed at source by sulphidic or graphitic sedimentary protoliths. The composition of the resulting melts reflects the domination of partial melting where conditions are hence buffered (open system) followed by subsequent late-stage, closed system fractionation of these extracted, reduced magmas.

Formation of the world's largest REE deposit through protracted fluxing of carbonatite by subduction-derived fluids

PubMed Central

Ling, Ming-Xing; Liu, Yu-Long; Williams, Ian S.; Teng, Fang-Zhen; Yang, Xiao-Yong; Ding, Xing; Wei, Gang-Jian; Xie, Lu-Hua; Deng, Wen-Feng; Sun, Wei-Dong

2013-01-01

Rare Earth Elements (REE) are essential to modern society but the origins of many large REE deposits remain unclear. The U-Th-Pb ages, chemical compositions and C, O and Mg isotopic compositions of Bayan Obo, the world's largest REE deposit, indicate a protracted mineralisation history with unusual chemical and isotopic features. Coexisting calcite and dolomite are in O isotope disequilibrium; some calcitic carbonatite samples show highly varied δ26Mg which increases with increasing Si and Mg; and ankerite crystals show decreases in Fe and REE from rim to centre, with highly varied REE patterns. These and many other observations are consistent with an unusual mineralisation process not previously considered; protracted fluxing of calcitic carbonatite by subduction-released high-Si fluids during the closure of the Palaeo-Asian Ocean. The fluids leached Fe and Mg from the mantle wedge and scavenged REE, Nb and Th from carbonatite, forming the deposit through metasomatism of overlying sedimentary carbonate.

Weaving a two-dimensional fishing net from titanoniobate nanosheets embedded with Fe3O4 nanocrystals for highly efficient capture and isotope labeling of phosphopeptides

NASA Astrophysics Data System (ADS)

Chen, Xueqin; Li, Siyuan; Zhang, Xiaoxia; Min, Qianhao; Zhu, Jun-Jie

2015-03-01

Qualitative and quantitative characterization of phosphopeptides by means of mass spectrometry (MS) is the main goal of MS-based phosphoproteomics, but suffers from their low abundance in the large haystack of various biological molecules. Herein, we introduce two-dimensional (2D) metal oxides to tackle this biological separation issue. A nanocomposite composed of titanoniobate nanosheets embedded with Fe3O4 nanocrystals (Fe3O4-TiNbNS) is constructed via a facile cation-exchange approach, and adopted for the capture and isotope labeling of phosphopeptides. In this nanoarchitecture, the 2D titanoniobate nanosheets offer enlarged surface area and a spacious microenvironment for capturing phosphopeptides, while the Fe3O4 nanocrystals not only incorporate a magnetic response into the composite but, more importantly, also disrupt the restacking process between the titanoniobate nanosheets and thus preserve a greater specific surface for binding phosphopeptides. Owing to the extended active surface, abundant Lewis acid sites and excellent magnetic controllability, Fe3O4-TiNbNS demonstrates superior sensitivity, selectivity and capacity over homogeneous bulk metal oxides, layered oxides, and even restacked nanosheets in phosphopeptide enrichment, and further allows in situ isotope labeling to quantify aberrantly-regulated phosphopeptides from sera of leukemia patients. This composite nanosheet greatly contributes to the MS analysis of phosphopeptides and gives inspiration in the pursuit of 2D structured materials for separation of other biological molecules of interests.Qualitative and quantitative characterization of phosphopeptides by means of mass spectrometry (MS) is the main goal of MS-based phosphoproteomics, but suffers from their low abundance in the large haystack of various biological molecules. Herein, we introduce two-dimensional (2D) metal oxides to tackle this biological separation issue. A nanocomposite composed of titanoniobate nanosheets embedded with Fe3O4 nanocrystals (Fe3O4-TiNbNS) is constructed via a facile cation-exchange approach, and adopted for the capture and isotope labeling of phosphopeptides. In this nanoarchitecture, the 2D titanoniobate nanosheets offer enlarged surface area and a spacious microenvironment for capturing phosphopeptides, while the Fe3O4 nanocrystals not only incorporate a magnetic response into the composite but, more importantly, also disrupt the restacking process between the titanoniobate nanosheets and thus preserve a greater specific surface for binding phosphopeptides. Owing to the extended active surface, abundant Lewis acid sites and excellent magnetic controllability, Fe3O4-TiNbNS demonstrates superior sensitivity, selectivity and capacity over homogeneous bulk metal oxides, layered oxides, and even restacked nanosheets in phosphopeptide enrichment, and further allows in situ isotope labeling to quantify aberrantly-regulated phosphopeptides from sera of leukemia patients. This composite nanosheet greatly contributes to the MS analysis of phosphopeptides and gives inspiration in the pursuit of 2D structured materials for separation of other biological molecules of interests. Electronic supplementary information (ESI) available: Sequence of phosphopeptides from the digests of α- and β-casein percentages of the 4 methylated products from peptide β1 at different labeling reaction times; sequence of serum phosphopeptides; XPS spectra of Nb 3d and Ti 2p in layered oxides and H+-stacked nanosheets; phosphopeptide enrichment sensitivity of bulk oxides, layered oxides and H+-stacked nanosheets; AFM image of TiNbNS; saturated adsorption isotherm for pNPP adsorbed on bulk oxides, layered oxides and H+-stacked nanosheets; XPS spectra of Fe3O4-TiNbNS nitrogen adsorption-desorption isotherms and pore size distribution curves for the Fe3O4 nanocrystals; phosphopeptide enrichment sensitivity, capacity and selectivity of the Fe3O4-TiNbNS composites; MS/MS spectra of phosphopeptides enriched from serum; linear relationship between the logarithms of peak area ratio and loading volume ratio. See DOI: 10.1039/c4nr07041k

Nucleosynthetic Heterogeneity Controls Vanadium Isotope Variations in Bulk Chondrites

NASA Technical Reports Server (NTRS)

Nielsen, S. G.; Righter, K.; Wu, F.; Owens, J. D.; Prytulak, J.; Burton, K.; Parkinson, I.; Davis, D.

2018-01-01

The vanadium (V) isotope composition of early solar system materials have been hypothesized to be sensitive to high energy irradiation that originated from the young Sun. Vanadium has two isotopes with masses 50 and 51 that have (51)V/(50)V ratio of approximately 410. High energy irradiation produces (50)V from various target isotopes of Ti, Cr and Fe, which would result in light V isotope compositions (expressed as delta (51)V in per mille = 1000 x (((51)V/(50)V(sub sample)/(51)V/(50)V(sub AlfaAesar)) - 1)) relative to a presumably chondritic starting composition. Recently published V isotope data for calcium aluminium inclusions (CAIs) has revealed some very negative values relative to chondrites (by almost -4 per mille) that were indeed interpreted to reflect irradiation processes despite the fact that the studied CAIs all exhibited significant initial abundances of (10)Be, while only a few CAIs displayed light V isotope compositions. It is difficult to relate V isotope variations directly to a singular process because V only possesses two isotopes. Therefore, V isotope variations can principally be produced both mass dependent and independent processes. Mass dependent kinetic stable isotope fractionation is common in CAIs for refractory elements due to partial condensation/evaporation processes. The element strontium (Sr) has an almost identical condensation temperature to V and studies of stable Sr isotope compositions in CAIs reveal both heavy and light values relative to chondrites of several permil. These variations are similar in magnitude to those reported for V isotopes in CAIs, which suggests it is possible that some of the V isotope variation in CAIs could be due to kinetic stable isotope fractionation during condensation/evaporation processes.

Chromium isotope fractionation in ferruginous sediments

NASA Astrophysics Data System (ADS)

Bauer, Kohen W.; Gueguen, Bleuenn; Cole, Devon B.; Francois, Roger; Kallmeyer, Jens; Planavsky, Noah; Crowe, Sean A.

2018-02-01

Ferrous Fe is a potent reductant of Cr(VI), and while a number of laboratory studies have characterized Cr isotope fractionation associated with Cr(VI) reduction by ferrous iron, the expression of this fractionation in real-world ferrous Fe-rich environments remains unconstrained. Here we determine the isotope fractionation associated with Cr(VI) reduction in modern ferrous Fe-rich sediments obtained from the previously well studied Lake Matano, Indonesia. Whole core incubations demonstrate that reduction of Cr(VI) within ferruginous sediments provides a sink for Cr(VI) leading to Cr(VI) concentration gradients and diffusive Cr(VI) fluxes across the sediment water interface. As reduction proceeded, Cr(VI) remaining in the overlying lake water became progressively enriched in the heavy isotope (53Cr), increasing δ53Cr by 2.0 ± 0.1‰ at the end of the incubation. Rayleigh distillation modelling of the evolution of Cr isotope ratios and Cr(VI) concentrations in the overlying water yields an effective isotope fractionation of εeff = 1.1 ± 0.2‰ (53Cr/52Cr), whereas more detailed diagenetic modelling implies an intrinsic isotope fractionation of εint = 1.80 ± 0.04‰. Parallel slurry experiments performed using anoxic ferruginous sediment yield an intrinsic isotope fractionation of εint = 2.2 ± 0.1‰. These modelled isotope fractionations are corroborated by direct measurement of the δ53Cr composition on the upper 0.5 cm of Lake Matano sediment, revealing an isotopic offset from the lake water of Δ53Cr = 0.21-1.81‰. The data and models reveal that effective isotope fractionations depend on the depth at which Cr(VI) reduction takes place below the sediment water interface-the deeper the oxic non-reactive zone, the smaller the effective fractionation relative to the intrinsic fractionation. Based on the geochemistry of the sediment we suggest the electron donors responsible for reduction are a combination of dissolved Fe(II) and 0.5 M HCl extractable (solid phase) Fe(II). Our results are in line with the range of intrinsic fractionation factors observed for such phases in previous laboratory studies. We suggest that intrinsic isotope fractionations of around 1.8‰, may be broadly characteristic of ferruginous environments, but we note that the partitioning of ferrous Fe between dissolved and solid phases may modulate this value. These results indicate that seawater δ53Cr is only captured with high-fidelity by ferruginous sediments when oxygen penetration, and therefore the upper boundary of the zone of Cr(VI) reduction, extends to more than 10 cm below the sediment-water-interface, as can be the case in sediments deposited below oligotrophic waters. In more productive regions, with thinner oxic zones, ferruginous sediments would record δ53Cr as much as 1.8‰ lower than seawater δ53Cr. This implies that a range of sediment δ53Cr compositions, that include that of the igneous silicate earth (ISE), are possible even when seawater is isotopically heavier than the ISE.

Kinetic control on Zn isotope signatures recorded in marine diatoms

NASA Astrophysics Data System (ADS)

Köbberich, Michael; Vance, Derek

2017-08-01

Marine diatoms dominate the oceanic cycle of the essential micronutrient zinc (Zn). The stable isotopes of zinc and other metals are increasingly used to understand trace metal micronutrient cycling in the oceans. One clear feature of the early isotope data is the heavy Zn isotope signature of the average oceanic dissolved pool relative to the inputs, potentially driven by uptake of light isotopes into phytoplankton cells and export to sediments. However, despite the fact that diatoms strip Zn from surface waters across the Antarctic polar front in the Southern Ocean, the local upper ocean is not isotopically heavy. Here we use culturing experiments to quantify the extent of Zn isotope fractionation by diatoms and to elucidate the mechanisms driving it. We have cultured two different open-ocean diatom species (T. oceanica and Chaetoceros sp.) in a series of experiments at constant medium Zn concentration but at bioavailable medium Fe ranging from limiting to replete. We find that T. oceanica can maintain high growth rates and Zn uptake rates over the full range of bioavailable iron (Fe) investigated, and that the Zn taken up has a δ66Zn that is unfractionated relative to that of the bioavailable free Zn in the medium. The studied representative of the genus Chaetoceros, on the other hand, shows more significantly reduced Zn uptake rates at low Fe and records more variable biomass δ66Zn signatures, of up to 0.85‰ heavier than the medium. We interpret the preferential uptake of heavy isotopes at extremely low Zn uptake rates as potentially due to either of the following two mechanisms. First, the release of extracellular polymeric substances (EPS), at low Fe levels, may preferentially scavenge heavy Zn isotopes. Second, the Zn uptake rate may be slow enough to establish pseudo-equilibrium conditions at the transporter site, with heavy Zn isotopes forming more stable surface complexes. Thus we find that, in our experiments, Fe-limitation exerts a key control that not only limits diatom growth, but also affects the Zn uptake physiology of diatoms. Uptake of heavy isotopes occurs under Fe-limiting conditions that drive extremely low Zn uptake rates. On the other hand, more rapid Zn uptake rates result in biomass that is indistinguishable from the external bioavailable free Zn pool. These experimental results can, in principle, explain the range of Zn isotopic compositions found in the real surface ocean, given the geographically variable interplay between Fe-limitation, Zn uptake rates, and the degree of organic complexation of oceanic Zn.

A Cerenkov-delta E-Cerenkov detector for high energy cosmic ray isotopes and an accelerator study of Ar-40 and Fe-56 fragmentation. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Lau, K. H.

1985-01-01

A high energy cosmic ray detector--the High Energy Isotope Spectrometer Telescope (HEIST) is described. It is a large area (0.25 m(swp 2) SR) balloon borne isotope spectrometer designed to make high resolution measurements of isotopes in the element range from neon to nickel (10 Z 28) at energies of about 2 GeV/nucleon. HEIST determines the mass of individual nuclei by measuring both the change in the Lorentz factor (delta gamma) that results from traversing the NaI stack, and the energy loss (delta E) in the stack. Since the total energy of an isotope is given by E = (gamma M), the mass M can be determined by M = delta E/delta, gamma. The instrument is designed to achieve a typical mass resolution of 0.2 amu. The isotopic composition of the fragments from the breakup of high energy An-40 and Fe-56 nuclei are measured experimentally. Isotope yields are compared with calculated yields based on semi-empirical cross-section formulae.

Iron isotope fractionation among magnetite, pyrrhotite, chalcopyrite, rhyolite melt and aqueous fluid at magmatic-hydrothermal conditions

NASA Astrophysics Data System (ADS)

Bilenker, L. D.; Simon, A.; Lundstrom, C.; Gajos, N.

2012-12-01

Fractionation of non-traditional stable isotopes (NTSI) such as Fe in magmatic systems is a relatively understudied subject. The fractionation of Fe stable isotopes has been quantified in some natural igneous samples, but there is a paucity of experimental data that could provide further insight into the causative processes of the observed fractionation. Substantial experimental work has been performed at higher temperatures pertaining to the formation of chondrites and the Earth's core, but only a handful of studies have addressed crustal rocks. To fill this knowledge gap, we performed isothermal, isobaric experiments containing mineral (e.g., magnetite, Fe-sulfides) and fluid, or mineral, rhyolite melt, and fluid assemblages to quantify equilibrium fractionation factors (α). These data, to our knowledge, are the first data that quantify the effect of a fluid phase on iron isotope fractionation at conditions appropriate for evolving magmatic systems. Charges were run inside gold capsules held in a René-41 cold seal vessel, and heated to 400, 600, or 800°C at 150 MPa for mineral-fluid, and 800°C and 100 MPa for mineral-melt-fluid runs. Use of the René vessel fixed the fO2 at the NNO buffer, an oxidation state consistent with arc magmas. The isotopic compositions of the starting and quenched phases were obtained by using a Multi-Collector Plasma Mass Spectrometer (MC-ICP-MS). Equilibrium was assessed by performing time-series runs and the three-isotope method, used only once before in a similar Fe isotope study. Correlation between Fe isotope mass and oxidation state is also being explored. Magnetite-fluid results indicate enrichment of heavy Fe isotopes in the mineral relative to the fluid, consistent with measurements of felsic igneous rocks. Magnetite-melt-fluid relationships are also consistent with measurements of natural samples. In the latter assemblage, over the course of the run, the rhyolite melt becomes heavy relative to the fluid while magnetite takes on a heavier Fe isotope signature than the starting value. These data corroborate the hypothesis that fluid exsolution caused the isotopic patterns observed in highly-differentiated igneous rocks. Further, owing to the ubiquitous importance of melt degassing as a critical process for the formation of magmatic-hydrothermal ore deposits, these data may be potentially serve as an exploration tool. This work contributes to our overall understanding of igneous processes by elucidating the Fe isotope fingerprints observed in the field as well as develop the laboratory techniques needed to study NTSI fractionation in magmatic systems and build a reliable dataset for interpretation of natural systems.

Molybdenum isotope fractionation during complexation with organic matter in the Critical Zone

NASA Astrophysics Data System (ADS)

King, E. K.; Pett-Ridge, J. C.; Perakis, S. S.

2016-12-01

Molybdenum (Mo) is a micronutrient and a redox sensitive trace metal that also forms strong complexes with organic matter (OM). The fractionation of Mo in sediments associated with adsorption onto both iron (Fe) and manganese (Mn) (oxyhydr)oxides under oxic conditions and sulfide phases under euxinic conditions has been used to constrain redox conditions in the ocean. Additionally, Mo isotope dynamics in terrestrial systems can shed light on the pedogenic mechanisms driving the riverine Mo isotopic composition and how atmospheric inputs alter the trace metal budget and isotopic composition of soils. As a result of these studies, it has been hypothesized that multiple mechanisms are responsible for fractionating Mo isotopes. In particular, Mo fractionation during adsorption onto OM is unknown, despite the fact this mechanism is 3x to more than 20x greater than adsorption onto Fe- and Mn- (oxyhydr)oxides across a range of soil types from Oregon, Iceland, and Hawaii1-3 (Marks et al., 2015; Siebert et al., 2015; King et al., 2016). In this study, we measured Mo adsorption and isotopic fractionation onto insolubilized humic acid (IHA), a proxy for OM, as a function of both adsorption time (2-170 h) and pH (2-7). Preliminary results suggest that for the time series experiment, Mo adsorption onto IHA increased from 35% to 64% and a plateau was reached after 24 hours. The average Mo isotope fractionation between the solution and the IHA was Δ98Mosolution-IHA = 1.8 ± 0.3‰. For the pH series experiment, the average Mo isotope fractionation was Δ98Mosolution-IHA = 2.0 ± 0.2‰. Next, we compared the Mo isotopic composition of foliage, O-horizon, and surface soil from 12 sites in the Oregon Coast Range to better understand the impact of OM on Mo isotope dynamics in natural samples. The potential isotopic offset between dissolved and adsorbed Mo onto OM is of the same order of magnitude and direction as fractionation onto Fe- and Mn- (oxyhydr)oxides such as ferrihydrite, hematite, and birnessite which have Δ98Mosolution-oxide values of 1.1‰, 2.2‰, and 1.8‰, respectively (Goldberg et al., 2009; Wasylenki et al., 2011). These results have important implications for the interpretation of the sedimentary Mo record, its use as a paleoredox tracer, and its potential to record changes in the terrestrial weathering environment.

Reconstructing the evolution of the submarine Monterey Canyon System from Os, Nd, and Pb isotopes in hydrogenetic Fe-Mn crusts

USGS Publications Warehouse

Conrad, T.A.; Nielsen, S.G.; Peucker-Ehrenbrink, Bernhard; Blusztajn, J.; Winslow, D.; Hein, James; Paytan, A.

2017-01-01

The sources of terrestrial material delivered to the California margin over the past 7 Myr were assessed using 187Os/188Os, Nd, and Pb isotopes in hydrogenetic ferromanganese crusts from three seamounts along the central and southern California margin. From 6.8 to 4.5 (± 0.5) Ma, all three isotope systems show more radiogenic values at Davidson Seamount, located near the base of the Monterey Canyon System, than in Fe-Mn crusts from the more remote Taney and Hoss seamounts. At the Taney seamounts, approximately 225 km farther offshore from Davidson Seamount, 187Os/188Os values, but not Pb and Nd isotope ratios, also deviate from the Cenozoic seawater curve towards more radiogenic values from 6.8 to 4.5 (± 0.5) Ma. However, none of the isotope systems in Fe-Mn crusts deviate from seawater at Hoss Seamount located approximately 450 km to the south. The regional gradients in isotope ratios indicate that substantial input of dissolved and particulate terrestrial material into the Monterey Canyon System is responsible for the local deviations in the seawater Nd, Pb, and Os isotope compositions from 6.8 to 4.5 (± 0.5) Ma. The isotope ratios recorded in Fe-Mn crusts are consistent with a southern Sierra Nevada or western Basin and Range provenance of the terrestrial material which was delivered by rivers to the canyon. The exhumation of the modern Monterey Canyon must have begun between 10 and 6.8 ± 0.5 Ma, as indicated by our data, the age of incised strata, and paleo-location of the Monterey Canyon relative to the paleo-coastline.

Reconstructing the Evolution of the Submarine Monterey Canyon System From Os, Nd, and Pb Isotopes in Hydrogenetic Fe-Mn Crusts

NASA Astrophysics Data System (ADS)

Conrad, T. A.; Nielsen, S. G.; Peucker-Ehrenbrink, B.; Blusztajn, J.; Winslow, D.; Hein, J. R.; Paytan, A.

2017-11-01

The sources of terrestrial material delivered to the California margin over the past 7 Myr were assessed using 187Os/188Os, Nd, and Pb isotopes in hydrogenetic ferromanganese crusts from three seamounts along the central and southern California margin. From 6.8 to 4.5 (±0.5) Ma, all three isotope systems show more radiogenic values at Davidson Seamount, located near the base of the Monterey Canyon System, than in Fe-Mn crusts from the more remote Taney and Hoss Seamounts. At the Taney Seamounts, approximately 225 km farther offshore from Davidson Seamount, 187Os/188Os values, but not Pb and Nd isotope ratios, also deviate from the Cenozoic seawater curve toward more radiogenic values from 6.8 to 4.5 (±0.5) Ma. However, none of the isotope systems in Fe-Mn crusts deviate from seawater at Hoss Seamount located approximately 450 km to the south. The regional gradients in isotope ratios indicate that substantial input of dissolved and particulate terrestrial material into the Monterey Canyon System is responsible for the local deviations in the seawater Nd, Pb, and Os isotope compositions from 6.8 to 4.5 (±0.5) Ma. The isotope ratios recorded in Fe-Mn crusts are consistent with a southern Sierra Nevada or western Basin and Range provenance of the terrestrial material which was delivered by rivers to the canyon. The exhumation of the modern Monterey Canyon must have begun between 10 and 6.8 ± 0.5 Ma, as indicated by our data, the age of incised strata, and paleo-location of the Monterey Canyon relative to the paleo-coastline.

Benthic iron cycling in a high-oxygen environment: Implications for interpreting the Archean sedimentary iron isotope record.

PubMed

McCoy, V E; Asael, D; Planavsky, N

2017-09-01

The most notable trend in the sedimentary iron isotope record is a shift at the end of the Archean from highly variable δ 56 Fe values with large negative excursions to less variable δ 56 Fe values with more limited negative values. The mechanistic explanation behind this trend has been extensively debated, with two main competing hypotheses: (i) a shift in marine redox conditions and the transition to quantitative iron oxidation; and (ii) a decrease in the signature of microbial iron reduction in the sedimentary record because of increased bacterial sulfate reduction (BSR). Here, we provide new insights into this debate and attempt to assess these two hypotheses by analyzing the iron isotope composition of siderite concretions from the Carboniferous Mazon Creek fossil site. These concretions precipitated in an environment with water column oxygenation, extensive sediment pile dissimilatory iron reduction (DIR) but limited bacterial sulfate reduction (BSR). Most of the concretions have slightly positive iron isotope values, with a mean of 0.15‰ and limited iron isotope variability compared to the Archean sedimentary record. This limited variability in an environment with high DIR and low BSR suggests that these conditions alone are insufficient to explain Archean iron isotope compositions. Therefore, these results support the idea that the unusually variable and negative iron isotope values in the Archean are due to dissimilatory iron reduction (DIR) coupled with extensive water column iron cycling. © 2017 John Wiley & Sons Ltd.

Stable Isotope Characteristics of Jarosite: The Acidic Aqueous History of Mars

NASA Technical Reports Server (NTRS)

Earl, Lyndsey D.

2005-01-01

The Mars Rover Opportunity found jarosite (Na(+) or K(+))Fe3SO4(OH)6 at the Meridiani Planum site. This mineral forms from the evaporation of an aqueous acidic sulfate brine. Oxygen isotope compositions may characterize formation conditions but subsequent isotope exchange may have occurred between the sulfate and hydroxide of jarosite and water. The rate of oxygen isotope exchange depends on the acidity and temperature of the brine, but it has not been investigated in detail. We performed laboratory experiments to determine the rate of oxygen isotope exchange under varying acidities and temperatures to learn more about this process. Barium sulfate samples were precipitated weekly from acidic sodium sulfate brines. The oxygen isotope composition of the precipitated sulfate was obtained using a Finnigan MAT253 Isotope Ratio Mass-Spectrometer. The results show that water was trapped in barium sulfate during precipitation. Trapped water may exchange with sulfate when exposed to high temperatures, thus changing the isotope composition of sulfate and the observed fractionation factor of oxygen isotope exchange between sulfate and water. The results of our research will contribute to the understanding of oxygen isotope exchange rates between water and sulfate under acidic conditions and provide experimental knowledge for the dehydration of barium sulfate samples.

Molybdenum isotopes reveal oxidation of Earth's continental crust during the 2.4 Ga Great Oxidation Event

NASA Astrophysics Data System (ADS)

Greaney, A. T.; Rudnick, R. L.; Romaniello, S. J.; Johnson, A.; Gaschnig, R. M.; Anbar, A. D.

2017-12-01

Concentrations of redox sensitive metals in ocean sediments have been used to infer the onset of oxidative weathering at the time of the GOE, however little is known about the complimentary continental reservoir from which these metals were sourced. Gaschnig et al. (2014) demonstrated that glacial diamictites, which are mixtures of weathered regolith and unweathered upper continental crust (UCC), are systematically depleted in Mo following the GOE. This depletion is attributed to the onset of oxidative weathering, which removed soluble oxidized Mo6+ from the UCC. To determine if Mo isotope fractionation supports this hypothesis, we measured Mo isotopes in twenty-four composites of glacial diamictites spanning depositional ages of 2.9 Ga to 300 Ma. The diamictites fall into three age groups: pre-GOE (2.43 - 2.90 Ga), syn-GOE (2.20 - 2.39 Ga), and syn/post-NOE (0.33 - 0.75 Ga). Pre-GOE composites have an average δ98MoNIST of +0.03‰, syn-GOE composites average -0.29‰, and syn/post-NOE composites average -0.45‰; these groups are statistically different at p=0.01. These data imply that the onset of oxidative weathering, which removed Mo from the UCC, also caused isotopic fractionation of Mo. We speculate that this fractionation is due to isotopically light Mo being adsorbed onto Fe-Mn oxides that formed in soils under an oxic atmosphere, leaving heavy Mo to be transported in solution to rivers. Rayleigh fractionation and mixing models support the incorporation of Fe-Mn oxides into soils that were sampled by the diamictites after the GOE. As these phases are not stable under an anoxic atmosphere, the pre-GOE diamictites are isotopically indistinguishable from igneous UCC (0.0 to +0.15‰, Liang et al., 2017; Willbold et al., 2017). The 2.39 Ga Duitschland diamictite is exceptionally light (-0.80‰), suggesting oxidative weathering was extreme in some locations at the onset of the GOE. We conclude that Mo isotopes have been fractionated upon removal from the UCC since the onset of oxidative weathering at 2.4 Ga, and mass balance requires that rivers have been isotopically heavier than UCC since that time. As paleosols retain 100% of Fe and Mn in the form of oxides since 1.85 Ga (Murakami et al. 2011), it is presumed that Mo has been fractionated during weathering to the same degree it is today.

Hydrogen Isotopic Composition of Apatite in Northwest Africa 7034: A Record of the "Intermediate" H-Isotopic Reservoir in the Martian Crust?

NASA Technical Reports Server (NTRS)

McCubbin, F. M.; Barnes, J. J.; Santos, A. R.; Boyce, J. W.; Anand, M.; Franchi, I. A.; Agee, C. B.

2016-01-01

Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to visible-infrared reflectance spectra of the martian surface measured from orbit [2]. The composition of the fine-grained matrix within NWA 7034 bears a striking resemblance to the major element composition estimated for the martian crust, with several exceptions. The NWA 7034 matrix is depleted in Fe, Ti, and Cr and enriched in Al, Na, and P [3]. The differences in Al and Fe are the most substantial, but the Fe content of NWA 7034 matrix falls within the range reported for the southern highlands crust [6]. It was previously suggested by [4] that NWA 7034 was sourced from the southern highlands based on the ancient 4.4 Ga ages recorded in NWA 7034/7533 zircons [4, 5]. In addition, the NWA 7034 matrix material is enriched in incompatible trace elements by a factor of 1.2-1.5 [7] relative to estimates of the bulk martian crust. The La/Yb ratio of the bulk martian crust is estimated to be approximately 3 [7], and the La/Yb of the NWA 7034 matrix materials ranges from approximately 3.9 to 4.4 [3, 8], indicating a higher degree of LREE enrichment in the NWA 7034 matrix materials. This elevated La/Yb ratio and enrichment in incompatible lithophile trace elements is consistent with NWA 7034 representing a more geochemically enriched crustal terrain than is represented by the bulk martian crust, which would be expected if NWA 7034 represents the bulk crust from the southern highlands. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the composition of the martian crust, particularly the ancient highlands. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034. Usui et al., [9] recently proposed that a H isotopic reservoir exists within the martian crust that has a H-isotopic composition that is intermediate (dD of 1000-2000per mille) between an isotopically light mantle (Delta D is less than 275per mille [10]) and an isotopically heavy atmosphere (dD of 2500-6100per mille [11, 12]). Apatites in NWA 7034 occur in a number of lithologic domains, however apatites across all lithologic domains have been affected by a Pb-loss event at about 1.5 Ga before present [5], so they are unlikely to have retained a primary composition and are more likely to have equilibrated with fluids within the martian crust that may or may not have exchanged with the martian atmosphere. Equilibration of apatite with crustal fluids is further supported by the chlorine-rich compositions exhibited by apatites in NWA 7034 in comparison to apatites from other martian meteorites (Figure 1; [13]). Cl is more hydrophilic than F, which promotes formation of Cl-rich apatite compositions in fluid-rich systems [e.g., 14, 15-17].

Iron Isotope Systematics of the Bushveld Complex, South Africa: Initial Results

NASA Astrophysics Data System (ADS)

Stausberg, N.; Lesher, C. E.; Hoffmann-Barfod, G.; Glessner, J. J.; Tegner, C.

2014-12-01

Iron isotopes show systematic changes in igneous rocks that have been ascribed to fractional crystallization, partial melting, as well as, diffusion effects. Layered mafic intrusions, such as the Paleoproterozoic Bushveld Igneous Complex, are ideally suited to investigate stable isotope fractionation arising principally by fractional crystallization. The upper 2.1km of the Bushveld Complex (Upper and Upper Main Zone, UUMZ) crystallized from a basaltic magma produced by a major recharge event, building up a sequence of tholeiitic, Fe-rich, gabbroic cumulate rocks that display systematic variations in mineralogy and mineral compositions consistent with fractional crystallization. Within this sequence, magnetite joins the liquidus assemblage at ˜260m, followed by olivine at 460m and apatite at 1000m. Here, we present iron isotope measurements of bulk cumulate rocks from the Bierkraal drill core of UUMZ of the western limb. Iron was chemically separated from its matrix and analyzed for δ56Fe (relative to IRMM- 014) with a Nu plasma MC-ICPMS at the University of California, Davis, using (pseudo-) high resolution and sample-standard bracketing. The δ56Fe values for Bushveld cumulates span a range from 0.04‰ to 0.36‰, and systematically correlate with the relative abundance of pyroxene + olivine, magnetite and plagioclase. Notably, the highest δ56Fe values are found in plagioclase-rich cumulates that formed prior to magnetite crystallization. δ56Fe is also high in magnetite-rich cumulates at the onset of magnetite crystallization, while subsequent cumulates exhibit lower and variable δ56Fe principally reflecting fractionation of and modal variations in magnetite, pyroxene and fayalitic olivine. The overall relationships for δ56Fe are consistent with positive mineral - liquid Fe isotope fractionation factors for magnetite and plagioclase, and negative to near zero values for pyroxene and olivine. These initial results are being integrated into a forward model of the Bushveld liquid line of descent and will be compared to complementary work on the Skaergaard intrusion.

Iron isotopic fractionation between silicate mantle and metallic core at high pressure

PubMed Central

Liu, Jin; Dauphas, Nicolas; Roskosz, Mathieu; Hu, Michael Y.; Yang, Hong; Bi, Wenli; Zhao, Jiyong; Alp, Esen E.; Hu, Justin Y.; Lin, Jung-Fu

2017-01-01

The +0.1‰ elevated 56Fe/54Fe ratio of terrestrial basalts relative to chondrites was proposed to be a fingerprint of core-mantle segregation. However, the extent of iron isotopic fractionation between molten metal and silicate under high pressure–temperature conditions is poorly known. Here we show that iron forms chemical bonds of similar strengths in basaltic glasses and iron-rich alloys, even at high pressure. From the measured mean force constants of iron bonds, we calculate an equilibrium iron isotope fractionation between silicate and iron under core formation conditions in Earth of ∼0–0.02‰, which is small relative to the +0.1‰ shift of terrestrial basalts. This result is unaffected by small amounts of nickel and candidate core-forming light elements, as the isotopic shifts associated with such alloying are small. This study suggests that the variability in iron isotopic composition in planetary objects cannot be due to core formation. PMID:28216664

Fragment emission from the mass-symmetric reactions 58Fe,58Ni +58Fe,58Ni at Ebeam=30 MeV/nucleon

NASA Astrophysics Data System (ADS)

Ramakrishnan, E.; Johnston, H.; Gimeno-Nogues, F.; Rowland, D. J.; Laforest, R.; Lui, Y.-W.; Ferro, S.; Vasal, S.; Yennello, S. J.

1998-04-01

The mass-symmetric reactions 58Fe,58Ni +58Fe,58Ni were studied at a beam energy of Ebeam=30 MeV/nucleon in order to investigate the isospin dependence of fragment emission. Ratios of inclusive yields of isotopic fragments from hydrogen through nitrogen were extracted as a function of laboratory angle. A moving source analysis of the data indicates that at laboratory angles around 40° the yield of intermediate mass fragments (IMF's) beyond Z=3 is predominantly from a midrapidity source. The angular dependence of the relative yields of isotopes beyond Z=3 indicates that the IMF's at more central angles originate from a source which is more neutron deficient than the source responsible for fragments emitted at forward angles. The charge distributions and kinetic energy spectra of the IMF's at various laboratory angles were well reproduced by calculations employing a quantum molecular-dynamics code followed by a statistical multifragmentation model for generating fragments. The calculations indicate that the measured IMF's originate mainly from a single source. The isotopic composition of the emitted fragments is, however, not reproduced by the same calculation. The measured isotopic and isobaric ratios indicate an emitting source that is more neutron rich in comparison to the source predicted by model calculations.

Chemical and Isotopic Characterization of Waters in Rio Tinto, Spain, Shows Possible Origin of the Blueberry Haematite Nodules in Meridiani Planum, Mars

NASA Astrophysics Data System (ADS)

Coleman, M. L.; Hubbard, C. G.; Mielke, R. E.; Black, S.

2005-12-01

Meridiani Planum sediments formed in an acid environment and include jarosite and other evaporitic sulfate minerals. Nodular spheroidal concretions appear to have grown in situ and are predominantly hematite. The source of the Rio Tinto, S. Spain, drains an area of extensive sulfide mineralization and is dominated by acid mine drainage processes. The system is not a Mars analog but potentially similar processes of sulfide oxidation produce sulfate rich waters which feed into the river and precipitate a large range of evaporitic sulfates including jarosite. Iron oxide minerals associated with the evaporites are either dispersed or bedded but not nodular. The water compositions appear to be mixtures of a few discreet end-members: the two most significant occur in undiluted form as inputs to the river and are relevant to many such systems. They both have all sulfur totally oxidized as sulfate. The first is a bright red water, pH ~1.5, Fe/S 0.5 and 23 g/L iron which is greater than 95% Fe3+. Its sulfate oxygen isotope composition is +2‰SMOW and about +7‰, relative to the water O isotope composition. These data indicate pyrite oxidation by Fe3+ with O in sulfate coming mainly from water. The second end-member is a pale green water, pH ~0.7, Fe/S 0.7, 50 g/L iron present mainly as Fe2+ and O isotope composition of sulfate about +6‰SMOW , about +12.5‰ relative to the water O value. Oxygen in sulfate comes mainly from atmospheric oxygen resulting from pyrite oxidation by molecular oxygen dissolved in water. Although the Rio Tinto system reactions probably are microbiologically mediated (relevant genera have been identified there) similar processes could occur abiotically but more slowly. Meridiani Planum sediments and nodules can be described by a plausible set of similar end-member processes. The primary source of sulfate is oxidation of sulfides present in basalt (pyrite, FeS2 or pyrrhotite, FeS) and weathering would have produced oxidized sulfate rich solutions at low pH. Ground water migration could produce evaporitic ponds where various bedded sulfate mineral sediments could form. The intergranular pore-spaces would be water filled. Most terrestrial spheroidal nodular concretions form by radial diffusion in pore-water of a chemical component of a very different oxidation state from that of the surrounding water. A nodular concretion is most usually formed by the reaction of the diffusive component with others in the pore-water. There are two main possible reaction sets for formation of the Blueberries that are consistent with all current data. 1. Local concentrations of organic matter (pre-biotic or biotic) formed reduction spots in which a small amount of Fe3+ either in solution or from evaporite mineral salts, was reduced to Fe2+ and then diffused radially to form an iron oxide nodule by reaction with inwardly diffusing dissolved oxygen. 2. Similar local concentrations of organic matter could also have engendered sulfate reduction and consequent outward diffusion of dissolved sulfide reacted with iron in solution to produce an iron sulfide nodule, subsequently oxidized in situ to hematite (maybe via goethite). Our current work is successfully identifying chemical and stable isotopic characteristics for both microbial and abiotic modes of all relevant reactions.

The isotopic composition of cosmic ray calcium

NASA Technical Reports Server (NTRS)

Krombel, K. E.; Wiedenbeck, M. E.

1985-01-01

Data from the high energy cosmic ray experiment on the international sun earth explorer 3 (ISEE-3) spacecraft have been used to study the isotopic composition of cosmic ray calcium at an energy of approx. 260 MeV/amu. The arriving calcium is found to consist of (32 + or - 6)%. A propagation model consistent with both the light and the subiron secondary element abundances was used for the interpretation of the observed calcium composition. The measured 42Ca+43Ca+44Ca abundance is consistent with the calculated secondary production, while the 40Ca abundance implies a source ratio of 40Ca/Fe = (7.0 + or - 1.7)%.

Thallium isotope composition of the upper continental crust and rivers - An investigation of the continental sources of dissolved marine thallium

USGS Publications Warehouse

Nielsen, S.G.; Rehkamper, M.; Porcelli, D.; Andersson, P.; Halliday, A.N.; Swarzenski, P.W.; Latkoczy, C.; Gunther, D.

2005-01-01

The thallium (Tl) concentrations and isotope compositions of various river and estuarine waters, suspended riverine particulates and loess have been determined. These data are used to evaluate whether weathering reactions are associated with significant Tl isotope fractionation and to estimate the average Tl isotope composition of the upper continental crust as well as the mean Tl concentration and isotope composition of river water. Such parameters provide key constraints on the dissolved Tl fluxes to the oceans from rivers and mineral aerosols. The Tl isotope data for loess and suspended riverine detritus are relatively uniform with a mean of ??205Tl = -2.0 ?? 0.3 (??205Tl represents the deviation of the 205Tl/203Tl isotope ratio of a sample from NIST SRM 997 Tl in parts per 104). For waters from four major and eight smaller rivers, the majority were found to have Tl concentrations between 1 and 7 ng/kg. Most have Tl isotope compositions very similar (within ??1.5 ??205Tl) to that deduced for the upper continental crust, which indicates that no significant Tl isotope fractionation occurs during weathering. Based on these results, it is estimated that rivers have a mean natural Tl concentration and isotope composition of 6 ?? 4 ng/kg and ??205Tl = -2.5 ?? 1.0, respectively. In the Amazon estuary, both additions and losses of Tl were observed, and these correlate with variations in Fe and Mn contents. The changes in Tl concentrations have much lower amplitudes, however, and are not associated with significant Tl isotope effects. In the Kalix estuary, the Tl concentrations and isotope compositions can be explained by two-component mixing between river water and a high-salinity end member that is enriched in Tl relative to seawater. These results indicate that Tl can display variable behavior in estuarine systems but large additions and losses of Tl were not observed in the present study. Copyright ?? 2005 Elsevier Ltd.

Concentration effect on inter-mineral equilibrium isotope fractionation: insights from Mg and Ca isotopic systems

NASA Astrophysics Data System (ADS)

Huang, F.; Wang, W.; Zhou, C.; Kang, J.; Wu, Z.

2017-12-01

Many naturally occurring minerals, such as carbonate, garnet, pyroxene, and feldspar, are solid solutions with large variations in chemical compositions. Such variations may affect mineral structures and modify the chemical bonding environment around atoms, which further impacts the equilibrium isotope fractionation factors among minerals. Here we investigated the effects of Mg content on equilibrium Mg and Ca isotope fractionation among carbonates and Ca content on equilibrium Ca isotope fractionation between orthopyroxene (opx) and clinopyroxene (cpx) using first-principles calculations. Our results show that the average Mg-O bond length increases with decreasing Mg/(Mg+Ca) in calcite when it is greater than 1/48[1] and the average Ca-O bond length significantly decreases with decreasing Ca/(Ca+Mg+Fe) in opx when it ranges from 2/16 to 1/48[2]. Equilibrium isotope fractionation is mainly controlled by bond strengths, which could be measured by bond lengths. Thus, 103lnα26Mg/24Mg between dolomite and calcite dramatically increases with decreasing Mg/(Mg+Ca) in calcite [1] and it reaches a constant value when it is lower than 1/48. 103lnα44Ca/40Ca between opx and cpx significantly increases with decreasing Ca content in opx when Ca/(Ca+Mg+Fe) ranges from 2/16 to 1/48 [2]. If Ca/(Ca+Mg+Fe) is below 1/48, 103lnα44Ca/40Ca is not sensitive to Ca content. Based on our results, we conclude that the concentration effect on equilibrium isotope fractionation could be significant within a certain range of chemical composition of minerals, which should be a ubiquitous phenomenon in solid solution systems. [1] Wang, W., Qin, T., Zhou, C., Huang, S., Wu, Z., Huang, F., 2017. GCA 208, 185-197. [2] Feng, C., Qin, T., Huang, S., Wu, Z., Huang, F., 2014. GCA 143, 132-142.

Coordinated mineralogical and isotopic analyses of a cosmic symplectite discovered in a comet 81P/Wild 2 sample

NASA Astrophysics Data System (ADS)

Nguyen, Ann N.; Berger, Eve L.; Nakamura-Messenger, Keiko; Messenger, Scott; Keller, Lindsay P.

2017-09-01

We have discovered in a Stardust mission terminal particle a unique mineralogical assemblage of symplectically intergrown pentlandite ((Fe,Ni)9S8) and nanocrystalline maghemite (γ-Fe2O3). Mineralogically similar cosmic symplectites (COS) have only been found in the primitive carbonaceous chondrite Acfer 094 and are believed to have formed by aqueous alteration. The O and S isotopic compositions of the Wild 2 COS are indistinguishable from terrestrial values. The metal and sulfide precursors were thus oxidized by an isotopically equilibrated aqueous reservoir either inside the snow line, in the Wild 2 comet, or in a larger Kuiper Belt object. Close association of the Stardust COS with a Kool mineral assemblage (kosmochloric Ca-rich pyroxene, FeO-rich olivine, and albite) that likely originated in the solar nebula suggests the COS precursors also had a nebular origin and were transported from the inner solar system to the comet-forming region after they were altered.

A Zn isotope perspective on the rise of continents.

PubMed

Pons, M-L; Fujii, T; Rosing, M; Quitté, G; Télouk, P; Albarède, F

2013-05-01

Zinc isotope abundances are fairly constant in igneous rocks and shales and are left unfractionated by hydrothermal processes at pH < 5.5. For that reason, Zn isotopes in sediments can be used to trace the changing chemistry of the hydrosphere. Here, we report Zn isotope compositions in Fe oxides from banded iron formations (BIFs) and iron formations of different ages. Zinc from early Archean samples is isotopically indistinguishable from the igneous average (δ(66) Zn ~0.3‰). At 2.9-2.7 Ga, δ(66) Zn becomes isotopically light (δ(66) Zn < 0‰) and then bounces back to values >1‰ during the ~2.35 Ga Great Oxygenation Event. By 1.8 Ga, BIF δ(66) Zn has settled to the modern value of FeMn nodules and encrustations (~0.9‰). The Zn cycle is largely controlled by two different mechanisms: Zn makes strong complexes with phosphates, and phosphates in turn are strongly adsorbed by Fe hydroxides. We therefore review the evidence that the surface geochemical cycles of Zn and P are closely related. The Zn isotope record echoes Sr isotope evidence, suggesting that erosion starts with the very large continental masses appearing at ~2.7 Ga. The lack of Zn fractionation in pre-2.9 Ga BIFs is argued to reflect the paucity of permanent subaerial continental exposure and consequently the insignificant phosphate input to the oceans and the small output of biochemical sediments. We link the early decline of δ(66) Zn between 3.0 and 2.7 Ga with the low solubility of phosphate in alkaline groundwater. The development of photosynthetic activity at the surface of the newly exposed continents increased the oxygen level in the atmosphere, which in turn triggered acid drainage and stepped up P dissolution and liberation of heavy Zn into the runoff. Zinc isotopes provide a new perspective on the rise of continents, the volume of carbonates on continents, changing weathering conditions, and compositions of the ocean through time. © 2013 Blackwell Publishing Ltd.

Linking Barbados Mineral Dust Aerosols to North African Sources Using Elemental Composition and Radiogenic Sr, Nd, and Pb Isotope Signatures

NASA Astrophysics Data System (ADS)

Bozlaker, Ayse; Prospero, Joseph M.; Price, Jim; Chellam, Shankararaman

2018-01-01

Large quantities of African dust are carried across the Atlantic to the Caribbean Basin and southern United States where it plays an important role in the biogeochemistry of soils and waters and in air quality. Dusts' elemental and isotopic composition was comprehensively characterized in Barbados during the summers of 2013 and 2014, the season of maximum dust transport. Although total suspended insoluble particulate matter (TSIP) mass concentrations varied significantly daily and between the two summers, the abundances (μg element/g TSIP) of 50 elements during "high-dust days" (HDD) were similar. Aerosols were regularly enriched in Na, Cu, Zn, As, Se, Mo, Cd, Sn, Sb, and W relative to the upper continental crust. Enrichment of these elements, many of which are anthropogenically emitted, was significantly reduced during HDD, attributed to mixing and dilution with desert dust over source regions. Generally, Ti/Al, Si/Al, Ca/Al, Ti/Fe, Si/Fe, and Ca/Fe ratios during HDD differed from their respective values in hypothesized North African source regions. Nd isotope composition was relatively invariant for "low-dust days" (LDD) and HDD. In contrast, HDD-aerosols were more radiogenic exhibiting higher 87Sr/86Sr, 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios compared to LDD. Generally, Barbados aerosols' composition ranged within narrow limits and was much more homogeneous than that of hypothesized African source soils. Our results suggest that summertime Barbados aerosols are dominated by a mixture of particles originating from sources in the Sahara-Sahel regions. The Bodélé Depression, long suspected as a major source, appears to be an insignificant contributor of summertime western Atlantic dust.

Modeling Equilibrium Fe Isotope Fractionation in Fe-Organic Complexes: Implications for the use of Fe Isotopes as a Biomarker and Trends Based on the Properties of Bound Ligands

NASA Astrophysics Data System (ADS)

Domagal-Goldman, S.; Kubicki, J. D.

2006-05-01

Fe Isotopes have been proposed as a useful tracer of biological and geochemical processes. Key to understanding the effects these various processes have on Fe isotopes is accurate modeling of the reactions responsible for the isotope fractionations. In this study, we examined the theoretical basis for the claims that Fe isotopes can be used as a biomarker. This was done by using molecular orbital/density functional theory (MO/DFT) calculations to predict the equilibrium fractionation of Fe isotopes due to changes in the redox state and the bonding environment of Fe. Specifically, we predicted vibrational frequencies for iron desferrioxamine (Fe-DFOB), iron triscatechol (Fe(cat)3), iron trisoxalate (Fe(ox)3), and hexaaquo iron (Fe(H2O)6) for complexes containing both ferrous (Fe2+) and ferric (Fe3+) iron. Using these vibrational frequencies, we then predicted fractionation factors between these six complexes. The predicted fractionation factors resulting from changes in the redox state of Fe fell in the range 2.5- 3.5‰. The fractionation factors resulting from changes in the bonding environment of Fe ranged from 0.2 to 1.4‰. These results indicate that changes in the bonding strength of Fe ligands are less important to Fe isotope fractionation processes than are changes to the redox state of Fe. The implications for use of Fe as a tracer of biological processes is clear: abiological redox changes must be ruled out in a sample before Fe isotopes are considered as a potential biomarker. Furthermore, the use of Fe isotopes to measure the redox state of the Earths surface environment through time is supported by this work, since changes in the redox state of Fe appear to be the more important driver of isotopic fractionations. In addition to the large differences between redox-driven fractionations and ligand-driven fractionations, we will also show general trends in the demand for heavy Fe isotopes as a function of properties of the bound ligand. This will help the future analysis of Fe isotope fractionation. Future directions in the theoretical study of metal isotope fractionations will also be discussed, including the modeling of reactions on mineral surfaces.

Recycling of Oceanic Lithosphere: Water, fO2 and Fe-isotope Constraints

NASA Technical Reports Server (NTRS)

Bizmis, M.; Peslier, A. H.; McCammon, C. A.; Keshav, S.; Williams, H. M.

2014-01-01

Spinel peridotite and garnet pyroxenite xenoliths from Hawaii provide important clues about the composition of the oceanic lithosphere, and can be used to assess its contribution to mantle heterogeneity upon recycling. The peridotites have lower bulk H2O (approximately 70-114 ppm) than the MORB source, qualitatively consistent with melt depletion. The garnet pyroxenites (high pressure cumulates) have higher H2O (200-460 ppm, up to 550 ppm accounting for phlogopite) and low H2O/Ce ratios (less than 100). The peridotites have relatively light Fe-isotopes (delta Fe -57 = -0.34 to 0.13) that decrease with increasing depletion, while the pyroxenites are significantly heavier (delta Fe-57 up to 0.3). The observed xenolith, as well as MORB and OIB total Fe-isotope variability is larger that can be explained by existing melting models. The high H2O and low H2O/Ce ratios of pyroxenites are similar to estimates of EM-type OIB sources, while their heavy delta Fe-57 are similar to some Society and Cook-Austral basalts. Therefore, recycling of mineralogically enriched oceanic lithosphere (i.e. pyroxenites) may contribute to OIB sources and mantle heterogeneity. The Fe(3+)/Sigma? systematics of these xenoliths also suggest that there might be lateral redox gradients within the lithosphere, between juxtaposed oxidized spinel peridotites (deltaFMQ = -0.7 to 1.6, at 15 kb) and more reduced pyroxenites (deltaFMQ = -2 to -0.4, at 20-25kb). Such mineralogically and compositionally imposed fO2 gradients may generate local redox melting due to changes in fluid speciation (e.g. reduced fluids from pyroxenite encountering more oxidized peridotite). Formation of such incipient, small degree melts could further contribute to metasomatic features seen in peridotites, mantle heterogeneity, as well as the low velocity and high electrical conductivity structures near the base of the lithosphere and upper mantle.

Intense molybdenum accumulation in sediments underneath a nitrogenous water column and implications for the reconstruction of paleo-redox conditions based on molybdenum isotopes

NASA Astrophysics Data System (ADS)

Scholz, Florian; Siebert, Christopher; Dale, Andrew W.; Frank, Martin

2017-09-01

The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 μg g-1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery caused the 'anomalously' high interglacial Mo accumulation rates in the paleo-record. Our findings suggest that Fe- and nitrate-dependent Mo shuttling under nitrogenous conditions needs to be considered a possible reason for sedimentary Mo enrichments during past periods of widespread anoxia in the open ocean.

Iron and sulfur isotope constraints on redox conditions associated with the 3.2 Ga barite deposits of the Mapepe Formation (Barberton Greenstone Belt, South Africa)

NASA Astrophysics Data System (ADS)

Busigny, Vincent; Marin-Carbonne, Johanna; Muller, Elodie; Cartigny, Pierre; Rollion-Bard, Claire; Assayag, Nelly; Philippot, Pascal

2017-08-01

The occurrence of Early Archean barite deposits is intriguing since this type of sediment requires high availability of dissolved sulfate (SO42-), the oxidized form of sulfur, although most authors argued that the Archean eon was dominated by reducing conditions, with low oceanic sulfate concentration (<10 μM) relative to present day levels of 28,000 μM. In order to better assess the redox state of the paleo-atmosphere and -oceans, we examined Fe and S isotope compositions in a sedimentary sequence from the 3.2 Ga-old Mendon and Mapepe formations (Kaapvaal craton, South Africa), recovered from the drill-core BBDP2 of the Barberton Barite Drilling Project. Major elements were also analyzed to constrain the respective imprints of detrital vs metasomatic processes, in particular using Al, Ti and K interrelations. Bulk rock Fe isotope compositions are linked to mineralogy, with δ56Fe values varying between -2.04‰ in Fe sulfide-dominated barite beds, to +2.14‰ in Fe oxide-bearing cherts. δ34S values of sulfides vary between -10.84 and +3.56‰, with Δ33S in a range comprised between -0.35 and +2.55‰, thus supporting an O2-depleted atmosphere (<10-5 PAL). Iron isotope variations together with major element correlations show that, although the sediments experienced a pervasive stage of hydrothermal alteration, the rocks preserved a primary/authigenic signature predating subsequent hydrothermal stage. Highly positive δ56Fe values recorded in primary Fe-oxides from ferruginous cherts support partial Fe oxidation in a reducing oceanic environment (O2 < 10-4 μM), but are incompatible with a model of complete oxidation at the redox boundary of a stratified water column. Iron oxide precipitation under low O2 levels was likely mediated by anoxygenic photosynthesis, and/or abiotic photo-oxidation processes. Our results are consistent with global anoxic conditions in the 3.2 Ga-old sediments, implying that the barite deposits were most likely sourced by atmospheric photolysis of S gases produced by large subaerial volcanic events, and possibly SO42- produced by magmatic SO2 disproportionation in hydrothermal systems.

Experimental Determination of Isotopic Fractionation of Chromium(III) During Oxidation by Manganese Oxides

NASA Astrophysics Data System (ADS)

Bain, D. J.; Bullen, T. D.

2004-12-01

In environmental conditions, chromium (Cr) exists in either the immobile, micronutrient trivalent form (Cr(III)) or the mobile, toxic hexavalent (Cr(VI)) form. Cr(VI) quickly reduces upon encountering Fe(II) or soil organic material (SOM). Therefore, it is often assumed that human Cr additions to terrestrial systems will impact localized areas and natural sources pose minimal threat to human or ecosystem health. However, oxidation and mobilization of Cr(III) by common manganese (Mn) oxides is less understood, especially in field settings. Moreover, Cr(VI)'s anionic form should enhance mobility through Fe- and SOM-poor soil and saprolite matrices. The variety of redox environments along a flowpath makes Cr source identification difficult with only concentration and speciation data. However, Cr has four stable isotopes (50, 52, 53, and 54), and characteristic fractionations during redox transformations might allow clarification of sources and flowpaths. For example, Cr(VI) reduction by a variety of reductants discriminates against heavy Cr, resulting in an increasingly heavy Cr(VI) fraction as reduction proceeds (α Cr(III)-Cr(VI) ˜ 0.996). Measurement of isotopic fractionation in other environmental Cr transformations, including oxidation, is necessary to understand Cr fate and transport. Recent estimates of isotopic fractionation between Cr aqueous species based on theoretical considerations indicate that at equilibrium α Cr(III)-Cr(VI) ˜ 0.994. To test this theoretical prediction, we are assessing the isotopic variability of aqueous Cr during oxidation of Cr(III) on MnO2 materials such as birnessite in laboratory experiments. Initial results indicate that the isotopic composition of the product Cr(VI) ranges from -2.50 to +0.71 ‰ δ 53Cr, suggesting an important role for kinetic isotope effects during the initial oxidation process. Large fluctuations in isotopic composition continue after dissolved Cr(VI) and Cr(III) ratios stabilize and net Cr(VI) production rates are very slow. Moreover, the Cr(VI) isotopic composition fluctuates between heavy and light compositions several times over the course of reaction. Overall, however, the long term trend appears to be toward the equilibrium fractionation predicted by theory. This adds further credence to hypothesized multiple oxidation pathways existing in the system and suggests that multiple processes with off-setting fractionations are driving the system. If these results are representative of natural systems, environmental Cr samples that have been oxidized or been oxidized/reduced multiple times along a flowpath, will have isotopic compositions that vary widely, depending predominantly on sample collection time. In turn, this suggests that Cr isotopic compositions alone will not clarify Cr fate and transport, especially at larger scales (e.g., catchments), and other geochemical and hydrologic constraints will be required.

Manganese oxide shuttling in pre-GOE oceans - evidence from molybdenum and iron isotopes

NASA Astrophysics Data System (ADS)

Kurzweil, Florian; Wille, Martin; Gantert, Niklas; Beukes, Nicolas J.; Schoenberg, Ronny

2016-10-01

The local occurrence of oxygen-rich shallow marine water environments has been suggested to significantly predate atmospheric oxygenation, which occurred during the Great Oxidation Event (GOE) ca. 2.4 billion years ago. However, the potential influence of such 'oxygen oases' on the mobility, distribution and isotopic composition of redox sensitive elements remains poorly understood. Here, we provide new molybdenum and iron isotopic data from shallow marine carbonate and silicate iron formations of the Koegas Subgroup, South Africa, that confirm local ocean redox stratification prior to the GOE. Mn concentrations correlate negatively with both δ98 Mo and δ56 Fe values, which highlights the substantial role of particulate manganese for the cycling of Mo and Fe in the Paleoproterozoic oceans. Based on these trends we propose that pore water molybdate was recharged (1) by the diffusional transport of seawater molybdate with high δ98 Mo and (2) by the re-liberation of adsorbed molybdate with low δ98 Mo during Mn oxide dissolution within the sediment. The relative contribution of isotopically light Mo is highest close to a Mn chemocline, where the flux of Mn oxides is largest, causing the negative correlation of Mn concentrations and δ98 Mo values in the Koegas sediments. The negative correlation between δ56 Fe values and Mn concentrations is likely related to Fe isotope fractionation during Fe(II) oxidation by Mn oxides, resulting in lower δ56 Fe values in the uppermost water column close to a Mn chemocline. We argue that the preservation of these signals within Paleoproterozoic sediments implies the existence of vertically extended chemoclines with a smoother gradient, probably as a result of low atmospheric oxygen concentrations. Furthermore, we suggest that abiotic oxidation of Fe(II) by a Mn oxide particle shuttle might have promoted the deposition of the Koegas iron formations.

Molybdenum isotopes in modern marine hydrothermal Fe/Mn deposits: Implications for Archean and Paleoproterozoic Mo cycles

NASA Astrophysics Data System (ADS)

Goto, K. T.; Hein, J. R.; Shimoda, G.; Aoki, S.; Ishikawa, A.; Suzuki, K.; Gordon, G. W.; Anbar, A. D.

2016-12-01

Molybdenum isotope (δ98/95Mo) variations recorded in Archean and Paleoproterozoic Fe/Mn-rich sediments have been used to constrain ocean redox conditions at the time of deposition (Canfield et al., 2013 PNAS; Planavsky et al., 2014 Nat. Geo.; Kurzweil et al., 2015 GCA). However, except for hydrogenous Fe-Mn crusts (Siebert et al., 2003), δ98/95Mo variation of modern Fe and Mn oxide deposits has been poorly investigated. Marine hydrothermal systems are thought to be the major source of Fe and Mn in Archean and Paleoproterozoic Fe- and Mn-rich sediments. Hence, to accurately interpret Mo isotope data of those ancient sedimentary rocks, it is important to evaluate the possible influence of hydrothermally derived Mo on δ98/95Mo of modern Fe- and Mn-rich sediments. In this study, we analyzed Mo isotopic compositions of one hydrothermal Fe oxide and 15 Mn oxides from five different hydrothermal systems in the modern ocean. The Fe oxide is composed mainly of goethite, and has a δ98/95Mo of 0.7‰, which is 1.4‰ lighter than that of present-day seawater. The observed offset is similar to isotope fractionation observed during adsorption experiments of Mo on goethite (Δ98/95Mogoethite-solution = -1.4 ± 0.5%; Goldberg et al., 2009 GCA). The 15 hydrothermal Mn oxides show large variations in δ98/95Mo ranging from -1.7 to 0.5‰. However, most of the values are similar to those of modern hydrogenous Fe-Mn crusts (Siebert et al., 2003 EPSL), and fall within the range of estimated δ98/95Mo of Mn oxides precipitated from present-day seawater using the isotope offset reported from adsorption experiments (Δ98/95Mo = -2.7 ± 0.3‰; Wasylenki et al., 2008 GCA). These findings indicate that seawater is the dominant source of Mo for modern hydrothermal Fe and Mn deposits. However, the observed large variation indicates that the contribution Mo from local hydrothermal systems is not negligible. The oceanic Mo inventory during the Archean and Paleoproterozoic is thought to be much smaller than that of present-day (Scott et al., 2008 Nature). Hence, δ98/95Mo of Archean and Paleoproterozoic Fe- and Mn-rich sediments could be strongly influenced by hydrothermally derived Mo, which may contrast to modern hydrothermal deposits. Possible Archean and Paleoproterozoic Mo cycles constrained by these data will also be discussed.

Planetary and meteoritic Mg/Si and δ30 Si variations inherited from solar nebula chemistry

NASA Astrophysics Data System (ADS)

Dauphas, Nicolas; Poitrasson, Franck; Burkhardt, Christoph; Kobayashi, Hiroshi; Kurosawa, Kosuke

2015-10-01

The bulk chemical compositions of planets are uncertain, even for major elements such as Mg and Si. This is due to the fact that the samples available for study all originate from relatively shallow depths. Comparison of the stable isotope compositions of planets and meteorites can help overcome this limitation. Specifically, the non-chondritic Si isotope composition of the Earth's mantle was interpreted to reflect the presence of Si in the core, which can also explain its low density relative to pure Fe-Ni alloy. However, we have found that angrite meteorites display a heavy Si isotope composition similar to the lunar and terrestrial mantles. Because core formation in the angrite parent-body (APB) occurred under oxidizing conditions at relatively low pressure and temperature, significant incorporation of Si in the core is ruled out as an explanation for this heavy Si isotope signature. Instead, we show that equilibrium isotopic fractionation between gaseous SiO and solid forsterite at ∼1370 K in the solar nebula could have produced the observed Si isotope variations. Nebular fractionation of forsterite should be accompanied by correlated variations between the Si isotopic composition and Mg/Si ratio following a slope of ∼1, which is observed in meteorites. Consideration of this nebular process leads to a revised Si concentration in the Earth's core of 3.6 (+ 6.0 / - 3.6) wt% and provides estimates of Mg/Si ratios of bulk planetary bodies.

Tracing sources of crustal contamination using multiple S and Fe isotopes in the Hart komatiite-associated Ni-Cu-PGE sulfide deposit, Abitibi greenstone belt, Ontario, Canada

NASA Astrophysics Data System (ADS)

Hiebert, R. S.; Bekker, A.; Houlé, M. G.; Wing, B. A.; Rouxel, O. J.

2016-10-01

Assimilation by mafic to ultramafic magmas of sulfur-bearing country rocks is considered an important contributing factor to reach sulfide saturation and form magmatic Ni-Cu-platinum group element (PGE) sulfide deposits. Sulfur-bearing sedimentary rocks in the Archean are generally characterized by mass-independent fractionation of sulfur isotopes that is a result of atmospheric photochemical reactions, which produces isotopically distinct pools of sulfur. Likewise, low-temperature processing of iron, through biological and abiotic redox cycling, produces a range of Fe isotope values in Archean sedimentary rocks that is distinct from the range of the mantle and magmatic Fe isotope values. Both of these signals can be used to identify potential country rock assimilants and their contribution to magmatic sulfide deposits. We use multiple S and Fe isotopes to characterize the composition of the potential iron and sulfur sources for the sulfide liquids that formed the Hart deposit in the Shaw Dome area within the Abitibi greenstone belt in Ontario (Canada). The Hart deposit is composed of two zones with komatiite-associated Ni-Cu-PGE mineralization; the main zone consists of a massive sulfide deposit at the base of the basal flow in the komatiite sequence, whereas the eastern extension consists of a semi-massive sulfide zone located 12 to 25 m above the base of the second flow in the komatiite sequence. Low δ56Fe values and non-zero δ34S and Δ33S values of the komatiitic rocks and associated mineralization at the Hart deposit is best explained by mixing and isotope exchange with crustal materials, such as exhalite and graphitic argillite, rather than intrinsic fractionation within the komatiite. This approach allows tracing the extent of crustal contamination away from the deposit and the degree of mixing between the sulfide and komatiite melts. The exhalite and graphitic argillite were the dominant contaminants for the main zone of mineralization and the eastern extension zone of the Hart deposit, respectively. Critically, the extent of contamination, as revealed by multiple S and Fe isotope systematics, is greatest within the deposit and decreases away from it within the komatiite flow. This pattern points to a local source of crustal contamination for the mantle-derived komatiitic melt and a low degree of homogenization between the mineralization and the surrounding lava flow. Coupled S and Fe isotope patterns like those identified at the Hart deposit may provide a useful tool for assessing the potential of a komatiitic sequence to host Ni-Cu-(PGE).

Equilibrium Tin Isotope Fractionation during Metal-Sulfide-Silicate Differentiation: A Nuclear Resonant Inelastic X-ray Scattering Approach

NASA Astrophysics Data System (ADS)

Roskosz, M.; Amet, Q.; Fitoussi, C.; Laporte, D.; Hu, M. Y.; Alp, E. E.

2016-12-01

Metal-silicate differentiation was recently addressed through the insight of the isotopic composition of siderophile elements (mainly Fe, Si and Cr isotopes) of planetary and extraterrestrial bodies. A key limitation of this approach is however the knowledge of equilibrium fractionation factors between coexisting phases (metal alloys, silicates and sulfides) used to interpret data on natural samples. These properties are difficult to determine experimentally. In this context, tin is generally classified as a chalcophile element but it is also siderophile and volatile. We applied a synchrotron-based method to circumvent difficulties related to determination of equilibrium isotope fractionation. The nuclear resonant inelastic x-ray scattering (NRIXS) was used to measure the phonon excitation spectrum and then to derive the force constant and finally the fractionation factors of Sn-bearing geomaterials. Spectroscopic measurements were carried out at room pressure at Sector 30-ID (APS, USA). A range of Fe-Ni alloys, rhyolitic and basaltic glasses and iron sulfides containing isotopically enriched 119Sn were synthesized. The tin content and the redox conditions prevailing during the synthesis were varied. The data evaluation was carried out using PHOENIX and SciPhon programs. A strong effect of both the redox state and the tin content was measured. In addition, the composition of the silicate glasses was found to be another important factor determining the tin isotope metal-silicate-sulfide fractionation factors. Our results are consistent with trends previously observed in the case of iron isotopes [1,2]. We will discuss the implications of our experimental results in terms of tin isotope planetary signatures. References: [1] Dauphas et al. (2014), EPSL, 398, 127-140; [2] Roskosz et al. (2015), GCA, 169, 184-199.

Iron availability influences 15N-isotope fractionation during nitrogen fixation by aerobic chemoheterotroph Azotobacter vinelandii

NASA Astrophysics Data System (ADS)

Zhang, X.; Kopf, S.; Lee, A. C.

2016-12-01

The N stable isotope composition (δ15N) of biomass provides a powerful tool for reconstructing present and past N cycling, but its interpretation hinges on a complete understanding of the isotopic signature of biological nitrogen fixation, which sets the δ15N of newly fixed N. All biological nitrogen fixation is catalyzed by the metalloenzyme nitrogenase in a complex reaction that reduces inert atmospheric N2 gas into bioavailable ammonium. Recent investigations into the metal cofactor variants of nitrogenase revealed that the canonical Mo-, and alternative V-, and Fe-only isoforms of nitrogenase impart different isotope fractionations during N2 fixation in vivo, challenging the traditional view that N2 fixation only imparts small, invariable isotope effects of 0-2‰. However, the mechanistic basis for the fractionation of N2 fixation remains largely unknown. To better understand mechanisms underlying fractionation, we varied Fe availability and measured in vivo fractionations for the aerobic chemoheterotroph Azotobacter vinelandii utilizing Mo- or V-nitrogenase under batch culture conditions. Under all iron conditions, N2 fixation based on Mo-nitrogenase yielded lower fractionations (heavier biomasss δ15N) compared to V-nitrogenase. For fractionations associated with a single metalloenzyme, higher Fe concentrations, which correlated with faster growth rates, yielded small but systematically larger fractionations ( 1 ‰ increase for Mo- and V- nitrogenases). To directly determine the effect of growth rate on fractionation, we grew Mo-nitrogenase expressing A. vinelandii in Fe-replete medium at different growth rates using chemostats and found that growth rate alone does not alter fractionation. The results indicate that Fe availability, in addition to the type of nitrogenase metalloenzyme, controls 15N fractionation during N2 fixation by A. vinelandii.

V isotope composition in modern marine hydrothermal sediments

NASA Astrophysics Data System (ADS)

Wu, F.; Owens, J. D.; Nielsen, S.; German, C. R.; Rachel, M.

2017-12-01

Vanadium is multivalence transition metal with two isotopes (51V and 50V). Recent work has shown that large V isotope variations occur with oxygen variations in modern sediments (Wu et al., 2016 and 2017 Goldschmidt Abstracts), providing its potential as a promising proxy for determining low oxygen conditions. However, the development of V isotopes as a proxy to probe past redox conditions requires a comprehensive understanding of the modern oceanic isotopic mass balance. Therein, the scavenging of V from the hydrous iron oxides in hydrothermal fluid has been shown to be an important removal process from seawater (Rudnicki and Elderfield, 1993 GCA) but remains unquantified. In this study, we analyzed V isotopic compositions of metalliferous sediments around the active TAG hydrothermal mound from the mid-Atlantic Ridge (26° degrees North) and the Eastern Pacific Zonal Transect (GEOTRACES EPZT cruise GP16). The TAG sediments deposited as Fe oxyhydroxides from plume fall-out, and have δ51V values between -0.3 to 0‰. The good correlation between Fe and V for these metalliferous sediments indicate that the accumulation of V in these samples is directly related to the deposition of Fe oxyhydroxides, which also control their V isotope signature. The EPZT samples cover 8,000 km in the South Pacific Ocean with sedimentary areas that underlie the Peru upwelling region and the well-oxygenated deep South Pacific Ocean influenced by hydtorthermal plume material from southern East Pacific Rise (EPR). The sediments collected at the east of the EPR have δ51V values between -1.2 to -0.7‰, similar to previous δ51V of oxic sediments. In contrast, the sediments from the west of the EPR have δ51V values (-0.4 to 0‰) similar to hydrothermal sediments from the mid-Atlantic Ridge, indicating the long transportation (more than 4,000 km, Fitzsimmons et al., 2017 NG) of Fe and Mn from hydrothermal plume and their incorporation into sediments have a major impact on the cycle of V in the ocean. The fingerprint of δ51V between oxic sediments and hydrothermal flux are significantly different and should be easily discernible in the geologic record. Consequently, our results show that the removal of V from hydrothermal sediments has an important influence on the marine V cycle, which needs to be considered for future modern and paleoclimatic studies.

Experimental determination of the Mo isotope fractionation factor between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, R. C.; Burkhardt, C.; Schmidt, M. W.; Bourdon, B.

2011-12-01

The conditions and chemical consequences of core formation have mainly been reconstructed from experimentally determined element partition coefficients between metal and silicate liquids. However, first order questions such as the mode of core formation or the nature of the light element(s) in the Earth's core are still debated [1]. In addition, the geocentric design of most experimental studies leaves the conditions of core formation on other terrestrial planets and asteroids even more uncertain than for Earth. Through mass spectrometry, records of mass-dependent stable isotope fractionation during high-temperature processes such as metal-silicate segregation are detectable. Stable isotope fractionation may thus yield additional constrains on core formation conditions and its consequences for the chemical evolution of planetary objects. Experimental investigations of equilibrium mass-dependent stable isotope fractionation have shown that Si isotopes fractionate between metal and silicate liquids at temperatures of 1800°C and pressures of 1 GPa, while Fe isotopes leave no resolvable traces of core formation processes [2,3]. Molybdenum is a refractory and siderophile trace element in the Earth, and thus much less prone to complications arising from mass balancing core and mantle and from potential volatile behaviour than other elements. To determine equilibrium mass-dependent Mo isotope fractionation during metal-silicate segregation, we have designed piston cylinder experiments with a basaltic silicate composition and an iron based metal with ~8 wt% Mo, using both graphite and MgO capsules. Metal and silicate phases are completely segregated by the use of a centrifuging piston cylinder at ETH Zurich, thus preventing analysis of mixed metal and silicate signatures. Molybdenum isotope compositions were measured using a Nu Instruments 1700 MC-ICP-MS at ETH Zurich. To ensure an accurate correction of analytical mass fractionation a 100Mo-97Mo double spike was admixed before chemical purification. Initial results provide an equilibrium 98Mo/95Mo isotope fractionation factor between metal and silicate liquids of -0.18±0.10% (2σ) at 1400°C and 1 GPa. Although the relative mass difference of these Mo isotopes is smaller than for Fe isotopes, this result implies that metal-silicate segregation may have led to mass-dependent stable Mo isotope fractionation, as opposed to Fe isotopes. A possible explanation is that the bonding environment of Mo may counterbalance its relatively small mass separation. At reducing conditions, Mo occurs in 4+ valence state in silicates [4] and thus its bond strength difference between metal and silicate may be more similar to that of Si than Fe. Stable Mo isotopes may thus become an important tool for constraining the conditions of core formation in asteroids and terrestrial planets. [1] Rubie et al. (2011) EPSL 301, 31-42. [2] Shahar et al. (2009) EPSL 288, 228-234. [3] Poitrasson et al. (2009) EPSL 278, 376-385. [4] Farges et al. (2006) Can. Min. 44, 731-753.

Zinc isotope systematics of subduction-zone magmas

NASA Astrophysics Data System (ADS)

Huang, J.; Zhang, X. C.; Huang, F.; Yu, H.

2016-12-01

Subduction-zone magmas are generated by partial melting of mantle wedge triggered by addition of fluids derived from subducted hydrothermally altered oceanic lithosphere. Source of the fluids may be sediment, altered oceanic crust and serpentinized peridotite/serpentinite. Knowledge of the exact fluid source can facilitate our better understanding of the mechanism of fluid flux, element cycling and crust-mantle interaction in subduction zones. Zinc isotopes have the potential to place a constraint on this issue, because (1) Zn has an intermediate mobility during fluid-rock interaction and is enriched in subduction-zone fluids (e.g., Li et al., 2013); (2) sediment, altered oceanic crust and serpentinite have distinct Zn isotopic compositions (Pons et al., 2011); and (3) the mantle has a homogeneous Zn isotope composition (δ66Zn = 0.28 ± 0.05‰, Chen et al., 2013). Thus, the Zn isotopic composition of subduction-zone magmas reflects the characteristics of slab-derived fluids of different sources. Here, high-precision Zn isotope analyses were conducted on igneous rocks from arcs of Central America, Kamchatka, South Lesser Antilles, and Aleutian. One rhyolite with 75.1 wt.% SiO2 and 0.2 wt.% FeOT displays the heaviest δ66Zn value of 0.394‰ (relative to JMC Lyon) that probably results from the crystallization of Fe-Ti oxides during the late-stage differentiation. The rest of rocks have Zn isotopic compositions (0.161 to 0.339‰) similar to or lighter than those of the mantle. In an individual arc, the δ66Zn values of rocks show broad negative correlations with Ba/Th and 87Sr/86Sr ratios, suggesting that the slab-derived fluids should have lighter δ66Zn as well as higher Ba/Th and 87Sr/86Sr ratios relative to the mantle. These features are in accordance with those of serpentinites. Thus, addition of serpentinite-derived 66Zn-depleted fluids into the mantle wedge can explain the declined δ66Zn of subduction-zone magmas. ReferenceChen et al. (2013) EPSL 369-370:34-42; Li et al. (2013) GCA 120:326-362; Pons et al. (2011) PNAS 108:17639-17643.

Fractionation of Fe isotopes by soil microbes and organic acids

USGS Publications Warehouse

Brantley, Susan L.; Liermann, Laura; Bullen, Thomas D.

2001-01-01

Small natural variations in Fe isotopes have been attributed to biological cycling. However, without understanding the mechanism of fractionation, it is impossible to interpret such variations. Here we show that the δ56Fe of Fe dissolved from a silicate soil mineral by siderophore-producing bacteria is as much as 0.8% lighter than bulk Fe in the mineral. A smaller isotopic shift is observed for Fe released abiotically by two chelates, and the magnitude of the shift increases with affinity of the ligand for Fe, consistent with a kinetic isotope effect during hydrolysis of Fe at the mineral surface. Fe dissolved abiotically without chelates shows no isotopic shift. The δ56Fe of the exchange fraction on soil grains is also lighter by ~0.6%-1% than Fe from both hornblende and iron oxyhydroxides. The kinetic isotope effect is therefore preserved in open systems such as soils. when recorded in the rock record, Fe isotopic fractionation could document Fe transport by organic molecules or by microbes where such entities were present in the geologic past.

Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

USGS Publications Warehouse

Fantle, M.S.; Bullen, T.D.

2009-01-01

The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a specific isotope system, it should be noted that the same methods can be used to evaluate any isotope system of interest. ?? 2008 Elsevier B.V.

In Situ Carbon Isotope Analysis by Laser Ablation MC-ICP-MS.

PubMed

Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Zhao, Kui-Dong; Duan, Deng-Fei

2017-12-19

Carbon isotopes have been widely used in tracing a wide variety of geological and environmental processes. The carbon isotope composition of bulk rocks and minerals was conventionally analyzed by isotope ratio mass spectrometry (IRMS), and, more recently, secondary ionization mass spectrometry (SIMS) has been widely used to determine carbon isotope composition of carbon-bearing solid materials with good spatial resolution. Here, we present a new method that couples a RESOlution S155 193 nm laser ablation system with a Nu Plasma II MC-ICP-MS, with the aim of measuring carbon isotopes in situ in carbonate minerals (i.e., calcite and aragonite). Under routine operating conditions for δ 13 C analysis, instrumental bias generally drifts by 0.8‰-2.0‰ in a typical analytical session of 2-3 h. Using a magmatic calcite as the standard, the carbon isotopic composition was determined for a suite of calcite samples with δ 13 C values in the range of -6.94‰ to 1.48‰. The obtained δ 13 C data are comparable to IRMS values. The combined standard uncertainty for magmatic calcite is <0.3‰ (1s). No significant matrix effects have been identified in calcite with the amplitude of chemical composition variation (i.e., MnO, SrO, MgO, or FeO) up to 2.5 wt %. Two modern corals were investigated using magmatic calcite as the calibration standard, and the average δ 13 C values for both corals are similar to the bulk IRMS values. Moreover, coral exhibits significant heterogeneity in carbon isotope compositions, with differences up to 4.85‰ within an individual coral. This study indicates that LA-MC-ICP-MS can serve as an appropriate method to analyze carbon isotopes of carbonate minerals in situ.

Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

DOE PAGES

Rolison, John M.; Stirling, Claudine H.; Middag, Rob; ...

2018-02-19

We present that the chemical response of the Precambrian oceans to rising atmospheric O 2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shiftmore » in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS 2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the ‘Great Oxidation Event’ around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.« less

Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rolison, John M.; Stirling, Claudine H.; Middag, Rob

We present that the chemical response of the Precambrian oceans to rising atmospheric O 2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shiftmore » in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS 2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the ‘Great Oxidation Event’ around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.« less

Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

NASA Astrophysics Data System (ADS)

Rolison, John M.; Stirling, Claudine H.; Middag, Rob; Gault-Ringold, Melanie; George, Ejin; Rijkenberg, Micha J. A.

2018-04-01

The chemical response of the Precambrian oceans to rising atmospheric O2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shift in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the 'Great Oxidation Event' around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.

Constraining Thermal Histories by Monte Carlo Simulation of Mg-Fe Isotopic Profiles in Olivine

NASA Astrophysics Data System (ADS)

Sio, C. K. I.; Dauphas, N.

2016-12-01

In thermochronology, random time-temperature (t-T) paths are generated and used as inputs to model fission track data. This random search method is used to identify a range of acceptable thermal histories that can describe the data. We have extended this modeling approach to magmatic systems. This approach utilizes both the chemical and stable isotope profiles measured in crystals as model constraints. Specifically, the isotopic profiles are used to determine the relative contribution of crystal growth vs. diffusion in generating chemical profiles, and to detect changes in melt composition. With this information, tighter constraints can be placed on the thermal evolution of magmatic bodies. We use an olivine phenocryst from the Kilauea Iki lava lake, HI, to demonstrate proof of concept. We treat this sample as one with little geologic context, then compare our modeling results to the known thermal history experienced by that sample. To complete forward modeling, we use MELTS to estimate the boundary condition, initial and quench temperatures. We also assume a simple relationship between crystal growth and cooling rate. Another important parameter is the isotopic effect for diffusion (i.e., the relative diffusivity of the light vs. heavy isotope of an element). The isotopic effects for Mg and Fe diffusion in olivine have been estimated based on natural samples; experiments to better constrain these parameters are underway. We find that 40% of the random t-T paths can be used to fit the Mg-Fe chemical profiles. However, only a few can be used to simultaneously fit the Mg-Fe isotopic profiles. These few t-T paths are close to the independently determined t-T history of the sample. This modeling approach can be further extended other igneous and metamorphic systems where data exist for diffusion rates, crystal growth rates, and isotopic effects for diffusion.

Isotopic signatures suggest important contributions from recycled gasoline, road dust and non-exhaust traffic sources for copper, zinc and lead in PM10 in London, United Kingdom

NASA Astrophysics Data System (ADS)

Dong, Shuofei; Ochoa Gonzalez, Raquel; Harrison, Roy M.; Green, David; North, Robin; Fowler, Geoff; Weiss, Dominik

2017-09-01

The aim of this study was to improve our understanding of what controls the isotope composition of Cu, Zn and Pb in particulate matter (PM) in the urban environment and to develop these isotope systems as possible source tracers. To this end, isotope ratios (Cu, Zn and Pb) and trace element concentrations (Fe, Al, Cu, Zn, Sb, Ba, Pb, Cr, Ni and V) were determined in PM10 collected at two road sites with contrasting traffic densities in central London, UK, during two weeks in summer 2010, and in potential sources, including non-combustion traffic emissions (tires and brakes), road furniture (road paint, manhole cover and road tarmac surface) and road dust. Iron, Ba and Sb were used as proxies for emissions derived from brake pads, and Ni, and V for emissions derived from fossil fuel oil. The isotopic composition of Pb (expressed using 206Pb/207Pb) ranged between 1.1137 and 1.1364. The isotope ratios of Cu and Zn expressed as δ65CuNIST976 and δ66ZnLyon ranged between -0.01‰ and +0.51‰ and between -0.21‰ and +0.33‰, respectively. We did not find significant differences in the isotope signatures in PM10 over the two weeks sampling period and between the two sites, suggesting similar sources for each metal at both sites despite their different traffic densities. The stable isotope composition of Pb suggests significant contribution from road dust resuspension and from recycled leaded gasoline. The Cu and Zn isotope signatures of tires, brakes and road dust overlap with those of PM10. The correlation between the enrichments of Sb, Cu, Ba and Fe in PM10 support the previously established hypothesis that Cu isotope ratios are controlled by non-exhaust traffic emission sources in urban environments (Ochoa Gonzalez et al., 2016). Analysis of the Zn isotope signatures in PM10 and possible sources at the two sites suggests significant contribution from tire wear. However, temporary additional sources, likely high temperature industrial emissions, need to be invoked to explain the isotopically light Zn found in 3 out of 18 samples of PM10.

NanoSIMS Determination of Carbon and Oxygen Isotopic Compositions of Presolar Graphites from the Murchison Meteorite

NASA Technical Reports Server (NTRS)

Stadermann, F. J.; Croat, T. K.; Bernatowicz, T.

2004-01-01

Graphite from the Murchison density separate KFC1 (2.15 - 2.20 g/cu cm) has previously been studied by combined SEM/EDX and ion microprobe analysis. These studies found several distinct morphological types of graphites and C isotopic compositions that vary over more than 3 orders of magnitude, clearly establishing their presolar origin. Subsequent TEM measurements of a subset of these particles found abundant embedded crystals of metal (Zr, Mo, Ti, Ru) carbides which were incorporated during the growth of the graphites. A new TEM study of a large set of KFC1 graphites led to the discovery of another type of presolar material, Ru-Fe metal. Here we report results of the C and O isotopic measurements in the same graphite sections, which makes it possible for the first time to directly correlate isotopic and TEM data of KFC1 grains.

Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

USGS Publications Warehouse

Ufnar, David F.; Gonzalez, Luis A.; Ludvigson, Greg A.; Brenner, Richard L.; Witzkes, Brian J.

2004-01-01

Meteoric sphaerosiderite lines (MSLs), defined by invariant ??18O and variable ??13C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre-scale FeCO3 nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well-preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO3) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca2+, Mg2+ and Mn2+ for Fe2+. Examples of diagenetically altered Cretaceous sphaerosiderite-bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic ??18O and ??13C values are preserved. All three units contain poikilotopic calcite cements with significantly different ??18O and ??13C values from the co-occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant ??18O vs. ??13C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric ??18O and ??13C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end-member compositions. Modelled hyperbolic fluid mixing curves for the Success S2 Formation suggest precipitation from fluids that were < 25% sea water. ?? 2004 International Association of Sedimentologists.

A model composition for Mars derived from the oxygen isotopic ratios of martian/SNC meteorites. [Abstract only

NASA Technical Reports Server (NTRS)

Delaney, J. S.

1994-01-01

Oxygen is the most abundant element in most meteorites, yet the ratios of its isotopes are seldom used to constrain the compositional history of achondrites. The two major achondrite groups have O isotope signatures that differ from any plausible chondritic precursors and lie between the ordinary and carbonaceous chondrite domains. If the assumption is made that the present global sampling of chondritic meteorites reflects the variability of O reservoirs at the time of planetessimal/planet aggregation in the early nebula, then the O in these groups must reflect mixing between known chondritic reservoirs. This approach, in combination with constraints based on Fe-Mn-Mg systematics, has been used previously to model the composition of the basaltic achondrite parent body (BAP) and provides a model precursor composition that is generally consistent with previous eucrite parent body (EPB) estimates. The same approach is applied to Mars exploiting the assumption that the SNC and related meteorites sample the martian lithosphere. Model planet and planetesimal compositions can be derived by mixing of known chondritic components using O isotope ratios as the fundamental compositional constraint. The major- and minor-element composition for Mars derived here and that derived previously for the basaltic achondrite parent body are, in many respects, compatible with model compositions generated using completely independent constraints. The role of volatile elements and alkalis in particular remains a major difficulty in applying such models.

Pathways of coupled arsenic and iron cycling in high arsenic groundwater of the Hetao basin, Inner Mongolia, China: an iron isotope approach

USGS Publications Warehouse

Guo, Huaming; Liu, Chen; Lu, Hai; Wanty, Richard B.; Wang, Jun; Zhou, Yinzhu

2013-01-01

High As groundwater is widely distributed all over the world, which has posed a significant health impact on millions of people. Iron isotopes have recently been used to characterize Fe cycling in aqueous environments, but there is no information on Fe isotope characteristics in the groundwater. Since groundwater As behavior is closely associated with Fe cycling in the aquifers, Fe isotope signatures may help to characterize geochemical processes controlling As concentrations of shallow groundwaters. This study provides the first observation of Fe isotope fractionation in high As groundwater and evaluation of Fe cycling and As behaviors in shallow aquifers in terms of Fe isotope signatures. Thirty groundwater samples were taken for chemical and isotopic analysis in the Hetao basin, Inner Mongolia. Thirty-two sediments were sampled as well from shallow aquifers for Fe isotope analysis. Results showed that groundwater was normally enriched in isotopically light Fe with δ56Fe values between −3.40‰ and 0.58‰ and median of −1.14‰, while heavier δ56Fe values were observed in the sediments (between −1.10‰ and 0.75‰, median +0.36‰). In reducing conditions, groundwaters generally had higher δ56Fe values, in comparison with oxic conditions. High As groundwaters, generally occurring in reducing conditions, had high δ56Fe values, while low As groundwaters normally had low δ56Fe values. Although sediment δ56Fe values were generally independent of lithological conditions, a large variation in sediment δ56Fe values was observed in the oxidation–reduction transition zone. Three pathways were identified for Fe cycling in shallow groundwater, including dissimilatory reduction of Fe(III) oxides, re-adsorption of Fe(II), and precipitation of pyrite and siderite. Dissimilatory reduction of Fe(III) oxides resulted in light δ56Fe values (around −1.0‰) and high As concentration (>50 μg/L) in groundwater in anoxic conditions. Re-adsorption of isotopically heavy Fe(II) produced by microbially mediated reduction of Fe(III) oxides led to further enrichment of isotopically light Fe in groundwater (up to −3.4‰ of δ56Fe) in anoxic–suboxic conditions. Arsenic re-adsorption was expected to occur along with Fe(II) re-adsorption, decreasing groundwater As concentrations. In strongly reducing conditions, precipitation of isotopically light Fe-pyrite and/or siderite increased groundwater δ56Fe values, reaching +0.58‰ δ56Fe, with a subsequent decrease in As concentrations via co-precipitation. The mixed effect of those pathways would regulate As and Fe cycling in most groundwaters.

Fluid sources and metallogenesis in the Blackbird Co-Cu-Au-Bi-Y-REE district, Idaho, U.S.A.: Insights from major-element and boron isotopic compositions of tourmaline

USGS Publications Warehouse

Trumbull, Robert B.; Slack, John F.; Krienitz, M.-S.; Belkin, Harvey E.; Wiedenbeck, M.

2011-01-01

Tourmaline is a widespread mineral in the Mesoproterozoic Blackbird Co–Cu–Au–Bi–Y–REE district, Idaho, where it occurs in both mineralized zones and wallrocks. We report here major-element and B-isotope compositions of tourmaline from stratabound sulfide deposits and their metasedimentary wallrocks, from mineralized and barren pipes of tourmaline breccia, from late barren quartz veins, and from Mesoproterozoic granite. The tourmalines are aluminous, intermediate in the schorl–dravite series, with Fe/(Fe + Mg) values of 0.30 to 0.85, and 10 to 50% X-site vacancies. Compositional zoning is prominent only in tourmaline from breccias and quartz veins; crystal rims are enriched in Mg, Ca and Ti, and depleted in Fe and Al relative to cores. The chemical composition of tourmaline does not correlate with the presence or absence of mineralization. The δ11B values fall into two groups. Isotopically light tourmaline (−21.7 to −7.6‰) occurs in unmineralized samples from wallrocks, late quartz veins and Mesoproterozoic granite, whereas heavy tourmaline (−6.9 to +3.2‰) is spatially associated with mineralization (stratabound and breccia-hosted), and is also found in barren breccia. At an inferred temperature of 300°C, boron in the hydrothermal fluid associated with mineralization had δ11B values of −3 to +7‰. The high end of this range indicates a marine source of the boron. A likely scenario involves leaching of boron principally from marine carbonate beds or B-bearing evaporites in Mesoproterozoic strata of the region. The δ11B values of the isotopically light tourmaline in the sulfide deposits are attributed to recrystallization during Cretaceous metamorphism, superimposed on a light boron component derived from footwall siliciclastic sediments (e.g., marine clays) during Mesoproterozoic mineralization, and possibly a minor component of light boron from a magmatic–hydrothermal fluid. The metal association of Bi–Be–Y–REE in the Blackbird ores suggests some magmatic input, but involvement of granite-derived fluids cannot be conclusively established from the present database.

Isotopic and Trace Element Compositions of Antarctic Micrometeorites and Comparison with IDPs

NASA Astrophysics Data System (ADS)

Stadermann, F. J.; Olinger, C. T.

1992-07-01

Antarctic micrometeorites (AMMs) show resemblances and differences to both stratospheric interplanetary dust particles (IDPs) and chondritic meteorites, but the exact nature of this relationship has yet to be established. We measured Ne, H, C, and N isotopic compositions, as well as trace element abundances in several AMMs in order to compare the results to similar measurements of IDPs (Stadermann, 1991). AMMs for this study were collected near Cap-Prudhomme (Maurette et al., 1989), and optically selected (Olinger et al., 1990). Noble gases of 23 selected AMMs were extracted through laser vaporization. Nine of these particles contained implanted solar Ne and one showed a clear signature from spallogenic Ne, confirming their extraterrestrial origin. We selected fragments from 6 of these particles, plus 2 containing apparent Ne excess and one with a roughly chondritic bulk chemistry but immeasurably low Ne, for further analyses. Secondary ion mass spectrometry (SIMS) was used to measure the H, C, and N isotopic compositions. These measurements turned out to be difficult, since the concentrations of H and C in the analyzed samples were significantly lower than in IDPs. The low concentration of C also affected the N isotopic measurements because N could only be measured as CN-. We were able to measure H in 9, as well as C and N in 3 AMMs. All measurements yielded isotopically normal results. Previous determinations of the O isotopic compositions of the same samples (Virag, pers. comm.) also gave no indication of isotopic anomalies. These results are significantly different from measurements of IDPs, where isotopic anomalies in H and N were found in roughly 1/2 and 1/3 of the particles, respectively. SIMS was also used to measure the rare earth and trace element abundances in up to 4 different fragments of 6 AMMs. Although most particles had roughly chondritic abundances, anomalous concentrations were found for Ca, Li, Co, Ni, and Ba. Significant Ca depletions up to 0.03 x C1 were observed in 5 out of 6 particles. This effect is well known from IDPs but nonetheless little understood. Enrichments up to 10 x C1 in Li and up to 100 x C1 in Ba were detected in 4 particles each. The Ba enrichment in AMMs has been observed before and can most likely be attributed to terrestrial contamination (Maurette et al., 1992). The origin of the unusual Li enrichment is unknown. Ni was depleted in all analyzed particles and was strongly correlated with Co, whose depletions relative to C1 were always smaller than for Ni. In the particle with the largest Ni-Co depletion, a melted sphere, this effect was accompanied by an Fe depletion. The Fe/Si, Co/Si and Ni/Si ratios relative to C1 were (0.4, 0.06, 0.02). Similar correlated depletions of Fe, Co, and Ni were also found in 2 out of 13 IDPs with otherwise chondritic abundances (Stadermann, 1991). The ratios of their Fe, Co, Ni depletions were (0.2, 0.07, 0.01) and (0.3, 0.03, 0.01), respectively. Interestingly, these 2 IDPs also contained H with isotopically normal composition and C concentrations that were too low for C and N isotopic measurements. One of these particles was a melted spherule. All these similarities suggest that some AMMs and some IDPs may have close relationships, although AMMs and IDPs in general do not represent the same class of extraterrestrial material. Maurette M. et al. (1989) Lunar Planet. Sci. 20, 644-645. Maurette M. et al. (1992) Lunar Planet. Sci. 23, 859-860. Olinger C.T. et al. (1990) Earth Planet. Sci. Lett. 100, 77-93. Stadermann F.J. (1991) Lunar Planet. Sci. 22, 1311-1312.

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

NASA Astrophysics Data System (ADS)

Kavner, Abby; Bonet, François; Shahar, Anat; Simon, Justin; Young, Edward

2005-06-01

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from -0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ 56Fe values (relative to IRMM-14) ranging from -0.18(±0.02) to -2.290(±0.006) ‰, and corresponding δ 57Fe values of -0.247(±0.014) and -3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus's theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.

A FIB/TEM/Nanosims Study of a Wark-Lovering Rim on an Allende CAI

NASA Technical Reports Server (NTRS)

Keller, L. P.; Needham, A. W.; Messenger, S.

2014-01-01

Ca- Al-rich inclusions (CAIs) are commonly surrounded by Wark-Lovering (WL) rims - thin (approx. 50 micrometers) multilayered sequences - whose mineralogy is dominated by high temperature minerals similar to those that occur in the cores of CAIs [1]. The origins of these WL rims involved high temperature events in the early nebula such as condensation, flashheating or reaction with a nebular reservoir, or combinations of these processes. These rims formed after CAI formation but prior to accretion into their parent bodies. We have undertaken a coordinated mineralogical and isotopic study of WL rims to determine the formation conditions of the individual layers and to constrain the isotopic reservoirs they interacted with during their history. We focus here on the spinel layer, the first-formed highest- temperature layer in the WL rim sequence. Results and Discussion: We have performed mineralogical, chemical and isotopic analyses of an unusual ultrarefractory inclusion from the Allende CV3 chondrite (SHAL) consisting of an approx. 500 micrometers long single crystal of hibonite and co-existing coarsegrained perovskite. SHAL is partially surrounded by WL rim. We previously reported on the mineralogy, isotopic compositions and trace elements in SHAL [2-4]. The spinel layer in the WL rim is present only on the hibonite and terminates abruptly at the contact with the coarse perovskite. This simple observation shows that the spinel layer is not a condensate in this case (otherwise spinel would have condensed on the perovskite as well). The spinel layer appears to have formed by gas-phase corrosion of the hibonite by Mg-rich vapors such that the spinel layer grew at the expense of the hibonite. We also found that the spinel layer has the same 16Orich composition as the hibonite. The spinel layer is polycrystalline and individual crystals do not show a crystallographic relationship with the hibonite. An Al-diopside layer overlies the spinel layer, and is present on both the hibonite and perovskite. While the spinel is 16O-rich, WL-rim perovskite and pyroxene are 16O-poor. This isotopic heterogeneity likely reflects O isotopic equilibration of WL-rim perovskite and pyroxene with a planetary O isotopic reservoir after the WL rim formation. The hibonite is zoned and contains wt.% levels of Ti, Mg and Fe in contact with the Fe-bearing spinel (Sp60Hc40) in the WL rim. The Fe enrichment in spinel is likely related to the Na-Fe metasomatism that is ubiquitous in Allende. Conclusions: The petrography and microstructure of the spinel layer in a WL rim sequence shows that it formed by gas phase reactions at high temperature in the nebula. The oxygen isotopic composition of the spinel indicates that this WL rim layer formed in the same (or similar) nebular gas reservoir as the host CAI.

Experimental production of indicators for microbial sulfur metabolism in the Chelyabinsk LL5 chondrite: meteorites as standards for biomarker detection on Mars

NASA Astrophysics Data System (ADS)

Tait, A. W.; Wilson, S. A.; Tomkins, A. G.; Gagen, E. J.; Southam, G.

2016-12-01

One hurdle to finding evidence for life beyond Earth is being able to identify its chemical, textural and isotopic fingerprints. This is a challenge in environments that can mask biomarker discovery and/or where geochemical and mineralogical limits are still being established. An ideal solution would be to use standards with known chemical and isotopic compositions to reduce/remove any ambiguity of detection. We propose that chondritic meteorites are ideal standards. Chondrites have narrow ranges in mineralogical, chemical and isotopic compositions, including δ34S values. As such, they could preserve biomarkers of theorized sulfur-based metabolisms on Mars. Here, we demonstrate that bacteria can alter the chemistry of chondrites in a detectable and recognisable manner. We exposed polished fragments of the Chelyabinsk LL5 chondrite to an inoculum of the sulfur/iron oxidising bacterium, Acidithiobacillus ferrooxidans. Cell counts and aqueous sulfate concentrations were recorded over the course of a month. Meteorite samples were taken after one, two and four week exposures for FEG-SEM and FIB-SEM imaging, XRD phase analysis, and stable isotope (δ34S) geochemistry. Our electron microscopy work shows that bacteria and associated extracellular polymeric substances coat grains of troilite (FeS) and FeNi alloys. Decreasing aqueous sulfate concentrations, compared to increasing sulfate in abiotic controls, suggests that A. ferrooxidans may have been assimilating the sulfur released by oxidation of troilite. Also, low abundances of secondary minerals that are capable of recording biological fractionation of stable sulfur and/or iron isotopes were also produced: rozenite, gypsum, goethite, lepidocrocite, and jarosite, and may explain the reduction in soluble sulfur. Our FIB-SEM results show that nutrients (e.g., carbon, sulfur and nitrogen) become concentrated in layers at the surfaces of troilite and FeNi alloys within 1 week of incubation. These nutrient-rich regions are encased and preserved beneath mm-scale efflorescences of Fe-oxyhydroxide minerals, essentially fossilizing them. Meteorites that have landed on the surface of Mars are therefore favourable targets for future sample return missions, because they can record unambiguous evidence of a putative biosphere in multiple ways.

A IAB-Complex Iron Meteorite Containing Low-Ca Clinopyroxene: Northwest Africa 468 and its Relationship to Iodranites and Formation by Impact Melting

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.

2002-01-01

Northwest Africa 468 (NWA 468) is a new ungrouped, silicate-rich member of the IAB complex of nonmagmatic iron meteorites. The silicates contain relatively coarse (approximately 300 micron-size) grains of low-Ca clinopyroxene with polysynthetic twinning and inclined extinction. Low-Ca clinopyroxene is indicative of quenching from high temperatures (either from protoenstatite in a few seconds or high-temperature clinoenstatite in a few hours). It seems likely that NWA 468 formed by impact melting followed by rapid cooling to less than or equal to 660 C. After the loss of a metal-sulfide melt from the silicates, sulfide was reintroduced, either from impact-mobilized FeS or as an S2 vapor that combined with metallic Fe to produce FeS. The O-isotopic composition (delta O-17 = -1.39 %) indicates that the precursor material of NWA 468 was a metal-rich (e.g., CR) carbonaceous chondrite. Lodranites are similar in bulk chemical and O-isotopic composition to the silicates in NWA 468; the MAC 88177 lodranite (which also contains low-Ca clinopyroxene) is close in bulk chemical composition. Both NWA 468 and MAC 88177 have relatively low abundances of REE (rare earth elements) and plagiophile elements. Siderophiles in the metal-rich areas of NWA 468 are similar to those in the MAC 88177 whole rock; both samples contain low Ir and relatively high Fe, Cu and Se. Most unweathered lodranites contain approximately 20 - 38 wt. % metallic Fe-Ni. These rocks may have formed in an analogous manner to NWA 468 (i.e., by impact melting of metal-rich carbonaceous-chondrite precursors) but with less separation of metal-rich melts from silicates.

Influence of redox fluctuations and rainfall on pedogenic iron alteration and soil magnetic properties (Invited)

NASA Astrophysics Data System (ADS)

Thompson, A.; Rancourt, D.; Chadwick, O.; Chorover, J. D.

2009-12-01

Soil iron mineral composition emerges from a dynamic interplay between processes causing selective mineral addition/removal (both physically and chemically-driven) and processes affecting in situ mineral transformation. Discerning the influence of these pedogenic processes in a temporally integrated manner is fundamentally relevant to many biogeochemical questions. Among them is to what extent the Fe-mineral system can be used to constrain paleo-interpretations of oceanic sediments and geological deposits. Here we describe results from field and laboratory experiments designed to explore the effects of variable redox conditions on soil iron mineral transformation. Our experimental systems include: (1) a climate gradient of basaltic soils from the island of Maui, HI (MCG) with a documented decrease in Eh. and (2) laboratory incubations where we subjected soil slurries to a series of bacterially-driven reduction-oxidation cycles. Our prior work in these systems examining the iron isotopic and mineral composition will be combined with in-progress analysis of magnetic susceptibility. Current results indicate that across the field gradient (MCG) we find average increases of 0.56‰±0.09‰ δ56Fe for the surface and subsurface soils that correlate very well (R2=0.88) with 57Fe Mössbauer-determined Fe-oxyhydroxide fraction. Such a correlation is difficult to explain on the basis of strict parameter co-variation with rainfall, and suggests isotopic and mineral composition may be coupled through in situ mineral transformation processes in these soils. In our soil slurry incubation experiments we reported previously that repeated redox oscillations generate a cumulative increase in Fe mineral crystallinity. Integration of these results with magnetic susceptibility measurements will provide the context for discussing how dynamic redox processes alter soil magnetic properties most often drawn on for paleoclimate interpretations.

Petrology of Anomalous Mafic Achondrite Polymict Breccia Pasamonte

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Berger, E. L.; Le, L.

2017-01-01

The most common asteroidal igneous meteorites are eucrite-type basalts and gabbros - rocks composed of ferroan pigeonite and augite, calcic plagioclase, silica, ilmenite, troilite, Ca-phosphate, chromite and Fe-metal [1]. These rocks are thought to have formed on a single asteroid, widely considered to be 4 Vesta, along with howardites and diogenites [1, 2]. High precision O-isotopic analyses have shown that some eucrites have small, well-resolved O-isotopic differences from the group mean [3-5]. These Oanomalous eucrites are thought to hail from asteroidal parents that are distinct from that of eucrites [5]. Three O-anomalous eucrites are PCA 82502, PCA 91007 (paired) and Pasamonte, all of which have the same O-isotopic composition [5, 6]. Our petrologic studies have shown that PCA 82502 and PCA 91007 have well-resolved anomalies in low-Ca pyroxene Fe/Mn compared to eucrites [6]. Divalent Mn and Fe are homologous species that do not greatly fractionate during igneous processes; mafic mineral Fe/Mn can be used to fingerprint parent object sources [7]. Previous petrological studies of Pasamonte [8-10] have not yielded sufficiently precise Fe/Mn ratios to allow distinction of anomalies of the scale of those found for the PCA basalts. We have begun petrological study of Pasamonte for comparison with our results on normal and anomalous eucrites [6], and to constrain its origin.

Abiologic silicon isotope fractionation between aqueous Si and Fe(III)-Si gel in simulated Archean seawater: Implications for Si isotope records in Precambrian sedimentary rocks

NASA Astrophysics Data System (ADS)

Zheng, Xin-Yuan; Beard, Brian L.; Reddy, Thiruchelvi R.; Roden, Eric E.; Johnson, Clark M.

2016-08-01

Precambrian Si-rich sedimentary rocks, including cherts and banded iron formations (BIFs), record a >7‰ spread in 30Si/28Si ratios (δ30Si values), yet interpretation of this large variability has been hindered by the paucity of data on Si isotope exchange kinetics and equilibrium fractionation factors in systems that are pertinent to Precambrian marine conditions. Using the three-isotope method and an enriched 29Si tracer, a series of experiments were conducted to constrain Si isotope exchange kinetics and fractionation factors between amorphous Fe(III)-Si gel, a likely precursor to Precambrian jaspers and BIFs, and aqueous Si in artificial Archean seawater under anoxic conditions. Experiments were conducted at room temperature, and in the presence and absence of aqueous Fe(II) (Fe(II)aq). Results of this study demonstrate that Si solubility is significantly lower for Fe-Si gel than that of amorphous Si, indicating that seawater Si concentrations in the Precambrian may have been lower than previous estimates. The experiments reached ∼70-90% Si isotope exchange after a period of 53-126 days, and the highest extents of exchange were obtained where Fe(II)aq was present, suggesting that Fe(II)-Fe(III) electron-transfer and atom-exchange reactions catalyze Si isotope exchange through breakage of Fe-Si bonds. All experiments except one showed little change in the instantaneous solid-aqueous Si isotope fractionation factor with time, allowing extraction of equilibrium Si isotope fractionation factors through extrapolation to 100% isotope exchange. The equilibrium 30Si/28Si fractionation between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -2.30 ± 0.25‰ (2σ) in the absence of Fe(II)aq. In the case where Fe(II)aq was present, which resulted in addition of ∼10% Fe(II) in the final solid, creating a mixed Fe(II)-Fe(III) Si gel, the equilibrium fractionation between Fe(II)-Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -3.23 ± 0.37‰ (2σ). Equilibrium Si isotope fractionation for Fe-Si gel systems is significantly larger in magnitude than estimates of a near-zero solid-aqueous fractionation factor between pure Si gel and aqueous Si, indicating a major influence of Fe atoms on Si-O bonds, and hence the isotopic properties, of Fe-Si gel. Larger Si isotope fractionation in the Fe(II)-bearing systems may be caused by incorporation of Fe(II) into the solid structure, which may further weaken Fe-Si bonds and thus change the Si isotope fractionation factor. The relatively large Si isotope fractionation for Fe-Si gel, relative to pure Si gel, provides a new explanation for the observed contrast in δ30Si values in the Precambrian BIFs and cherts, as well as an explanation for the relatively negative δ30Si values in BIFs, in contrast to previous proposals that the more negative δ30Si values in BIFs reflect hydrothermal sources of Si or sorption to Fe oxides/hydroxides.

Chemistry and Ni-isotope composition of ureilites and their components

NASA Astrophysics Data System (ADS)

Gabriel, A. D.; Quitté, G.; Pack, A.

2008-09-01

Ureilites are olivine-pigeonite bearing achondrites with interstitial carbonaceous material and metal. The latter is present as <1 μm metal inclusions in reduced rims of silicate grains, 5-20 μm spherical inclusions in clear silicate grains, and in association with interstitial carbonaceous material. We have studied the composition of metal and silicates in 9 ureilites with a fayalite content of Fa2 to Fa21. Vein metal contains 3.7 to 5.4 wt% Ni and 0.35 to 0.54 wt% Co. Cobalt and Ni contents in vein metal and fayalite in olivine do not correlate. Mass balance calculations assuming a chondritic parent body yield a metal core with 7 to 11 wt% Ni and 0.3 to 0.55 wt% Co. Thermodynamic calculations of Fe-Ni and Fe-Co exchange between olivine and vein metal show that vein metal cannot be in equilibrium with the olivine at any temperature. We conclude that the vein metal is genetically not linked to the ureilite olivine and may have been injected into the parent body by an impactor. Recently published data show a deficit in 60Ni of - 0.24+/-0.02 ɛ-units for various achondrites including ureilites [1]. This has been interpreted as evidence for a late injection of 60Fe after formation of these achondrites. However, our chemical data for vein metal, which is the dominant Ni host in ureilites, demonstrate that bulk Ni isotope data have little meaning with respect to the formation of ureilite silicates. In this work we present Ni isotope data for bulk samples but also vein material and the silicate phase of 4 ureilites (ALHA77257, EET87157, EET96041, Kenna). Bulk ureilites have a ɛ60 between -0.05+/-0.12 and 0.08+/-0.12; the vein metal gives ɛ60 = -0.05+/-0.13 to 0.11+/-0.16. No resolvable deficit in ɛ60 was found, in disagreement with results reported in Bizzarro et al. (2007). The vein material and the bulk samples have, within uncertainty, the same isotopic composition, confirming that the global Ni budget is controlled by the vein material. In ureilite silicates ɛ60 varies from -0.77+/-0.31 to -0.12+/-0.21. Due to the high Fe/Ni ratio of silicates, clear excesses of 60Ni (at least several ɛ-units) are expected if they formed early in the solar system. This is not observed. There is thus no evidence for life 60Fe in ureilites, which may be interpreted in different ways: either 60Fe was injected at a later time into the protoplanetary disk as suggested by [1] (but this is difficult to reconcile with data obtained in other meteorites [2]), or several isotopically distinct reservoirs co-existed at the beginning of the solar system. The isotopic difference between vein material and silicates rather supports the second hypothesis, even if further studies are required to confirm it. It may also be that the Fe-Ni system has been disturbed at a later stage after formation of ureilites. References [1] Bizzarro M. et al. 2007. Science 316 (5828), 1178- 1181. [2] Quitté G. et al. 2007. LPSC 38, abstract #1900.

Iron Isotopic Fractionation in Igneous Systems: Looking for Anharmonicity

NASA Astrophysics Data System (ADS)

Dauphas, N.; Roskosz, M.; Hu, M. Y.; Neuville, D. R.; Alp, E. E.; Hu, J.; Heard, A.; Zhao, J.

2017-12-01

Igneous rocks display variations in their Fe isotopic compositions that can be used to trace partial melting, magma differentiation, the origin of mineral zoning, and metasomatic processes. While tremendous progress has been made in our understanding of how iron isotopes can be fractionated at equilibrium or during diffusion, significant work remains to be done to establish equilibrium fractionation factors between phases relevant to igneous petrology. A virtue of iron isotope systematics is that iron possesses a Mössbauer isotope, 57Fe, and one can use the method of NRIXS to measure the force constant of iron bonds, from which beta-factors can be calculated. These measurements are done at a few synchrotron beamlines around the world, such as sector 3ID of the APS (Argonne). Tremendous insights have already been gained by applying this technique to Earth science materials. It was shown for instance that significant equilibrium fractionation exists between Fe2+ and Fe3+ at magmatic temperature, that the iron isotopic fractionation resulting from core formation must be small, and that iron isotopic fractionation is influenced by the polymerization of the melt. Combining NRIXS and ab initio studies, there are approximately 130 geologically-relevant solids and aqueous species for which beta-factors have been reported. A potential limitation of applying published NRIXS data to igneous petrology is that all the force constants have been measured at room temperature and the beta-factors are extrapolated to magmatic temperatures assuming that the systems are harmonic, which has never been demonstrated. One way to test this critical assumption is to measure the apparent force constant of iron bonds at various temperatures, so that the interatomic potential of iron bonds can be probed. A further virtue of NRIXS is that the data also allows us to derive the mean square displacement. If significant anharmonicity is present, it should be manifested as a decrease in the apparent force constant with increasing temperature and increasing mean square displacement. We have measured the Fe force constant of basalt glass and olivine using a wire furnace. At the conference, we will report on these experiments and will discuss some implications for igneous petrology.

Linking Specific Heterotrophic Bacterial Populations to Bioreduction of Uranium and Nitrate in Contaminated Subsurface Sediments by Using Stable Isotope Probing▿†

PubMed Central

Akob, Denise M.; Kerkhof, Lee; Küsel, Kirsten; Watson, David B.; Palumbo, Anthony V.; Kostka, Joel E.

2011-01-01

Shifts in terminal electron-accepting processes during biostimulation of uranium-contaminated sediments were linked to the composition of stimulated microbial populations using DNA-based stable isotope probing. Nitrate reduction preceded U(VI) and Fe(III) reduction in [13C]ethanol-amended microcosms. The predominant, active denitrifying microbial groups were identified as members of the Betaproteobacteria, whereas Actinobacteria dominated under metal-reducing conditions. PMID:21948831

Petrologic and Oxygen-Isotopic Investigations of Eucritic and Anomalous Mafic Achondrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Greenwood, R. C.; Peng, Z. X.; Ross, D. K.; Berger, E. L.; Barrett, T. J.

2016-01-01

The most common asteroidal igneous meteorites are eucrite-type basalts and gabbros rocks composed of ferroan pigeonite and augite, calcic plagioclase, silica, ilmenite, troilite, Ca-phosphate, chromite and Fe-metal. These rocks are thought to have formed on a single asteroid along with howardites and diogenites (HEDs). However, Northwest Africa (NWA) 011 is mineralogically identical to eucrites, but has an O-isotopic composition distinct from them and was derived from a different asteroid. Modern analyses with higher precision have shown that some eucrites have smaller O-isotopic differences that are nevertheless well-resolved from the group mean.

Zinc isotope anomalies. [in Allende meteorite

NASA Technical Reports Server (NTRS)

Volkening, J.; Papanastassiou, D. A.

1990-01-01

The Zn isotope composition in refractory-element-rich inclusions of the Allende meteorite are determined. Typical inclusions contain normal Zn. A unique inclusion of the Allende meteorite shows an excess for Zn-66 of 16.7 + or - 3.7 eu (1 eu = 0.01 percent) and a deficit for Zn-70 of 21 + or - 13 eu. These results indicate the preservation of exotic components even for volatile elements in this inclusion. The observed excess Zn-66 correlates with excesses for the neutron-rich isotopes of Ca-48, Ti-50, Cr-54, and Fe-58 in the same inclusion.

Iron isotope effect in the iron arsenide superconductor (Ca0.4Na0.6)Fe2As2

NASA Astrophysics Data System (ADS)

Tsuge, Y.; Nishio, T.; Iyo, A.; Tanaka, Y.; Eisaki, H.

2014-05-01

We report a new sample synthesis technique for polycrystalline (Ca1-xNax)Fe2As2 (0

Absolute measurements and certified reference material for iron isotopes using multiple-collector inductively coupled mass spectrometry.

PubMed

Zhou, Tao; Zhao, Motian; Wang, Jun; Lu, Hai

2008-01-01

Two enriched isotopes, 99.94 at.% 56Fe and 99.90 at.% 54Fe, were blended under gravimetric control to prepare ten synthetic isotope samples whose 56Fe isotope abundances ranged from 95% to 20%. For multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements typical polyatomic interferences were removed by using Ar and H2 as collision gas and operating the MC-ICP-MS system in soft mode. Thus high-precision measurements of the Fe isotope abundance ratios were accomplished. Based on the measurement of the synthetic isotope abundance ratios by MC-ICP-MS, the correction factor for mass discrimination was calculated and the results were in agreement with results from IRMM014. The precision of all ten correction factors was 0.044%, indicating a good linearity of the MC-ICP-MS method for different isotope abundance ratio values. An isotopic reference material was certified under the same conditions as the instrument was calibrated. The uncertainties of ten correction factors K were calculated and the final extended uncertainties of the isotopic certified Fe reference material were 5.8363(37) at.% 54Fe, 91.7621(51) at.% 56Fe, 2.1219(23) at.% 57Fe, and 0.2797(32) at.% 58Fe.

Nature and geodynamic setting of the protoliths of the UHP metamorphic Complex and migmatites in Bixiling area, the Dabie Orogen, China

NASA Astrophysics Data System (ADS)

Li, H.; Jahn, B.; Wang, D.; Yu, H.; Liu, Z.; Hou, G.

2013-12-01

As the largest coesite-bearing mafic-ultramafic body in the Dabie-Sulu orogen, the Bixiling Complex is composed of meta-ultramafic rocks, MgAl-rich eclogites and FeTi-rich eclogites. The FeTi-rich eclogites are further divided into low-Si-high-Fe type (Type I) and high-Si-low-Fe type (Type II) according to their mineral assemblages and bulk chemical composition. Field, petrographic, petrological and geochemical characteristics of these rocks, although suffered an ultra-high pressure metamorphism, still show a magmatic differentiation process among the protoliths of the meta-ultramafic rocks, MgAl-rich eclogites and Type I FeTi-rich eclogites. A small degree of lower crustal contamination occurred during their magma chamber process. Amphibolite is widespread in the periphery of the complex. Non-foliation and fine-grained texture are their obvious characteristics. Geochemical and isotopic affinities suggest that the amphibolites represent a product of complete retrogression from type II FeTi-rich eclogites. The UHP complex is enclosed in granitic gneisses, which variably include two-mica plagioclase gneiss, epidote two-mica plagioclase gneiss, or white-mica plagioclase gneiss. They all show TTG, especially trondjhemitic composition. A migmatite outcrop was found near the northeastern end of the complex. The migmatites consist of dark colored, non-foliated amphibolites and light-colored, fine-grained trondhjemitic gneisses. Field occurrences, microstructures observed under optical microscope and SEM, Sr-Nd isotopic data suggest an origin of partial melting. Chemical composition of two stages of amphiboles occurred in both the amphibolites and the trondhjemitic gneisses also imply a partial melting process occurred. Trace element, Sr-Nd isotope and SHRIMP zircon U-Pb dating of MgAl-rich eclogite, amphibolites and trondhjemite suggest that the migmatites represent a partial melting of crustal materials at about 780Ma, possibly accompanied by the coeval emplacement of a differentiated mafic intrusive body. These rocks were deeply subducted into a mantle depth during the Triassic continental collision between the Yangtze Craton and North China Craton, and thereafter were exhumed to the surface. Their residual geochemical characteristics and spatial / temporal relationship could impose constraints on the tectonic evolution of the Dabieshan UHP terrane.

Ferropericlase inclusions in ultradeep diamonds from Sao Luiz (Brazil): high Li abundances and diverse Li-isotope and trace element compositions suggest an origin from a subduction mélange

NASA Astrophysics Data System (ADS)

Seitz, Hans-Michael; Brey, Gerhard P.; Harris, Jeffrey W.; Durali-Müller, Soodabeh; Ludwig, Thomas; Höfer, Heidi E.

2018-05-01

The most remarkable feature of the inclusion suite in ultradeep alluvial and kimberlitic diamonds from Sao Luiz (Juina area in Brazil) is the enormous range in Mg# [100xMg/(Mg + Fe)] of the ferropericlases (fper). The Mg-richer ferropericlases are from the boundary to the lower mantle or from the lower mantle itself when they coexist with ringwoodite or Mg- perovskite (bridgmanite). This, however, is not an explanation for the more Fe-rich members and a lowermost mantle or a "D" layer origin has been proposed for them. Such a suggested ultra-deep origin separates the Fe-rich fper-bearing diamonds from the rest of the Sao Luiz ultradeep diamond inclusion suite, which also contains Ca-rich phases. These are now thought to have an origin in the uppermost lower mantle and in the transition zone and to belong either to a peridotitic or mafic (subducted oceanic crust) protolith lithology. We analysed a new set of more Fe-rich ferropericlase inclusions from 10 Sao Luiz ultradeep alluvial diamonds for their Li isotope composition by solution MC-ICP-MS (multi collector inductively coupled plasma mass spectrometry), their major and minor elements by EPMA (electron probe micro-analyser) and their Li-contents by SIMS (secondary ion mass spectrometry), with the aim to understand the origin of the ferropericlase protoliths. Our new data confirm the wide range of ferropericlase Mg# that were reported before and augment the known lack of correlation between major and minor elements. Four pooled ferropericlase inclusions from four diamonds provided sufficient material to determine for the first time their Li isotope composition, which ranges from δ7Li + 9.6 ‰ to -3.9 ‰. This wide Li isotopic range encompasses that of serpentinized ocean floor peridotites including rodingites and ophicarbonates, fresh and altered MORB (mid ocean ridge basalt), seafloor sediments and of eclogites. This large range in Li isotopic composition, up to 5 times higher than `primitive upper mantle' Li-abundances, and an extremely large and incoherent range in Mg# and Cr, Ni, Mn, Na contents in the ferropericlase inclusions suggests that their protoliths were members of the above lithologies. This mélange of altered rocks originally contained a variety of carbonates (calcite, magnesite, dolomite, siderite) and brucite as the secondary products in veins and as patches and Ca-rich members like rodingites and ophicarbonates. Dehydration and redox reactions during or after deep subduction into the transition zone and the upper parts of the lower mantle led to the formation of diamond and ferropericlase inclusions with variable compositions and a predominance of the Ca-rich, high-pressure silicate inclusions. We suggest that the latter originated from peridotites, mafic rocks and sedimentary rocks as redox products between calcite and SiO2.

Carbon isotopic composition and origin of SiC from kimberlites of Yakutia, Russia

NASA Astrophysics Data System (ADS)

Mathez, E. A.; Fogel, R. A.; Hutcheon, I. D.; Marshintsev, V. K.

1995-02-01

The stability of moissanite (SiC) has been computed for upper mantle conditions using the internally optimized thermodynamic dataset for the MgSiO compounds of Fei et al. (1990). The computations consider the effects of pressure and temperature on the elastic properties of phases involved in the reactions. The maximum stability of moissanite throughout the upper mantle is typically five to six orders of magnitude lower in oxygen fugacity ( fO2) than the Fe metal-wüstite oxygen buffer at equivalent temperature and pressure, in agreement with previous calculations. Under conditions of SiC stability, silicates will be Fe-free, Fe metal will contain substantial amounts of Si but little C in solution, and Mg-rich sulfides will be stable. Moissanite from the heavy mineral concentrate of the Mir and Aikhal kimberlite pipes, Yakutia, has been studied. Moissanite crystals are gemmy and vary in color from a characteristic blue-green to pale green to nearly colorless to blue-black. Most exhibit crystallographic faces and are in the size range 0.5 to 1 mm in long dimension. Their compositions include small quantities of Fe, which is ubiquitous, Al, Ca, V, Cr, and Mn, all of which may be present in concentrations > 100 ppmwt. Mineral inclusions are present in some crystals. Silicon metal is the most common; inclusions of ferrosilicite (Fe 3Si 7), FeTi silicides, REE silicate, and sinoite (Si 2N 2O) have also been observed. The carbon isotopic compositions of individual moissanite grains have been determined by ion microprobe. The nine analyzed crystals from Aikhal and fourteen from Mir are characterized by a narrow range in δ 13C values of -22 to -29‰; the majority of crystals fall within a more restricted range of -24 to -27‰. Two grains were analyzed for N and found to have a δ 15N of +9.7 ± 4.0 and +5.6 ± 2.0‰. Five mechanisms for the formation of moissanite are considered. Moissanite may be a relict of a reduced, primordial Earth and now present only as a trace phase in an otherwise oxidized mantle. Alternatively, there may be present-day global regions of the Earth that are both highly reduced and characterized by light carbon isotopic compositions. Although these possiblities cannot be disproved, they are not supported by observations. Two other possibilities, namely that moissanite stability extends to more oxidized conditions at pressures of the lower mantle or that it may form metastably, cannot be evaluated with present knowledge. The possibility most consistent with, although not proven by, the isotopic data is that moissanite formed by metamorphism of reduced, carbonaceous sediments during subduction.

Fe Isotope Fractionation During Fe(III) Reduction to Fe(II)

NASA Astrophysics Data System (ADS)

Baker, E. A.; Greene, S.; Hardin, E. E.; Hodierne, C. E.; Rosenberg, A.; John, S.

2014-12-01

The redox chemistry of Fe(III) and Fe(II) is tied to a variety of earth processes, including biological, chemical, or photochemical reduction of Fe(III) to Fe(II). Each process may fractionate Fe isotopes, but the magnitudes of the kinetic isotope effects have not been greatly explored in laboratory conditions. Here, we present the isotopic fractionation of Fe during reduction experiments under a variety of experimental conditions including photochemical reduction of Fe(III) bound to EDTA or glucaric acid, and chemical reduction of Fe-EDTA by sodium dithionite, hydroxylamine hydrochloride, Mn(II), and ascorbic acid. A variety of temperatures and pHs were tested. In all experiments, Fe(III) bound to an organic ligand was reduced in the presence of ferrozine. Ferrozine binds with Fe(II), forming a purple complex which allows us to measure the extent of reaction. The absorbance of the experimental solutions was measured over time to determine the Fe(II)-ferrozine concentration and thus the reduction rate. After about 5% of the Fe(III) was reduced, Fe(III)-EDTA and Fe(II)-ferrozine were separated using a C-18 column to which Fe(II)-ferrozine binds. The Fe(II) was eluted and purified through anion exchange chromatography for analysis of δ56Fe by MC-ICPMS. Preliminary results show that temperature and pH both affect reduction rate. All chemical reductants tested reduce Fe(III) at a greater rate as temperature increases. The photochemical reductant EDTA reduces Fe(III) at a greater rate under more acidic conditions. Comparison of the two photochemical reductants shows that glucaric acid reduces Fe(III) significantly faster than EDTA. For chemical reduction, the magnitude of isotopic fractionation depends on the reductant used. Temperature and pH also affect the isotopic fractionation of Fe. Experiments using chemical reductants show that an increase in temperature at low temperatures produces lighter 56Fe ratios, while at high temperatures some reductants produce heavier 56Fe ratios. The magnitude of isotope fractionation is not related to the reduction rate generalized over all reductants. The measured isotopic fractionations produce δ56Fe from -3.82 to +3.05 across all of the reductants tested, highlighting the large impact that redox chemistry may have on fractionating Fe isotopes in the environment.

Tracing dust transport from Middle-East over Delhi in March 2012 using metal and lead isotope composition

NASA Astrophysics Data System (ADS)

Kumar, S.; Aggarwal, S. G.; Malherbe, J.; Barre, J. P. G.; Berail, S.; Gupta, P. K.; Donard, O. F. X.

2016-05-01

A severe dust-storm which was originated in Middle-East crossed over Delhi during March 20-22, 2012. We have collected these dust-storm (DS) aerosol samples, and analyzed them for selected metals (As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, Se, Sn, Sr, V and Zn) together with after dust-storm (ADS) and winter (WS) samples. High aerosol mass loadings were observed in DS samples (1097-1965 μg/m3). On the contrary, metals derived prominently from the anthropogenic sources were found lower in concentration compared to that of ADS and WS aerosols. We observed significantly high concentrations of Ni and V (which are abundantly found in crude oils of Middle-East origin) in the DS samples than that of ADS and WS samples. Also enrichment factor (EF) of these metals with respect to Fe shows no significant enrichment (<10). Fe (and Sr) concentrations were also 3-5 fold higher in DS samples compared to ADS and WS. These results suggest that Ni and V can be used as tracers for dust aerosols transported from Middle-East region. Lead isotope signatures can tell about the variation in the sources of urban aerosols. Therefore Pb isotope analyses of these samples were performed using MC-ICP-MS. The isotope ratios, 208Pb/206Pb is determined to be (mean ± sd) 2.1315 ± 0.0018, 2.1370 ± 0.0022 and 2.1389 ± 0.0016, whereas 206Pb/207Pb is 1.1311 ± 0.0022, 1.1244 ± 0.0017 and 1.1233 ± 0.0016 in DS, ADS and WS aerosols, respectively. There is a clear distinction in Pb isotope composition between DS and urban (ADS and WS) aerosols. Further, these results suggest that in urban aerosols, Pb is less radiogenic in nature compared to that of in transported dust aerosols collected in New Delhi.

Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

NASA Technical Reports Server (NTRS)

Baur, M. E.; Hayes, J. M.; Studley, S. A.; Walter, M. R.

1985-01-01

Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

USGS Publications Warehouse

Borrok, D.M.; Wanty, R.B.; Ian, Ridley W.; Lamothe, P.J.; Kimball, B.A.; Verplanck, P.L.; Runkel, R.L.

2009-01-01

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, ??56Fe and ??66Zn isotopic signatures of filtered stream water samples varied by ???3.5??? and 0.4???, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in ??56Fe were linked to redox and precipitation reactions occurring in the stream, while changes in ??66Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<-2.0???) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4???). Acidic drainage from mine wastes contributed heavier dissolved Fe (???+0.5???) and lighter Zn (???+0.2???) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe (??56Fe ??? 0???) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds. ?? 2009 Elsevier Ltd.

Oxygen-isotopic Compositions of Low-FeO relicts in High-FeO Host Chondrules in Acfer 094, a Type 3.0 Carbonaceous Chondrite Closely Related to CM

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Kunihiro, Tak; Wasson, John T.

2006-01-01

With one exception, the low-FeO relict olivine grains within high-FeO porphyritic chondrules in the type 3.0 Acfer 094 carbonaceous chondrite have DELTA O-17 ( = delta O-17 - 0.52 X delta O-18) values that are substantially more negative than those of the high-FeO olivine host materials. These results are similar to observations made earlier on chondrules in C03.0 chondrites and are consistent with two independent models: (1) Nebular solids evolved from low-FeO, low-DELTA O-17 compositions towards high-FeO, more positive DELTA O-17 compositions; and (2) the range of compositions resulted from the mixing of two independently formed components. The two models predict different trajectories on a DELTA O-17 vs. log Fe/Mg (olivine) diagram, but our sample set has too few values at intermediate Fe/Mg ratios to yield a definitive answer. Published data showing that Acfer 094 has higher volatile contents than CO chondrites suggest a closer link to CM chondrites. This is consistent with the high modal matrix abundance in Acfer 094 (49 vol.%). Acfer 094 may be an unaltered CM chondrite or an exceptionally matrix-rich CO chondrite. Chondrules in Acfer 094 and in CO and CM carbonaceous chondrites appear to sample the same population. Textural differences between Acfer 094 and CM chondrites are largely attributable to the high degree of hydrothermal alteration that the CM chondrites experienced in an asteroidal setting.

Magnesium Isotopic Compositions of Continental Basalts From Various Tectonic Settings

NASA Astrophysics Data System (ADS)

Yang, W.; Li, S.; Tian, H.; Ke, S.

2016-12-01

Recycled sedimentary carbonate through subduction is the main light Mg isotopic reservoir in Earth's deep interior, thus Mg isotopic variation of mantle-derived melts provides a fresh perspective on investigating deep carbon cycling. Here we investigate Mg isotopic compositions of continental basalts from various tectonic settings: (1) The Cenozoic basalts from eastern China, coinciding with the stagnant Pacific slab in the mantle transition zone revealed by seismic tomography; (2) The Cenozoic basalts from Tengchong area, southwestern China, which comprises a crucial part of the collision zone between the Indian and Eurasian plates; (3) The Permian basalts from Emeishan large igneous province, related to a mantle plume. The Cenozoic basalts from both eastern China and Tengchong area exhibit light Mg isotopic compositions (δ26Mg = -0.60 to -0.30‰ and -0.51 to -0.33‰), suggesting recycled sedimentary carbonates in their mantle sources. This is supported by their low Fe/Mn, high CaO/Al2O3, low Hf/Hf* and low Ti/Ti* ratios, which are typical features of carbonated peridotite-derived melt. The Tengchong basalts also show high 87Sr/86Sr, high radiogenic Pb and upper crustal-like trace element pattern, indicating contribution of recycled continental crustal materials. By contrast, all Emeishan basalts display a mantle-like Mg isotopic composition, with δ26Mg ranging from -0.35 to -0.19‰. Since the Emeishan basalts derived from a mantle plume, their mantle-like Mg isotopic composition may indicate limited sedimentary carbonated recycled into the lower mantle. This is consistent with a recent experimental study which concluded that direct recycling of carbon into the lower mantle may have been highly restricted throughout most of the Earth's history.

Workshop on Oxygen in the Terrestrial Planets

NASA Technical Reports Server (NTRS)

2004-01-01

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe Oxidation State of Vanadium in Spinel-Melt Pairs; 44) Testing the Magma Ocean Hypothesis Using Metal-Silicate Partitioning of Te, Se and S; 45) Solubility of Oxygen in Liquid Iron at High Pressure and Consequences for the Early Differentiation of Earth and Mars Metallic Liquid Segregation in Planetesimals; 46) Oxygen Fugacity of Lunar Basalts and the Lunar Mantle. Range of fo2 and the Effectiveness of Oxybarometers; 47) Thermodynamic Study of Dissociation Processes of Molecular Oxygen in Vapor over Oxide Compounds; 48) Oxygen Profile of a Thermo-Haliophilic Community in the Badwater Salt Flat; 49) Oxygen Barometry Using Synchrotron MicroXANES of Vanadium; 50) Mass-Independent Isotopic Fractionation of Sulfur from Sulfides in the Huronian Supergroup, Canada; 51) Mass Independent Isotopes and Applications to Planetary Atmospheres; 52) Electrical Conductivity, Oxygen Fugacity, and Mantle Materials; 53) Crustal Evolution and Maturation on Earth: Oxygen Isotope Evidence; 54) The Oxygen Isotope Composition of the Moon: Implications for Planet Formation; 55) Oxygen Isotope Composition of Eucrites and Implications for the Formation of Crust on the HED Parent Body; and 56) The Role of Water in Determining the Oxygen Isotopic Composition of Planets.

Isotopic evolution of Mauna Kea volcano: Results from the initial phase of the Hawaii Scientific Drilling Project

USGS Publications Warehouse

Lassiter, J.C.; DePaolo, D.J.; Tatsumoto, M.

1996-01-01

We have examined the Sr, Nd, and Pb isotopic compositions of Mauna Kea lavas recovered by the first drilling phase of the Hawaii Scientific Drilling Project. These lavas, which range in age from ???200 to 400 ka, provide a detailed record of chemical and isotopic changes in basalt composition during the shied/postshield transition and extend our record of Mauna Kea volcanism to a late-shield period roughly equivalent to the last ???100 ka of Mauna Loa activity. Stratigraphic variations in isotopic composition reveal a gradual shift over time toward a more depleted source composition (e.g., higher 143Nd/144Nd, lower 87Sr/86Sr, and lower 3He/4He). This gradual evolution is in sharp contrast with the abrupt appearance of alkalic lavas at ???240 ka recorded by the upper 50 m of Mauna Kea lavas from the core. Intercalated tholeiitic and alkalic lavas from the uppermost Mauna Kea section are isotopically indistinguishable. Combined with major element evidence (e.g., decreasing SiO2 and increasing FeO) that the depth of melt segregation increased during the transition from tholeiitic to alkalic volcanism, the isotopic similarity of tholeiitic and alkalic lavas argues against significant lithosphere involvement during melt generation. Instead, the depleted isotopic signatures found in late shield-stage lavas are best explained by increasing the proportion of melt generated from a depleted upper mantle component entrained and heated by the rising central plume. Direct comparison of Mauna Kea and Mauna Loa lavas erupted at equivalent stages in these volcanoes' life cycles reveals persistent chemical and isotopic differences independent of the temporal evolution of each volcano. The oldest lavas recovered from the drillcore are similar to modern Kilauea lavas, but are distinct from Mauna Loa lavas. Mauna Kea lavas have higher 143Nd/144Nd and 206Pb/204Pb and lower 87Sr/86Sr. Higher concentrations of incompatible trace elements in primary magmas, lower SiO2, and higher FeO also indicate that Mauna Kea lavas formed through smaller degrees of partial melting at greater depth than Mauna Loa lavas. These chemical and isotopic differences are consistently found between volcanoes along the western "Loa" and eastern "Kea" trends and reflect large-scale variations in source composition and melting environment. We propose a simple model of a radially zoned plume centered beneath the Loa trend. Loa trend lavas generated from the hot plume axis reflect high degrees of partial melting from a source containing a mixture of enriched plume-source material and entrained lower mantle. Kea trend lavas, in contrast, are generated from the cooler, peripheral portions of the plume, record lower degrees of partial melting, and tap a source containing a greater proportion of depleted upper mantle.

Intracellular Cadmium Isotope Fractionation

NASA Astrophysics Data System (ADS)

Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

2011-12-01

Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

Geochronological, geochemical and Sr-Nd-Hf isotopic constraints on the petrogenesis of Late Cretaceous A-type granites from the Sibumasu Block, Southern Myanmar, SE Asia

NASA Astrophysics Data System (ADS)

Jiang, Hai; Li, Wen-Qian; Jiang, Shao-Yong; Wang, He; Wei, Xiao-Peng

2017-01-01

The Late Cretaceous to Paleogene granitoids occur widespread in the Sibumasu block within Myanmar (SE Asia), which show a close association with tin-tungsten mineralization. However, the precise timing, petrogenesis and tectonic significance of these granitoids are poorly constrained so far. In this study, we present a detailed study on geochronology, elemental and Sr-Nd-Hf isotopic geochemistry for the Hermyingyi and Taungphila granites in southern Myanmar, with the aim of determining their petrogenesis and tectonic implications. LA-ICP-MS U-Pb dating of zircon grains from the two granites yield ages of 69-70 Ma, indicating a Late Cretaceous magmatic event. These granitic rocks are weakly peraluminous and belong to the high-K calc-alkaline series. They are both characterized by high SiO2, K2O + Na2O, FeOT/(FeOT + MgO) and Ga/Al ratios and low Al2O3, CaO, MgO, P2O5 and TiO2 contents, enriched in Rb, Th, U and Y, but depleted in Ba, Sr, P, and Eu, suggesting an A-type granite affinity. Moreover, they display prominent tetrad REE patterns and non-CHARAC trace element behavior, which are common in late magmatic differentiates with strong hydrothermal interaction or deuteric alteration. The granites belong to A2-type and probably formed at a high temperature and anhydrous condition. They have zircon εHf(t) values from - 12.4 to - 10.0 and whole-rock εNd(t) values from - 11.3 to - 10.6, with Paleoproterozoic TDM2 ages (1741-1922 Ma) for both Hf and Nd isotopes. Geochemical and isotopic data suggest that these A-type granites were derived from partial melting of the Paleoproterozoic continental crust dominated by metaigneous rocks with tonalitic to granodioritic compositions, without significant input of mantle-derived magma and followed by subsequent fractional crystallization. By integrating all available data for the regional tectonic evolution in SE Asia and adjacent regions, we attribute the formation of the Late Cretaceous A-type granites to a back-arc extension in the hinterland behind the subduction zone, which is induced by the rollback of the flat Neo-Tethyan subducting slab around ca. 70 Ma. Table 2 Major (wt.%) and trace element (ppm) compositions from the Hermyingyi and Taungphila granites. LOI is loss on ignition; A/CNK = Al2O3/(CaO + Na2O + K2O) (molar ratio); FeOT = FeO + Fe2O3 × 0.8998. Eu/Eu* is a measure of the Eu anomaly when compare to Sm and Gd. Eu/Eu* = EuN/[(SmN) × (GdN)]0.5. Table 3 Sr-Nd isotopic compositions of the Hermyingyi and Taungphila granites. Table 4 Hf isotopic compositions of zircons from the Hermyingyi and Taungphila granites. (176Lu/177Hf)CHUR = 0.0032, (176Hf/177Hf)CHUR,0 = 0.282772 (Blichert-Toft and Albarède, 1997); (176Lu/177Hf)DM = 0.0384, (176Hf/177Hf)DM,0 = 0.28325 (Griffin et al., 2000); λ = 1.867 × 10- 11/year (Soderlund et al., 2004).

GEMS Revealed: Spectrum Imaging of Aggregate Grains in Interplanetary Dust

NASA Technical Reports Server (NTRS)

Keller, L. P.; Messenger, S.; Christoffersen, R.

2005-01-01

Anhydrous interplanetary dust particles (IDPs) of cometary origin contain abundant materials that formed in the early solar nebula. These materials were transported outward and subsequently mixed with molecular cloud materials and presolar grains in the region where comets accreted [1]. GEMS (glass with embedded metal and sulfides) grains are a major component of these primitive anhydrous IDPs, along with crystalline Mg-rich silicates, Fe-Ni sulfides, carbonaceous material, and other trace phases. Some GEMS grains (5%) are demonstrably presolar based on their oxygen isotopic compositions [2]. However, most GEMS grains are isotopically solar and have bulk chemical compositions that are incompatible with inferred compositions of interstellar dust, suggesting a solar system origin [3]. An alternative hypothesis is that GEMS grains represent highly irradiated interstellar grains whose oxygen isotopic compositions were homogenized through processing in the interstellar medium (ISM) [4]. We have obtained the first quantitative X-ray maps (spectrum images) showing the distribution of major and minor elements in individual GEMS grains. Nanometer-scale chemical maps provide critical data required to evaluate the differing models regarding the origin of GEMS grains.

Pyroxene Homogenization and the Isotopic Systematics of Eucrites

NASA Technical Reports Server (NTRS)

Nyquist, L. E.; Bogard, D. D.

1996-01-01

The original Mg-Fe zoning of eucritic pyroxenes has in nearly all cases been partly homogenized, an observation that has been combined with other petrographic and compositional criteria to establish a scale of thermal "metamorphism" for eucrites. To evaluate hypotheses explaining development of conditions on the HED parent body (Vesta?) leading to pyroxene homogenization against their chronological implications, it is necessary to know whether pyroxene metamorphism was recorded in the isotopic systems. However, identifying the effects of the thermal metamorphism with specific effects in the isotopic systems has been difficult, due in part to a lack of correlated isotopic and mineralogical studies of the same eucrites. Furthermore, isotopic studies often place high demands on analytical capabilities, resulting in slow growth of the isotopic database. Additionally, some isotopic systems would not respond in a direct and sensitive way to pyroxene homogenization. Nevertheless, sufficient data exist to generalize some observations, and to identify directions of potentially fruitful investigations.

Evolution of the Ureilite Parent Body

NASA Technical Reports Server (NTRS)

Hudson, P.; Romanek, C.; Paddock, Lindy; Mittlefehldt, D. W.

2004-01-01

Ureilites are ultramafic achondrites composed primarily of olivine and pyroxene with intergranular fine-grained metal, sulfides, and silicates. Ureilites contain significant amounts of carbon (up to about 6.5 wt%) as graphite, lonsdaleite, and/or diamond. It has been shown that carbon-silicate redox (i.e. "smelting") reactions are responsible for the negative FeO-MnO (or positive Fe/Mn-Fe/Mg with constant Mn/Mg) trend seen in the mineral and bulk compositions of ureilites and for the positive correlation between modal percent pigeonite and mg#. Carbon redox reactions are strongly exothermic and pressure dependent; so ureilites with the largest mg# are the most reduced, experienced the highest temperatures, and formed at the lowest pressures, i.e. near the surface of the ureilite parent body. Ureilites with the largest mg# have the smallest the delta(sup 18)O and the largest Delta(sup 17)O. To explain this, Singletary and Grove proposed that heterogeneous accretion took place on the ureilite parent body, which lead to a radial distribution of the oxygen isotopes. To further investigate possible relationships, we performed carbon isotope and electron probe measurements on a suite of 27 ureilites in order to see the type of correlation that exists between mg#, oxygen isotopes, and carbon.

The isotopic effects of electron transfer: an explanation for Fe isotope fractionation in nature

NASA Astrophysics Data System (ADS)

Kavner, A.; Shahar, A.; Bonet, F.; Simon, J. I.; Young, E.

2004-12-01

Recent developments in mass spectrometry techniques have created opportunities to examine the partitioning behavior of stable isotopes of transition metals with a focus on application to iron isotopes. Iron oxidizing and reducing bacteria have been shown to cause isotope fractionations similar in magnitude to those observed in sedimentary environments and it is believed that biological activity is responsible for the most significant Fe isotope fractionation in natural settings. Debate over the use of Fe isotopes as a biological marker resulted from subsequent measurements of fractionations in a variety of abiotic systems. The accumulated evidence, in both biotic and abiotic systems, points to a connection between redox processes and Fe isotope fractionation, however the exact mechanism for isotope fractionation is not yet well understood. Here, we present both a newly-developed theory based on chemical kinetics and preliminary experimental results that quantitatively delineate the relationship between driving force in a charge transfer reaction and resulting Fe isotope fractionation. The theory, based on R. Marcus's chemical kinetics theory for electron transfer (Ann. Rev. Phys. Chem. 15 (1964), 155), predicts that fractionation increases linearly with driving force with a proportionality related to two factors: the difference between isotopic equilibrium exchange of products and reactants, and the reorganization energy along the reaction coordinate. The theoretical predictions were confirmed by measurements of isotopic fractionation associated with electroplating iron metal from a ferrous chloride solution. Isotope fractionation of Fe electroplated under potentiostatic conditions was measured as a function of applied electrochemical potential. As plating voltage was varied from -50 mV to -2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ 56Fe values ranging from -0.106(±0.01) to -2.290(±±0.006)‰ , and corresponding δ 57Fe values of -0.145(±.011) and -3.354(±.019)‰ . The slope of the line created by plotting δ 56Fe vs δ 57Fe is equal to 0.6723(±.0032), consistent with fractionation due to a kinetic process involving unsolvated iron atoms. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. The magnitude of fractionation is similar to observations of Fe reduction by certain bacteria, suggesting that electrochemical processes may be responsible for observed biogeochemical signatures. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.

Iron-Isotopic Fractionation Studies Using Multiple Collector Inductively Coupled Plasma Mass Spectrometry

NASA Technical Reports Server (NTRS)

Anbar, A. D.; Zhang, C.; Barling, J.; Roe, J. E.; Nealson, K. H.

1999-01-01

The importance of Fe biogeochemistry has stimulated interest in Fe isotope fractionation. Recent studies using thermal ionization mass spectrometry (TIMS) and a "double spike" demonstrate the existence of biogenic Fe isotope effects. Here, we assess the utility of multiple-collector inductively-coupled plasma mass spectrometry(MC-ICP-MS) with a desolvating sample introduction system for Fe isotope studies, and present data on Fe biominerals produced by a thermophilic bacterium. Additional information is contained in the original extended abstract.

Anisotropic Morphological Changes in Goethite during Fe(2+)-Catalyzed Recrystallization.

PubMed

Joshi, Prachi; Gorski, Christopher A

2016-07-19

When goethite is exposed to aqueous Fe(2+), rapid and extensive Fe atom exchange can occur between solid-phase Fe(3+) and aqueous Fe(2+) in a process referred to as Fe(2+)-catalyzed recrystallization. This process can lead to the structural incorporation or release of trace elements, which has important implications for contaminant remediation and nutrient biogeochemical cycling. Prior work found that the process did not cause major changes to the goethite structure or morphology. Here, we further investigated if and how goethite morphology and aggregation behavior changed temporally during Fe(2+)-catalyzed recrystallization. On the basis of existing literature, we hypothesized that Fe(2+)-catalyzed recrystallization of goethite would not result in changes to individual particle morphology or interparticle interactions. To test this, we reacted nanoparticulate goethite with aqueous Fe(2+) at pH 7.5 over 30 days and used transmission electron microscopy (TEM), cryogenic TEM, and (55)Fe as an isotope tracer to observe changes in particle dimensions, aggregation, and isotopic composition over time. Over the course of 30 days, the goethite particles substantially recrystallized, and the particle dimensions changed anisotropically, resulting in a preferential increase in the mean particle width. The temporal changes in goethite morphology could not be completely explained by a single mineral-transformation mechanism but rather indicated that multiple transformation mechanisms occurred concurrently. Collectively, these results demonstrate that the morphology of goethite nanoparticles does change during recrystallization, which is an important step toward identifying the driving force(s) of recrystallization.

Assessment of shock effects on amphibole water contents and hydrogen isotope compositions: 1. Amphibolite experiments

NASA Astrophysics Data System (ADS)

Minitti, Michelle E.; Rutherford, Malcolm J.; Taylor, Bruce E.; Dyar, M. Darby; Schultz, Peter H.

2008-02-01

Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10‰). Extrapolating the shock signature of the regrouped data to grains that experienced Martian meteorite-like shock pressures suggests that shock-induced water losses and hydrogen isotope enrichments could approach 1 wt.% H 2O and Δ D = + 100‰, respectively. If these values are valid, then impact shock effects could explain a substantial fraction of the low water contents and variable hydrogen isotope compositions of the Martian meteorite kaersutites.

Comment on “Isotopic fractionation between Fe(III) and Fe(II) in aqueous solutions” by Clark Johnson et al., [Earth Planet. Sci. Lett. 195 (2002) 141–153

USGS Publications Warehouse

Bullen, Thomas D.; White, Arthur F.; Childs, Cyril W.

2003-01-01

In a recent contribution [1], Johnson et al. reported the equilibrium isotope fractionation factor between dissolved Fe(II) and Fe(III) in aqueous solutions at pH=2.5 and 5.5. They suggest that because the iron isotope fractionation observed in their experiments spans virtually the entire range observed in sedimentary rocks, Fe(II)–Fe(III) aqueous speciation may play a major role in determining iron isotope variations in nature where Fe(II) and Fe(III) can become physically separated. They discounted earlier conclusions by us and others [2] ;  [3] that significant equilibrium fractionation between specific coexisting Fe(II)- or Fe(III)-aqueous complexes (e.g., between aqueous Fe(II)(OH)x(aq)and Fe(II)(aq) ion) is capable of producing iron isotope contrasts that can be preserved in nature. This is an important contribution not only because the authors recognize the importance of abiotic equilibrium iron isotope fractionation in nature in contrast to previous assertions [4], but also because it will help to focus discussion on the development and evaluation of experimental approaches that can reveal abiotic fractionation mechanisms. However, in this Comment we propose that the experiments presented in this paper cannot be interpreted as straightforwardly as Johnson et al. contend. In particular, we show that in one of their critical experiments attainment of either isotope mass balance or equilibrium was not demonstrated, and thus the results of that experiment cannot be used to calculate an Fe(II)–Fe(III) equilibrium fractionation factor.

Anthropogenic and natural lead isotopes in Fe-hydroxides and Fe-sulphates in a watershed associated with arsenic-enriched groundwater, Maine, USA

USGS Publications Warehouse

Ayuso, Robert A.; Foley, Nora K.

2008-01-01

A survey of the natural and anthropogenic sources of lead contributing to secondary minerals in sulphidic schists associated with arsenic-enriched groundwater in Coastal Maine shows that the most likely source is natural Pb, particularly from coexisting sulphide minerals. The secondary minerals also reflect notable contributions from anthropogenic Pb. The Pb isotopes establish pathways by which Pb, and by inference As, could have been transported from As-bearing minerals (arsenian pyrite, arsenopyrite, lollingite, orpiment, arsenic oxide and others), via sulphide oxidation or carbonation reactions into multiple generations of secondary minerals (goethite, hematite, jarosite, natrojarosite and others). Lead isotopic compositions of the sulphides and secondary minerals determined by thermal ionization mass spectrometry (n=53) range widely. Lead and As contents of the sulphides and secondary minerals overlap, and are generally positively correlated. Pyrite, the dominant sulphide in sulphidic schists associated with As-enriched groundwater in Coastal Maine, has values of 206Pb/204Pb from 18.186 to 18.391, 207Pb/204Pb from 15.617 to 15.657, 208Pb/204Pb from 38.052 to 38.210, 206Pb/207Pb from c. 1.1625 to 1.1760 and 208Pb/207Pb from c. 2.4276 to 2.4394. Mixtures of Fe-hydroxide and oxide minerals (predominantly goethite and hematite) and secondary Fe-sulphate minerals (jarosite, natrojarosite, rozenite and melanterite) in the sulphidic schists have overlapping but generally higher values of 206Pb/204Pb from 18.495 to 19.747 (one sample at 21.495), 207Pb/204Pb from 15.595 to 15.722 (one sample at 15.839), 208Pb/204Pb from 38.186 to 39.162,206Pb/207Pb from c.1.1860 to 1.2575 (one sample at 1.3855) and 208Pb/207Pb from c. 2.4441 to 2.4865 than the sulphides. Sulphides from Zn-Pb metal mines are somewhat less radiogenic than sulphides from the schists. Other sulphides (mostly pyrite) associated with pegmatites and granitic rocks are heterogeneous and more radiogenic than the pyrite-rich sulphidic schists. Sulphides from other regional bedrock units also have heterogeneous isotope values. Lead isotopic compositions of the sulphides from the sulphidic schists and coexisting Fe-oxides and Fe-sulphates produced by weathering and alteration overlap, but the secondary minerals extend toward more radiogenic values that broadly indicate the addition of Pb from anthropogenic origin. As a component of Pb from extensively used arsenical pesticides may also be present in the secondary minerals, the range in Pb isotope values is consistent with multiple sources: natural Pb from the schists and anthropogenic Pb (industrial and possibly from agricultural activities). Contributions from past mining activities or from other bedrock sources are not implicated.

Geochemistry of Pallasite Olivines and the Origin of Main-Group Pallasites

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Rumble, D., III

2006-01-01

Main-group pallasites (PMG) are mixtures of iron-nickel metal and magnesian olivine thought to have been formed at the core-mantle boundary of an asteroid [1]. Some have anomalous metal compositions (PMG-am) and a few have atypically ferroan olivines (PMG-as) [2]. PMG metal is consistent with an origin as a late fractionate of the IIIAB iron core [2]. Most PMG olivines have very similar Fe/Mg ratios, likely due to subsolidus redox reaction with the metal [3]. In contrast, minor and trace elements show substantial variation, which may be explained by either: (i) PMG were formed at a range of depths in the parent asteroid; the element variations reflect variations in igneous evolution with depth, (ii) the pallasite parent asteroid was chemically heterogeneous; the heterogeneity partially survived igneous processing, or (iii) PMG represent the core-mantle boundaries of several distinct parent asteroids [4, 5]. We have continued doing major, minor and trace elements by EMPA and INAA on a wider suite of PMG olivines, and have begun doing precise oxygen isotope analyses to test these hypotheses. Manganese is homologous with Fe(2+), and can be used to distinguish between magmatic and redox processes as causes for Fe/Mg variations. PMG olivines have a range in molar 1000*Mn/Mg of 2.3-4.6 indicating substantial igneous fractionation in olivines with very similar Fe/Mg (0.138-0.148). The Mg-Mn-Fe distributions can be explained by a fractional crystallization-reduction model; higher Mn/Mg ratios reflect more evolved olivines while Fe/Mg is buffered by redox reactions with the metal. There is a positive association between Mn/Mg and Sc content that is consistent with igneous fractionation. However, most PMG olivines fall within a narrow Mn/Mg range (3.0-3.6), but these show a substantial range in Sc (1.00-2.29 micro-g/g). Assuming fractional crystallization, this Sc range could have resulted from approx.65% crystallization of an ultramafic magma. This is inconsistent with formation at the core-mantle boundary of a single asteroid [4]. One alternative is that the PMG are fragments of several asteroids, and these could have had different initial Sc contents, Mn/Mg and differences in igneous history. Our preliminary O isotope data and those of [6, 7] do not support this, although the coverage of PMG olivines is incomplete. The PMG-as Springwater is not easily fit in any scenario. Its olivine has among the highest Mn/Mg suggesting it is one of the most evolved, but the lowest Sc content suggesting it is the least evolved. The O isotopic composition of Springwater olivine is the same as that of other PMG. Thus there is no indication that it represents a distinct parent asteroid. Our preliminary O isotopic data favor a single PMG parent asteroid. In this case, the olivines are more likely melt-residues, and that the parent asteroid was initially heterogeneous in chemical, but not isotopic, composition.

Tracing alteration of mantle peridotite in the Samail ophiolite using Mg isotopes

NASA Astrophysics Data System (ADS)

de Obeso, J. C.; Kelemen, P. B.; Higgins, J. A.

2017-12-01

Magnesium is one of the main constituents of mantle peridotite ( 22.8 wt%), which has a homogeneous Mg isotopic composition (d26Mg = -0.25 ± 0.04 ‰ (2 sd) DSM3, Teng et al 2010 GCA). Mg isotopes are used as tracers of continental and oceanic weathering as they exhibit variable degrees of fractionation during alteration depending on the lithology. Here we report some of the first Mg isotopic compositions of the mantle section of the Samail ophiolite in Oman and its alteration products. The mantle section of the ophiolite is composed mainly of depleted harzburgites and dunites with mantle-like d26Mg (-0.25, -0.21 ‰). Mantle peridotite is far from equilibrium in near surface conditions leading to rapid, extensive serpentinization, carbonation and oxidation, as well as other geochemical changes. Our analyzed samples encompass most of the alteration of peridotite products observed in Oman including listvenites (completely carbonated peridotite) near the basal thrust of the ophiolite, massive magnesite veins within peridotite outcrops, and heavily altered harzburgites. Magnesite listvenites have d26Mg slightly below mantle values (-0.33, -0.33‰) while dolomite listvenites are significantly lighter (-1.46, -0.89‰). This suggests that heavy Mg isotopes were removed from the listvenites during ophiolite emplacement. Heavily altered peridotite from Wadi Fins exhibit alteration halos with drastic changes in composition. The most oxidized areas are enriched in Fe and depleted in Mg compared to the cores of the samples. These variations in Mg concentrations are complemented by a shift to heavy Mg isotopic compositions (0.74, 0.86‰), among the heaviest d26Mg values that have been reported in altered peridotite. Potential sinks for light isotopes removed from such alteration zones are massive magnesite veins with very light compositions (-3.39, -3.14‰). The fractionation of Mg isotopes observed in the mantle section of the ophiolite spans more than 50% of the known terrestrial fractionation.

Detrital sources and water mass circulation in the tropical North Atlantic during the Late Cretaceous to Paleogene

NASA Astrophysics Data System (ADS)

Martin, E. E.; Pugh, E.; Kamenov, G. D.; MacLeod, K. G.

2014-12-01

Seawater Nd isotopes from fossil fish teeth in Campanian to Paleogene calcareous claystone on Demerara Rise in the tropical North Atlantic record a change from epsilon Nd values of -17 to -11 during the late Maastrichtian. This shift has been identified in three different Ocean Drilling Program (ODP) sites that span from 600 to 1500 m paleodepths (ODP sites 1259, 1260 and 1261) and has been interpreted as a transition from a warm saline intermediate water mass formed on the South American margin, referred to as Demerara Bottom Water, to a source from the North Atlantic. A study of corresponding detrital Sr, Nd and Pb isotopes was undertaken to confirm the isotopic values derived from fish teeth record water mass compositions rather than diagenesis or boundary exchange. Several leaching procedures designed to remove Fe-Mn oxide coatings and the seawater signature they carry from the detrital fractions were tested. Sr isotopic data indicate a 0.02 M hydroxylamine hydrochloride (HH) leach was ineffective at removing the Fe-Mn oxides whereas a 1.0 M HH leach produced detrital Sr isotopic values that were consistent for all three sites and plotted farther from the seawater value. Detrital isotopic results can be divided into three intervals: 1) 73 - 66 Ma, when DBW is present, 2) 66 - 61 Ma, during the transition to North Atlantic sources, and 3) <61 Ma, when North Atlantic sources appear to dominate. During interval 1, detrital Nd isotopes increase gradually, while Sr and Pb isotopic ratios are relatively constant. Leading into interval 2, detrital Nd isotopes are fairly constant while there is a stepwise increase in Sr and Pb isotopes. Leading into interval 3, there is a large increase in Nd and decrease in Sr isotopes and a slight decrease in Pb isotopes. The subtle differences in the timing of changes in fish teeth and detrital Nd isotopes suggest the seawater signal is responding to changes in water mass rather than changes in sediment composition (boundary exchange). The timing of the changes in detrital inputs indicates changes in provenance may correlate with the rearrangement of the currents transporting sediment to the region associated with the transition from a water mass sourced from the tropics to a more northern source.

Origin and fate of sulfide liquids in hotspot volcanism (La Réunion): Pb isotope constraints from residual Fe-Cu oxides

NASA Astrophysics Data System (ADS)

Vlastélic, I.; Gannoun, A.; Di Muro, A.; Gurioli, L.; Bachèlery, P.; Henot, J. M.

2016-12-01

Immiscible sulfide liquids in basaltic magmas play an important role in trace metal transport and the sulfur budget of volcanic eruptions. However, sulfides are transient phases, whose origin and fate are poorly constrained. We address these issues by analyzing sulfide destabilization products preserved in lavas from La Réunion Island. Iron oxide globules and coatings, typically 20-80 μm in size, were found to occur in vesicles of differentiated lavas from Piton des Neiges, and recent pumice samples from Piton de la Fournaise. Field and mineralogical evidence indicates that the iron oxides are syn-eruptive phases not resulting from hydrothermal processes. Samples were first studied by Scanning Electron Microscopy. The globules were separated, whereas the smaller spherules and coatings were concentrated by magnetic sorting and acid leaching, and samples were processed through wet chemistry. The Fe oxide phases comprise 49-74 wt.% Fe, 26-40 wt.% O, and up to 6 wt.% Cu, 811 ppm Ni, 140 ppm Bi, and 8.5 ppm Pb. Compared to the host lava, Cu, Ni, and Bi are enriched by a factor of 101-103. Systematic Pb isotope disequilibrium (between 500 ppm and 2.9% for 206Pb/204Pb) exists between Fe oxides and host rocks, with Fe oxides generally displaying less radiogenic ratios. Unradiogenic Pb is a typical signature of sulfide, which tends to concentrate Pb, but not its parent elements U and Th. Thus, both the chemical and isotopic compositions of the vesicle-hosted Fe oxides suggest that they are more or less direct products of the destabilization of immiscible sulfide liquids. Although Pb dominantly partitions into the gas phase during sulfide breakdown, the original Pb isotope signature of sulfide is preserved in the residual oxide. The composition estimated for the parent sulfides (206Pb/204Pb = 18.20-18.77, 207Pb/204Pb = 15.575, and 208Pb/204Pb = 38.2-38.8) precludes a genetic link with the La Réunion plume, and suggests a lithospheric or crustal origin. It is estimated that magma ascent velocities at Piton de la Fournaise are high enough to counterbalance the settling velocities of millimeter-size sulfides. Despite their high density, sulfide liquids are thus transferred upward during eruptions and their destabilization contributes to SO2 emanations. Assimilation of foreign sulfides from the lithosphere can explain why SO2 emissions sometimes (e.g., during the April 2007 eruption) exceed those predicted from the S content of melt inclusions.

Determining the N and O isotope effects of microbial nitrite reduction: the global N cycle implications of an enzyme-dependent isotope effect

NASA Astrophysics Data System (ADS)

Martin, T. S.; Casciotti, K. L.

2014-12-01

The marine nitrogen (N) cycle is a dynamic system of critical importance, since nitrogen is the limiting nutrient in over half of the world's oceans. Denitrification and anammox, the main N loss processes from the ocean, have different effects on carbon cycling and greenhouse gas emission. Understanding the balance between the two processes is vital to understanding the role of the N cycle in global climate change. One approach for investigating these processes is by using stable isotope analysis to estimate the relative magnitudes of N fluxes, particularly for biologically mediated processes. In order to make the most of the currently available isotope analysis techniques, it is necessary to know the isotope effects for each processes occurring in the environment. Nitrite reduction is an important step in denitrification. Previous work had begun to explore the N isotope effects for nitrite reduction, but no oxygen (O) isotope effect has been measured. Additionally, no consideration has been given to the type of nitrite reductase carrying out the reaction. There are two main types of respiratory nitrite reductase, one that is Cu-based and another that is Fe-based. We performed batch culture experiments with denitrifier strains possessing either a Cu-type or Fe-type nitrite reductase. Both N and O isotope effects for nitrite reduction were determined for each of these experiments by measuring the NO2- concentration, as well as the N and O isotopes of nitrite and applying a Rayleigh fractionation model. Both the N and O isotope effects were found to be significantly different between the two types of enzymes. This enzyme-linked difference in isotope effects emphasizes the importance of microbial community composition within the global N cycle.

Core formation conditons in planetesimals: constraints from isotope fractionation experiments.

NASA Astrophysics Data System (ADS)

Guignard, J.; Quitté, G.; Toplis, M. J.; Poitrasson, F.

2016-12-01

Planetesimals are small objects (10 to 1000 km) early accreted in the history of the solar system which show a wide variety of thermal history due to the initial amount of radiogenic elements [1] (26Al and 60Fe), from a simple metamorphism to a complete metal-silicate differentiation. Moreover, isotope compositions of siderophile element, e.g. Fe, Ni, and W in meteorites spread on a range that can be attributed to the process of core-mantle segregation. We therefore performed isotope fractionation experiments of nickel and tungsten between metal and silicate in a gas-mixing (CO-CO2) vertical furnace, at different temperatures (from 1270°C to 1600°C), oxygen fugacity (from IW+2 to IW-6) and annealing times (from 20 minutes to 48 hours). The starting silicate is an anorthite-diopside eutectic composition glass, synthesize from the respective oxides. The starting metal is either a nickel or tungsten wire according to the element to study. After each experiment, metal and silicate are mechanically separated and digested in acids. Nickel and Tungsten separation have been made according to the methods developed by [2] and [3] and isotopes measurements have been made using a high resolution MC-ICP-MS (Neptune; Thermofisher©). Results show evidence for a strong kinetic isotope fractionation during the first annealing times with a faster diffusion of lightest isotopes than heaviest. Similar mechanism has been already highlighted for iron isotope fractionation between silicate and metal [4]. Chemical and isotopic equilibrium is also reached in our experiments but the time required dependent on the conditions of temperature and oxygen fugacity. Therefore, at equilibrium, metal-silicate isotope fractionation has also been quantified as well its temperature dependence. These experimental data can be used in order to bring new constraints on the metal silicate segregation in the planetesimals early accreted. [1] Lee T., et al., GRL, 3, 41-44 (1976) [2] Quitté G., and Oberli F., JAAS, 21, 1249-1255 (2006) [3] Breton T., and Quitté G., JAAS, 29, 2284-2293 (2014) [4] Roskosz M., et al., EPSL, 248, 851-867 (2006)

An Achondritic Micrometeorite from Antarctica: Expanding the Solar System Inventory of Basaltic Asteroids

NASA Technical Reports Server (NTRS)

Gounelle, M.; Engrand, C.; Chaussidon, M.; Zolensky, M. E.; Maurette, M.

2005-01-01

Micrometeorites with sizes below 1 mm are collected in a diversity of environments such as deep-sea sediments and polar caps. Chemical, mineralogical and isotopic studies indicate that micrometeorites are closely related to primitive carbonaceous chondrites that amount to only approximately 2% of meteorite falls. While thousands of micrometeorites have been studied in detail, no micrometeorite has been found so far with an unambiguous achondritic composition and texture. One melted cosmic spherule has a low Fe/Mn ratio similar to that of eucrites, the most common basaltic meteorite group. Here we report on the texture, mineralogy, Rare Earth Elements (REEs) abundance and oxygen isotopic composition of the unmelted Antarctic micrometeorite 99-21-40 that has an unambiguous basaltic origin.

Further analysis of the IRIS iron isotope experiment

NASA Technical Reports Server (NTRS)

Tarle, G.; Ahlen, S. P.; Cartwright, B. G.; Solarz, M.

1980-01-01

The IRIS Fe isotope experiment was extended to atomic charges of Z = 19, with isotopic distributions for 500 events ranging from 18 to 28. Normalization of the detector response functions at Fe-56 produced a single well resolved peak at Sc-45, establishing the resolution and mass scale of the device over the entire charge region. The abundance distributions for the predominantly primary isotopes Ca-40, Fe-54, Fe-56, Ni-58, and Ni-60 do not indicate a large admixture of material with distinctly nonsolar abundances.

Thorium distributions in high- and low-dust regions and the significance for iron supply

NASA Astrophysics Data System (ADS)

Hayes, Christopher T.; Rosen, Jeffrey; McGee, David; Boyle, Edward A.

2017-02-01

Thorium and uranium isotopes (232Th, 230Th, 238U, and 234U) were investigated to refine their use for estimating mineral dust deposition and Fe delivery to the ocean. U concentrations and isotope ratios were consistent with conservative behavior and can safely be described using published U-salinity relationships and global average seawater isotopic composition. Near Barbados, waters affected by the Amazon outflow contained elevated 232Th. This signals one region where the thorium-dust method is inaccurate because of a confounding continental input. Dissolved 232Th fluxes in this region suggest that Amazonian Fe supply to the adjacent open ocean is much larger than local atmospheric deposition. The colloidal content of dissolved Th south of Bermuda was found to be quite small (2-6%), similar to that found north of Hawaii, despite the order of magnitude higher dust deposition in the Atlantic. This finding supports the assumption that dissolved 232Th and 230Th are scavenged at the same rate despite their different sources and also sheds light on the increase of dissolved 232Th fluxes with integrated depth. Outside the region influenced by Amazon River waters, dissolved 232Th fluxes are compared with Bermudan aerosol Fe deposition to estimate that fractional Th solubility is around 20% in this region. Finally, new dissolved and soluble Fe, Mn, and Cr data from the subtropical North Pacific support the idea that Fe concentrations in the remote ocean are highly buffered, whereas 232Th has a larger dynamic range between high- and low-dust regions.

Silicon isotope fractionations in pure Si and Fe-Si systems and their geological implications

NASA Astrophysics Data System (ADS)

Zheng, X. Y.; Beard, B. L.; Reddy, T. R.; Roden, E. E.; Johnson, C.

2016-12-01

Amorphous Si or Si-bearing materials are ubiquitous in nature, and are likely precursors to various rock types, such as cherts and banded iron formations (BIFs). Si isotope exchange kinetics and fractionation factors between these materials and aqueous Si, however, are poorly constrained, preventing a mechanistic or quantitative understanding of geological δ30Si records. A series of laboratory experiments were conducted to provide better estimates on Si isotope exchange kinetics and fractionation factors. Equilibrium Si isotope fractionation factors between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aq) in artificial Archean seawater (AAS), determined by a three-isotope method with a 29Si tracer, are -2.3‰ where Fe2+ is absent from the solution, and -3.2‰ where Fe2+ is present in the solution[1]. Aqueous Fe2+ catalyzes Si isotope exchange, and causes larger Si isotope fractionation due to incorporation into the solid that may have changed Si bonding. In contrast, our preliminary results show that Δ30Sigel-aq between pure Si gel and aqueous Si at equilibrium is -0.13‰. Ongoing experiments are intended to approach the isotope equilibrium from multiple directions to resolve potential kinetic effects, and to explore temperature dependence. Nonetheless, the contrast in Δ30Sigel-aq between Fe-Si and pure Si systems highlights a significant impact of Fe on Si isotope fractionations. These results have important implications for Si isotopes in Precambrian cherts and BIFs, as well as in weathering systems in general. Silicon isotope fractionation was also studied in experiments that involved dissimilatory iron reduction of Fe(III)-Si gel by Desulfuromonas acetoxidans in AAS[2], and was found to become larger with progression of Fe reduction. A Δ30Sigel-aq of -3.5‰ was observed at 32% reduction of Fe3+. This result explains lower δ30Si values in magnetite-associated quartz that those in hematite-associated quartz in some BIFs. The large Si isotope fractionation produced in the microbial experiment, even larger than that seen in our Fe(II)-bearing abiologic experiments, suggests that δ30Si can be a potential tracer for magnetite of a microbial origin, or, vice versa, for microbial activities in magnetite. [1] Zheng et al., 2016, GCA 187, 102-122. [2] Reddy et al., 2016, GCA 190, 85-99.

Biotic and abiotic pathways of phosphorus cycling in minerals and sediments: insights from oxygen isotopes in phosphate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaisi, Deb P.; Kukkadapu, Ravi K.; Stout, Lisa M.

2011-07-06

A key question to address in the development of oxygen isotope ratios in phosphate (18Op) as a tracer of biogeochemical cycling of phosphorus in ancient and modern environments is the nature of isotopic signatures associated with uptake and cycling of mineral-bound phosphate by microorganisms. Here we present experimental results aimed at understanding the biotic and abiotic pathway of P cycling during biological uptake of phosphate sorbed to ferrihydrite and the selective uptake of specific sedimentary phosphate phases by Escherichia coli, Vibrio fischeri and Marinobacter aquaeolei. Results indicate that a significant fraction of ferrihydrite-bound phosphate is biologically available. The fraction ofmore » phosphate taken up by E. coli attained an equilibrium isotopic composition in a short time (<50 hrs) due to efficient O-isotope exchange between phosphate and water (biotic pathway). The difference in isotopic composition between newly equilibrated aqueous and residual sorbed phosphate promoted the exchange of intact phosphate radicals (abiotic pathway) so that this difference gradually became negligible. In sediment containing different P phases, E. coli and V. fischeri ‘extracted’ loosely sorbed phosphate first while M. aquaeolei preferred iron-oxide bound phosphate. Each bacterium imprinted a biotic isotopic signature on each P phase that it took up and cycled. For example, the 18Op value of the sorbed phosphate phase shifted gradually towards equilibrium isotopic composition and the value of Fe oxide-bound phosphate showed slight changes at first, but when new iron oxides were formed, co-precipitated/occluded phosphate retained 18O values of aqueous phosphate at that time. Concentrations and isotopic compositions of authigenic and detrital phosphates did not change, suggesting that these phosphate phases were not utilized by bacteria. These findings support burgeoning applications of 18Op as a tracer of phosphorus cycling in sediments, soils and aquatic environments and as an indicator of paleo- environmental conditions.« less

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, II

NASA Technical Reports Server (NTRS)

2004-01-01

The Special Session: Oxygen in the Solar System, II, included the following reports:Evolution of Oxygen Isotopes in the Solar Nebula; Disequilibrium Melting of Refractory Inclusions: A Mechanism for High-Temperature Oxygen; Isotope Exchange in the Solar Nebula; Oxygen Isotopic Compositions of the Al-rich Chondrules in the CR Carbonaceous Chondrites: Evidence for a Genetic Link to Ca-Al-rich Inclusions and for Oxygen Isotope Exchange During Chondrule Melting; Nebular Formation of Fayalitic Olivine: Ineffectiveness of Dust Enrichment; Water in Terrestrial Planets: Always an Oxidant?; Oxygen Barometry of Basaltic Glasses Based on Vanadium Valence Determination Using Synchrotron MicroXANES; A New Oxygen Barometer for Solar System Basaltic Glasses Based on Vanadium Valence; The Relationship Between Clinopyroxene Fe3+ Content and Oxygen Fugacity ; and Olivine-Silicate Melt Partitioning of Iridium.

Pyritic event beds and sulfidized Fe (oxyhydr)oxide aggregates in metalliferous black mudstones of the Paleoproterozoic Talvivaara formation, Finland

NASA Astrophysics Data System (ADS)

Virtasalo, Joonas J.; Laitala, Jaakko J.; Lahtinen, Raimo; Whitehouse, Martin J.

2015-12-01

The Paleoproterozoic, 2.0-1.9 Ga Talvivaara formation of Finland was deposited during the Shunga Event, a worldwide episode of enhanced accumulation of organic-rich sediments in the aftermath of the Lomagundi-Jatuli carbon isotope excursion. Sulfidic carbonaceous mudstones in the Talvivaara formation contain one of the largest known shale-hosted nickel deposits. In order to gain new insight into this Shungian sedimentary environment, sedimentological, petrographical and in situ S and Fe isotopic microanalyses were carried out on samples representing depositional and early-diagenetic conditions. The event-bedded lithology with tidal signatures in the organic-rich mudstones strongly indicates deposition from predominantly river-delivered mud on a highly-productive coastal area, below storm-wave base. The riverine supply of phosphorus, sulfate and iron supported high primary productivity and resulted in strong lateral and vertical chemical gradients in the nearshore waters with a shallow oxic surface layer underlain by euxinic water. The stratigraphic upper part of the Talvivaara formation contains banded intervals of thin alternating pyrite beds and carbonaceous mudstone beds. The pyrite beds were deposited by seaward excursions of the concentrated, acidic Fe-rich river plume subsequent to droughts or dry seasons, which led to intense pyrite precipitation upon mixing with euxinic waters. δ34S and δ56Fe values of the bedded pyrite (median δ34S = - 10.3 ‰ and δ56Fe = - 0.79 ‰) are consistent with the reaction of dissolved Fe(II) with H2S from bacterial sulfate reduction. Organic-rich clayey Fe-monosulfide-bearing granules were transported from the muddy estuary, and enclosed in Fe (oxyhydr)oxide aggregates that were forming by wave and current reworking in nearshore accumulations of river-delivered iron. The isotopic composition of these presently pyrrhotitic inclusions (median δ34S = - 3.3 ‰ and δ56Fe = - 1.6 ‰) indicates microbial iron reduction. The Fe (oxyhydr)oxide aggregates were transported in muddy debris flows to the distal euxinic seafloor. Their Fe (oxyhydr)oxide matrix was replaced by pyrite (median δ34S = + 5.8 ‰ and δ56Fe = + 0.81 ‰) at shallow sediment depths with 34S and 56Fe-enriched porewater. Wavy-crinkly laminae of possible microbial origin developed on the euxinic seafloor during low sedimentation. These results indicate episodic deposition at seasonal to multiannual time scales. δ34S and δ56Fe values in the studied Fe-sulfides provide evidence of microbial isotope fractionation processes and syndepositional and early-diagenetic origin, finding no support for the previously proposed local hydrothermal activity in the Talvivaara mudstones.

Thermal equilibration of iron meteorite and pallasite parent bodies recorded at the mineral scale by Fe and Ni isotope systematics

NASA Astrophysics Data System (ADS)

Chernonozhkin, Stepan M.; Weyrauch, Mona; Goderis, Steven; Oeser, Martin; McKibbin, Seann J.; Horn, Ingo; Hecht, Lutz; Weyer, Stefan; Claeys, Philippe; Vanhaecke, Frank

2017-11-01

In this work, a femtosecond laser ablation (LA) system coupled to a multi-collector inductively coupled plasma-mass spectrometer (fs-LA-MC-ICP-MS) was used to obtain laterally resolved (30-80 μm), high-precision combined Ni and Fe stable isotope ratio data for a variety of mineral phases (olivine, kamacite, taenite, schreibersite and troilite) composing main group pallasites (PMG) and iron meteorites. The stable isotopic signatures of Fe and Ni at the mineral scale, in combination with the factors governing the kinetic or equilibrium isotope fractionation processes, are used to interpret the thermal histories of small differentiated asteroidal bodies. As Fe isotopic zoning is only barely resolvable within the internal precision level of the isotope ratio measurements within a single olivine in Esquel PMG, the isotopically lighter olivine core relative to the rim (Δ56/54Ferim-core = 0.059‰) suggests that the olivines were largely thermally equilibrated. The observed hint of an isotopic and concentration gradient for Fe of crudely similar width is interpreted here to reflect Fe loss from olivine in the process of partial reduction of the olivine rim. The ranges of the determined Fe and Ni isotopic signatures of troilite (δ56/54Fe of -0.66 to -0.09‰) and schreibersite (δ56/54Fe of -0.48 to -0.09‰, and δ62/60Ni of -0.64 to +0.29‰) may result from thermal equilibration. Schreibersite and troilite likely remained in equilibrium with their enclosing metal to temperatures significantly below their point of crystallization. The Ni isotopic signatures of bulk metal and schreibersite correlate negatively, with isotopically lighter Ni in the metal of PMGs and isotopically heavier Ni in the metal of the iron meteorites analyzed. As such, the light Ni isotopic signatures previously observed in PMG metal relative to chondrites may not result from heterogeneity in the Solar Nebula, but rather reflect fractionation in the metal-schreibersite system. Comparison between the isotope ratio profiles of Fe and Ni determined across kamacite-taenite interfaces (Δ56/54Fekam-tae = -0.51 to -0.69‰ and Δ62/60Nikam-tae = +1.59 to +2.50‰) and theoretical taenite sub-solidus diffusive isotopic zoning broadly constrain the cooling rates of Esquel, CMS 04071 PMGs and Udei Station IAB to between ∼25 and 500 °C/Myr.

Processes and time scales of magmatic evolution as revealed by Fe-Mg chemical and isotopic zoning in natural olivines

NASA Astrophysics Data System (ADS)

Oeser, Martin; Dohmen, Ralf; Horn, Ingo; Schuth, Stephan; Weyer, Stefan

2015-04-01

In this study, we applied high-precision in situ Fe and Mg isotope analyses by femtosecond laser ablation (fs-LA) MC-ICP-MS on chemically zoned olivine xeno- and phenocrysts from intra-plate volcanic regions in order to investigate the magnitude of Fe and Mg isotope fractionation and its suitability to gain information on magma evolution. Our results show that chemical zoning (i.e., Mg#) in magmatic olivines is commonly associated with significant zoning in δ56Fe and δ26Mg (up to 1.7‰ and 0.7‰, respectively). We explored different cases of kinetic fractionation of Fe and Mg isotopes by modeling diffusion in the melt or olivine and simultaneous growth or dissolution. Combining the information of chemical and isotopic zoning in olivine allows to distinguish between various processes that may occur during magma evolution, namely diffusive Fe-Mg exchange between olivine and melt, rapid crystal growth, and Fe-Mg inter-diffusion simultaneous to crystal dissolution or growth. Chemical diffusion in olivine appears to be the dominant process that drives isotope fractionation in magmatic olivine. Simplified modeling of Fe and Mg diffusion is suitable to reproduce both the chemical and the isotopic zoning in most of the investigated olivines and, additionally, provides time information about magmatic processes. For the Massif Central (France), modeling of diffusive re-equilibration of mantle olivines in basanites revealed a short time span (<2 years) between the entrainment of a mantle xenolith in an intra-plate basaltic magma and the eruption of the magma. Furthermore, we determined high cooling rates (on the order of a few tens to hundreds of °C per year) for basanite samples from a single large outcrop in the Massif Central, which probably reflects the cooling of a massive lava flow after eruption. Results from the modeling of Fe and Mg isotope fractionation in olivine point to a systematic difference between βFe and βMg (i.e., βFe/βMg ≈ 2), implying that the diffusivity ratio of 54Fe and 56Fe (i.e., D54Fe/D56Fe) is very similar to that of 24Mg and 26Mg, despite the smaller relative mass difference for the 54Fe-56Fe pair. This study demonstrates that a combined investigation of Fe-Mg chemical and isotopic zoning in olivine provides additional and more reliable information on magma evolution than chemical zoning alone.

A negative excursion at 14-16 Ma in seawater osmium isotope record: Implications for paleoceanographic studies using Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Goto, K. T.; Tejada, M. L. G.; Suzuki, K.

2017-12-01

Osmium isotope stratigraphy is a recently proposed method to determine the depositional age of Fe-Mn crusts [1, 2]. Seawater Os isotope (187Os/188Os) is roughly determined by the balance of riverine Os inputs with radiogenic value (187Os/188Os = 1.4), and mantle-derived and extra-terrestrial Os inputs with non-radiogenic value (187Os/188Os = 0.12) [3]. Secular variation of global seawater Os isotope (seawater Os isotope curve) has been reconstructed by the analysis of pelagic sediments and exhibits large variations ranging from 0.2 to 1.0 with several negative excursions [3]. Hence, the depositional age of Fe-Mn crusts can be approximately estimated by fitting their Os isotope depth profiles to the seawater Os isotope curve (Osmium isotope stratigraphy). However, this method allows multiple interpretations which are partly due to the lack of high-resolution seawater Os isotope curve [1, 2]. For example, the available seawater Os isotope curve does not exhibit negative anomaly during the Miocene, which contrasts with Os isotope records of Fe-Mn crusts [4]. In the present study, we obtained a high-resolution Os isotope record of Miocene seawater using hemipelagic sediments from IODP Expedition 351 SiteU1438. We found a small negative Os isotope anomaly as low as 0.7 from sediments deposited at 14-16 Ma. The magnitude of this anomaly is similar to those reported from Fe-Mn crusts. Although the extrapolation of Be-10 ages for Fe-Mn crust indicate a younger age for the anomaly ( 11 Ma) [4], we could not find any discernable isotope anomaly at 11 Ma. Our finding is consistent with the timing of major eruption of the Columbia River flood basalts (CFRB) which could provide non-radiogenic Os to seawater at 14-16 Ma [5]. Hence, we suggest that the observed isotope anomaly reflect eruption and subsequent weathering of the CFRB. As the similar Os isotope anomaly is commonly found from Fe-Mn crusts, the Os isotope anomaly at 14-16 Ma could be used as a key event to constrain depositional ages of Fe-Mn crusts. In the presentation, we will also discuss the significance of our findings to paleoceanographic studies using Fe-Mn crusts. References: [1] Klemm et al., 2005 EPSL; [2] Nielsen et al., 2009 EPSL; [3] Peucker-Ehrenbrink & Ravizza, 2012 The Geologic Time Scale 2012; [4] Klemm et al., 2008 EPSL; [5] Hopper et al., 2002 GSA Bulletin

Modern water/rock reactions in Oman hyperalkaline peridotite aquifers and implications for microbial habitability

NASA Astrophysics Data System (ADS)

Miller, Hannah M.; Matter, Jürg M.; Kelemen, Peter; Ellison, Eric T.; Conrad, Mark E.; Fierer, Noah; Ruchala, Tyler; Tominaga, Masako; Templeton, Alexis S.

2016-04-01

The Samail ophiolite in Oman is undergoing modern hydration and carbonation of peridotite and may host a deep subsurface biosphere. Previous investigations of hyperalkaline fluids in Oman have focused on fluids released at surface seeps, which quickly lose their reducing character and precipitate carbonates upon contact with the O2/CO2-rich atmosphere. In this work, geochemical analysis of rocks and fluids from the subsurface provides new insights into the operative reactions in serpentinizing aquifers. Serpentinite rock and hyperalkaline fluids (pH > 10), which exhibit millimolar concentrations of Ca2+, H2 and CH4, as well as variable sulfate and nitrate, were accessed from wells situated in mantle peridotite near Ibra and studied to investigate their aqueous geochemistry, gas concentrations, isotopic signatures, mineralogy, Fe speciation and microbial community composition. The bulk mineralogy of drill cuttings is dominated by olivine, pyroxene, brucite, serpentine and magnetite. At depth, Fe-bearing brucite is commonly intermixed with serpentine, whereas near the surface, olivine and brucite are lost and increased magnetite and serpentine is detected. Micro-Raman spectroscopy reveals at least two distinct generations of serpentine present in drill cuttings recovered from several depths from two wells. Fe K-edge X-ray absorption near-edge spectroscopy (XANES) analysis of the lizardite shows a strong tetrahedral Fe coordination, suggesting a mixture of both Fe(II) and Fe(III) in the serpentine. Magnetite veins are also closely associated with this second generation serpentine, and 2-10 μm magnetite grains overprint all minerals in the drill cuttings. Thus we propose that the dissolved H2 that accumulates in the subsurface hyperalkaline fluids was evolved through low temperature oxidation and hydration of relict olivine, as well as destabilization of pre-existing brucite present in the partially serpentinized dunites and harzburgites. In particular, we hypothesize that Fe-bearing brucite is currently reacting with dissolved silica in the aquifer fluids to generate late-stage magnetite, additional serpentine and dissolved H2. Dissolved CH4 in the fluids exhibits the most isotopically heavy carbon in CH4 reported in the literature thus far. The CH4 may have formed through abiotic reduction of dissolved CO2 or through biogenic pathways under extreme carbon limitation. The methane isotopic composition may have also been modified by significant methane oxidation. 16S rRNA sequencing of DNA recovered from filtered hyperalkaline well fluids reveals an abundance of Meiothermus, Thermodesulfovibrionaceae (sulfate-reducers) and Clostridia (fermenters). The fluids also contain candidate phyla OP1 and OD1, as well as Methanobacterium (methanogen) and Methylococcus sp. (methanotroph). The composition of these microbial communities suggests that low-temperature hydrogen and methane generation, coupled with the presence of electron acceptors such as nitrate and sulfate, sustains subsurface microbial life within the Oman ophiolite.

MG Isotopic Measurement of FIB-Isolated Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

Messenger, Scott R.; Nguyen, A.; Ito, M.; Rahman, Z.

2010-01-01

The majority of presolar oxide and silicate grains are ascribed to origins in low-mass red giant and asymptotic giant branch (AGB) stars based on their O isotopic ratios. However, a minor population of these grains (< 10%) has O isotopic ratios incompatible with these sources. Two principle alternative sources are higher-than-solar metallicity (Z) stars or, more likely, supernovae (SN) [1-3]. These rare (Group 4) grains [3] are characterized by enrichments in O-18, and typically also enrichments in O-17. An even rarer subset of grains with extremely large enrichments in O-17 and smaller depletions in O-18 were suggested to come from binary star systems [2]. To establish the origins of these isotopically unusual grains, it is necessary to examine isotopic systems in addition to O. Presolar silicates offer several elements diagnostic of their stellar sources and nuclear processes, including O, Si, Mg, Fe and Ca. However, the database for minor element isotopic compositions in silicates is seriously lacking. To date only two silicate grains have been analyzed for Mg [4] or Fe [5]. One major complicating factor is their small size (average 230 nm), which greatly limits the number of measurements that can be performed on any one grain and makes it more difficult to obtain statistically relevant data. This problem is compounded because the grains are identified among isotopically solar silicates, which contribute a diluting signal in isotopic measurements [1]. Thus, relatively small isotopic anomalies are missed due to this dilution effect. By applying focused ion beam (FIB) milling, we obtain undiluted Mg isotopic ratios of isolated rare presolar silicate grains to investigate their sources.

Oxygen and iron isotope studies of magnetite produced by magnetotactic bacteria

USGS Publications Warehouse

Mandernack, K.W.; Bazylinski, D.A.; Shanks, Wayne C.; Bullen, T.D.

1999-01-01

A series of carefully controlled laboratory studies was carried out to investigate oxygen and iron isotope fractionation during the intracellular production of magnetite (Fe3O4) by two different species of magnetotactic bacteria at temperatures between 4??and 35??C under microaerobic and anaerobic conditions. No detectable fractionation of iron isotopes in the bacterial magnetites was observed. However, oxygen isotope measurements indicated a temperature-dependent fractionation for Fe3O4 and water that is consistent with that observed for Fe3O4 produced extracellularly by thermophilic Fe3+-reducing bacteria. These results contrast with established fractionation curves estimated from either high-temperature experiments or theoretical calculations. With the fractionation curve established in this report, oxygen-18 isotope values of bacterial Fe3O4 may be useful in paleoenvironmental studies for determining the oxygen-18 isotope values of formation waters and for inferring paleotemperatures.

Iron assimilation by the clam Laternula elliptica: Do stable isotopes (δ⁵⁶Fe) help to decipher the sources?

PubMed

Poigner, Harald; Wilhelms-Dick, Dorothee; Abele, Doris; Staubwasser, Michael; Henkel, Susann

2015-09-01

Iron stable isotope signatures (δ(56)Fe) in hemolymph (bivalve blood) of the Antarctic bivalve Laternula elliptica were analyzed by Multiple Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS) to test whether the isotopic fingerprint can be tracked back to the predominant sources of the assimilated Fe. An earlier investigation of Fe concentrations in L. elliptica hemolymph suggested that an assimilation of reactive and bioavailable Fe (oxyhydr)oxide particles (i.e. ferrihydrite), precipitated from pore water Fe around the benthic boundary, is responsible for the high Fe concentration in L. elliptica (Poigner et al., 2013 b). At two stations in Potter Cove (King George Island, Antarctica) bivalve hemolymph showed mean δ(56)Fe values of -1.19 ± 0.34‰ and -1.04 ± 0.39 ‰, respectively, which is between 0.5‰ and 0.85‰ lighter than the pool of easily reducible Fe (oxyhydr)oxides of the surface sediments (-0.3‰ to -0.6‰). This is in agreement with the enrichment of lighter Fe isotopes at higher trophic levels, resulting from the preferential assimilation of light isotopes from nutrition. Nevertheless, δ(56)Fe hemolymph values from both stations showed a high variability, ranging between -0.21‰ (value close to unaltered/primary Fe(oxyhydr)oxide minerals) and -1.91‰ (typical for pore water Fe or diagenetic Fe precipitates), which we interpret as a "mixed" δ(56)Fe signature caused by Fe assimilation from different sources with varying Fe contents and δ(56)Fe values. Furthermore, mass dependent Fe fractionation related to physiological processes within the bivalve cannot be ruled out. This is the first study addressing the potential of Fe isotopes for tracing back food sources of bivalves. Copyright © 2015 Elsevier Ltd. All rights reserved.

Processes in Early Planetesimals: Evidence from Ureilite Meteorites

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Downes, H.

2007-01-01

Ureilites are primitive ultramafic achondrites composed largely of olivine and pigeonite, with minor augite, carbon, sulphide and metal. They represent very early material in the history of the Solar System and form a bridge between undifferentiated chondrites and fully differentiated asteroids. They show a mixture of chemical characteristics, some of which are considered to be nebula-derived (e.g. a negative correlation between Mg/Fe and Delta O-17 that resembles that of the ordinary chondrites but at lower Delta O-17 values) whereas others have been imposed by asteroidal differentiation. Carbon isotope data show a striking negative correlation of delta C-13 values with mg# in olivine. delta C-13 also correlates positively with Delta O-17, and therefore this isotopic variation was probably also nebula-derived. Thus, oxygen and carbon isotope compositions and Fe-Mg systematics of each monomict ureilite were established before differentiation processes began. Heated by decay of short-lived radioactive isotopes, the ureilite asteroid started to melt. Metal and sulphide would have melted first, forming a Fe-S eutectic liquid, which removed chalcophile elements and incompatible siderophile elements, and basaltic melts that removed Al, Ca and the LREE. Several elements show different abundances and/or correlations with Fo content in olivine, e.g. carbon shows a positive correlation in ferroan ureilites, and a weak or even negative correlation in more magnesian compositions. HSE such as Os and Ir also show different distributions, i.e. ureilites with Fo < 82 have very scattered Os and Ir concentrations, which reach high values, whereas ureilites with Fo > 82 tend to have much less scattered and overall lower Os and Ir abundances. A similar change in elemental behaviour is shown by the Fe-Mn relations in ureilitic olivines: those with Fo contents < 85 show a good negative correlation, whereas those with Fo > 85 show much greater scatter. This suggests that a major change affected the parent body at a time when melting had reached relatively magnesian bulk compositions. We consider that this event may have been a hit and run collision in which the ureilite parent body collided with a larger object. During the collision, the ureilite mantle broke up catastrophically but re-accreted in a jumbled state around the still-intact core. Mg-rich basaltic melts that were in the process of being formed at the time of break-up were retained in part as melt clasts that re-accreted to the regolith and are found in polymict ureilites.

Fractionation of Fe isotopes during granite weathering, soil formation, and plant uptake in an Alpine glacier forefield

NASA Astrophysics Data System (ADS)

Kretzschmar, R.; Kiczka, M.; Wiederhold, J. G.; Voegelin, A.; Kraemer, S.; Bourdon, B.

2010-12-01

Iron (Fe) is not only an essential element for almost all organisms, but is also involved in many biogeochemical processes including silicate weathering and soil formation. The aim of this study was to gain a better understanding of Fe isotope fractionation during initial silicate weathering and soil formation processes. Therefore, we investigated changes in Fe speciation and Fe isotope signatures in total soils and selected Fe pools along a weathering chronosequence within an Alpine glacier forefield on granite. The sampling sites along the dated chronosequence were deglaciated since up to 150 years, and we included two additional sites which were ice-free since several thousands of years. Changes in Fe speciation were investigated using Fe K-edge X-ray absorption spectroscopy (XAS) and also qualitatively documented by optical microscopy of soil thin sections. Iron in the unweathered rock was mainly present as structural Fe in biotite, with smaller amounts in chlorite, epidote, and magnetite. Within 150 years of deglaciation, the fraction of Fe(III) relative to total Fe increased from 34 to 53%, clearly documenting oxidation of Fe(II) in primary phyllosilicates. After 100 years of deglaciation, secondary Fe(III)-oxyhydroxides were detected by XAS and were also clearly evident in soil thin sections. Elemental analysis and Fe isotope analysis of particle size fractions by MC-ICP-MS showed that the clay fractions were significantly enriched in Fe and their δ56Fe signatures were up to 0.35‰ lower than those of the bulk soils (<2 mm). In addition, the hydroxylamine-hydrochloride extractable Fe pool (1 M HA-HCl in 25% acetic acid, pH 1.5), representing mainly poorly-crystalline Fe(III)-oxyhydroxides, increased with time of deglaciation and also had a significantly (by up to 0.7‰) lighter δ56Fe signature than the respective bulk soils. Thus, our data show that weathering of primary silicates, mainly biotite and chlorite, preferentially releases light Fe isotopes during oxidative weathering, which are subsequently enriched in secondary Fe(III)-oxyhydroxides with a rather constant isotopic offset of -0.7‰ in δ56Fe relative to the bulk soils. These findings are consistent with previous laboratory experiments on silicate weathering by proton- and ligand-promoted dissolution. The data suggest a kinetic isotope effect during Fe release from primary silicates, combined with quantitative oxidation and precipitation of Fe(III) as poorly-crystalline oxyhydroxides. Analysis of plants collected along the chronosequence revealed additional fractionation towards light Fe isotopes, but the plant contribution to total Fe cycling in this young ecosystem was still minor.

Final Summary of Research Report to the National Aeronautics and Space Administration Origins of Solar Systems Program

NASA Technical Reports Server (NTRS)

O'D. Alexander, Conel

2003-01-01

The chondrites are aggregates of components (e.g. chondrules, chondrule rims and matrix) that formed in the nebula but, at present, there is no consensus on how any of these components formed or whether their formation produced or post dated the chemical fractionations between the chondrites. Chondrites are, at present, the most primitive Solar System objects available for laboratory study and the conditions under which their principle components formed would provide the most direct constraints for models of nebula formation and evolution. The conditions under which chondrules formed is of particular importance because, if their relative abundance in chondrites approximates that in the nebula, they are the products of one of the most energetic and pervasive processes that operated in the early Solar System. The goal of this proposal was to combine theoretical modeling with a comprehensive study of the elemental and isotopic compositions of the major components in unequilibrated ordinary chondrites (UOCs), with the aim of determining the conditions in the nebula at the time of their formation. The isotopes of volatile and moderately volatile elements should be particularly revealing of conditions during chondrule formation, as evaporation under most conditions would lead to isotopic mass fractionation. Modeling of chondrule and matrix formation requires the development of a kinetic model of evaporation and condensation, and calibration of this model against experiments. Cosmic spherules present an opportunity to test our evaporation models under flash heating conditions that would be difficult to simulate experimentally. However, there is surprisingly little known about the isotopic compositions of silicate cosmic spherules, and a number of questions need to be addressed. Is the range of compositions they exhibit due to evaporation? If they are, are the relative volatilities consistent with the models/experiments and are the isotopic fractionations consistent with Rayleigh conditions? For instance, do the alkalis and S evaporate prior to significant melting so that conditions did not meet the Rayleigh criteria of rapid diffusion? If so, their isotopic fractionation might be considerably suppressed. Could this mechanism of K loss apply to chondrule formation? The Fe isotopic fractionation during evaporation of silicates has not been measured, so cosmic spherules might provide a clue to whether FeO diffusion is fast enough to maintain Rayleigh conditions during evaporation. And so on.

Fast chemical and isotopic exchange of nitrogen during reaction with hot molybdenum

NASA Astrophysics Data System (ADS)

Yokochi, Reika; Marty, Bernard

2006-07-01

Molybdenum crucibles are commonly used to extract nitrogen from geological samples by induction heating. Because nitrogen is known to be reactive with certain metals (e.g., Ti and Fe), we have tested the reactivity of gaseous nitrogen with a Mo crucible held at 1800°C. The consumption of nitrogen, determined by monitoring the N2/40Ar ratio of the gas phase, varied between 25 and 100%, depending on the reaction duration. Nitrogen of the reacted gas was found to be systematically enriched in 15N relative to 14N by 10‰ compared to the initial isotopic composition, without any correlation with nitrogen consumption. We propose that a rapid isotopic exchange occurs between nitrogen originally trapped in the crucible and nitrogen from the gas phase, which modifies the isotopic composition of the reacted gas. This process can significantly bias the isotopic determination of nitrogen in rocks and minerals when a Mo furnace is used for gas extraction. Meanwhile, the rate of N-Mo chemical bonding may be controlled by the formation of nitride (rather than solid solution), a process slower than the isotopic exchange. The use of a Mo furnace for the extraction of trace nitrogen from rocks and minerals should therefore be avoided.

Application of Fe Isotopes to the Search for Life and Habitable Planets

NASA Technical Reports Server (NTRS)

Johnson, Clark M.; Beard, Brian L.; Nealson, Kenneth L.

2001-01-01

The relatively new field of Fe isotope geochemistry can make important contributions to tracing the geochemical cycling of Fe, which bears on issues such as metabolic processing of Fe, surface redox conditions, and development of planetary atmospheres and biospheres. It appears that Fe isotope fractionation in nature and the lab spans about 4 per mil (%) in Fe-56/Fe-54, and although this range is small, our new analytical methods produce a precision of +/- 0.05% on sample sizes as small as 100 ng (10(exp -7) g); this now provides us with a sufficient "signal-to-noise" ratio to make this isotope system useful. We review our work in three areas: 1) the terrestrial and lunar rock record, 2) experiments on inorganic fractionation, and 3) experiments involving biological processing of Fe. Additional information is contained in the original extended abstract.

Groundwater table fluctuations recorded in zonation of microbial siderites from end-Triassic strata

NASA Astrophysics Data System (ADS)

Weibel, R.; Lindström, S.; Pedersen, G. K.; Johansson, L.; Dybkjær, K.; Whitehouse, M. J.; Boyce, A. J.; Leng, M. J.

2016-08-01

In a terrestrial Triassic-Jurassic boundary succession of southern Sweden, perfectly zoned sphaerosiderites are restricted to a specific sandy interval deposited during the end-Triassic event. Underlying and overlying this sand interval there are several other types of siderite micromorphologies, i.e. poorly zoned sphaerosiderite, spheroidal (ellipsoid) siderite, spherical siderite and rhombohedral siderite. Siderite overgrowths occur mainly as rhombohedral crystals on perfectly zoned sphaerosiderite and as radiating fibrous crystals on spheroidal siderite. Concretionary sparry, microspar and/or micritic siderite cement postdate all of these micromorphologies. The carbon isotope composition of the siderite measured by conventional mass spectrometry shows the characteristic broad span of data, probably as a result of multiple stages of microbial activity. SIMS (secondary ion mass spectrometry) revealed generally higher δ13C values for the concretionary cement than the perfectly zoned sphaerosiderite, spheroidal siderite and their overgrowths, which marks a change in the carbon source during burial. All the various siderite morphologies have almost identical oxygen isotope values reflecting the palaeo-groundwater composition. A pedogenic/freshwater origin is supported by the trace element compositions of varying Fe:Mn ratios and low Mg contents. Fluctuating groundwater is the most likely explanation for uniform repeated siderite zones of varying Fe:Mn ratios reflecting alternating physiochemical conditions and hostility to microbial life/activity. Bacterially mediated siderite precipitation likely incorporated Mn and other metal ions during conditions that are not favourable for the bacteria and continued with Fe-rich siderite precipitation as the physico-chemical conditions changed into optimal conditions again, reflecting the response to groundwater fluctuations.

Pb isotopic constraints on the formation of the Dikulushi Cu-Pb-Zn-Ag mineralisation, Kundelungu Plateau (Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Haest, Maarten; Schneider, Jens; Cloquet, Christophe; Latruwe, Kris; Vanhaecke, Frank; Muchez, Philippe

2010-04-01

Base metal-Ag mineralisation at Dikulushi and in other deposits on the Kundelungu Plateau (Democratic Republic of Congo) developed during two episodes. Subeconomic Cu-Pb-Zn-Fe polysulphide ores were generated during the Lufilian Orogeny (c. 520 Ma ago) in a set of E-W- and NE-SW-oriented faults. Their lead has a relatively unradiogenic and internally inhomogeneous isotopic composition (206Pb/204Pb = 18.07-18.49), most likely generated by mixing of Pb from isotopically heterogeneous clastic sources. These sulphides were remobilised and enriched after the Lufilian Orogeny, along reactivated and newly formed NE-SW-oriented faults into a chalcocite-dominated Cu-Ag mineralisation of high economic interest. The chalcocite samples contain only trace amounts of lead and show mostly radiogenic Pb isotope signatures that fall along a linear trend in the 207Pb/204Pb vs. 206Pb/204Pb diagram (206Pb/204Pb = 18.66-23.65; 207Pb/204Pb = 15.72-16.02). These anomalous characteristics reflect a two-stage evolution involving admixture of both radiogenic lead and uranium during a young fluid event possibly c. 100 Ma ago. The Pb isotope systematics of local host rocks to mineralisation also indicate some comparable young disturbance of their U-Th-Pb systems, related to the same event. They could have provided Pb with sufficiently radiogenic compositions that was added to less radiogenic Pb remobilised from precursor Cu-Pb-Zn-Fe polysulphides, whereas the U most likely originated from external sources. Local metal sources are also suggested by the 208Pb/204Pb-206Pb/204Pb systematics of combined ore and rock lead, which indicate a pronounced and diversified lithological control of the immediate host rocks on the chalcocite-dominated Cu-Ag ores. The Pb isotope systematics of polysulphide mineralisation on the Kundelungu Plateau clearly record a diachronous evolution.

Equilibrium isotopic fractionation of copper during oxidation/reduction, aqueous complexation and ore-forming processes: Predictions from hybrid density functional theory

NASA Astrophysics Data System (ADS)

Sherman, David M.

2013-10-01

Copper exists as two isotopes: 65Cu (∼30.85%) and 63Cu (∼69.15%). The isotopic composition of copper in secondary minerals, surface waters and oxic groundwaters is 1-12‰ heavier than that of copper in primary sulfides. Changes in oxidation state and complexation should yield substantial isotopic fractionation between copper species but it is unclear to what extent the observed Cu isotopic variations reflect equilibrium fractionation. Here, I calculate the reduced partition function ratios for chalcopyrite (CuFeS2), cuprite (Cu2O), tenorite (CuO) and aqueous Cu+, Cu+2 complexes using periodic and molecular hybrid density functional theory to predict the equilibrium isotopic fractionation of Cu resulting from oxidation of Cu+ to Cu+2 and by complexation of dissolved Cu. Among the various copper(II) complexes in aqueous environments, there is a significant (1.3‰) range in the reduced partition function ratios. Oxidation and congruent dissolution of chalcopyrite (CuFeS2) to dissolved Cu+2 (as Cu(H2O)5+2) yields 65-63δ(Cu+2-CuFeS2) = 3.1‰ at 25 °C; however, chalcopyrite oxidation/dissolution is incongruent so that the observed isotopic fractionation will be less. Secondary precipitation of cuprite (Cu2O) would yield further enrichment of dissolved 65Cu since 65-63δ(Cu+2-Cu2O) is 1.2‰ at 25 °C. However, precipitation of tenorite (CuO) will favor the heavy isotope by +1.0‰ making dissolved Cu isotopically lighter. These are upper-limit estimates for equilibrium fractionation. Therefore, the extremely large (9‰) fractionations between dissolved Cu+2 (or Cu+2 minerals) and primary Cu+ sulfides observed in supergene environments must reflect Rayleigh (open-system) or kinetic fractionation. Finally the previously proposed (Asael et al., 2009) use of δ65Cu in chalcopyrite to estimate the oxidation state of fluids that transported Cu in stratiform sediment-hosted copper deposits is refined.

Influence of liquid structure on diffusive isotope separation in molten silicates and aqueous solutions

NASA Astrophysics Data System (ADS)

Watkins, James M.; DePaolo, Donald J.; Ryerson, Frederick J.; Peterson, Brook T.

2011-06-01

Molecular diffusion in natural volcanic liquids discriminates between isotopes of major ions (e.g., Fe, Mg, Ca, and Li). Although isotope separation by diffusion is expected on theoretical grounds, the dependence on mass is highly variable for different elements and in different media. Silicate liquid diffusion experiments using simple liquid compositions were carried out to further probe the compositional dependence of diffusive isotopic discrimination and its relationship to liquid structure. Two diffusion couples consisting of the mineral constituents anorthite (CaAl 2Si 2O 8; denoted AN), albite (NaAlSi 3O 8; denoted AB), and diopside (CaMgSi 2O 6; denoted DI) were held at 1450 °C for 2 h and then quenched to ambient pressure and temperature. Major-element as well as Ca and Mg isotope profiles were measured on the recovered quenched glasses. In both experiments, Ca diffuses rapidly with respect to Si. In the AB-AN experiment, D Ca/ D Si ≈ 20 and the efficiency of isotope separation for Ca is much greater than in natural liquid experiments where D Ca/ D Si ≈ 1. In the AB-DI experiment, D Ca/ D Si ≈ 6 and the efficiency of isotope separation is between that of the natural liquid experiments and the AB-AN experiment. In the AB-DI experiment, D Mg/ D Si ≈ 1 and the efficiency of isotope separation for Mg is smaller than it is for Ca yet similar to that observed for Mg in natural liquids. The results from the experiments reported here, in combination with results from natural volcanic liquids, show clearly that the efficiency of diffusive separation of Ca isotopes is systematically related to the solvent-normalized diffusivity - the ratio of the diffusivity of the cation ( D Ca) to the diffusivity of silicon ( D Si). The results on Ca isotopes are consistent with available data on Fe, Li, and Mg isotopes in silicate liquids, when considered in terms of the parameter D cation/ D Si. Cations diffusing in aqueous solutions display a similar relationship between isotopic separation efficiency and Dcation/D, although the efficiencies are smaller than in silicate liquids. Our empirical relationship provides a tool for predicting the magnitude of diffusive isotopic effects in many geologic environments and a basis for a more comprehensive theory of isotope separation in liquid solutions. We present a conceptual model for the relationship between diffusivity and liquid structure that is consistent with available data.

Ni Isotope Signatures in Banded Iron Formations Before, During, and After the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Wasylenki, L.; Wang, S.

2016-12-01

We have measured the Ni isotope compositions of banded iron formations (BIF) in an effort to test the hypothesis of Konhauser et al. that a decrease in supply of Ni to the Late Archean oceans may have triggered a decline in methanogen productivity [1,2]. These microorganisms are critically dependent on Ni, and their decline may have triggered a drop in atmospheric CH4 that allowed the first sustained rise of free O2 in the atmosphere at 2.4 Ga. While simultaneously considering other processes that may have controlled the Ni isotope composition of Precambrian seawater, and in turn the BIF, we are looking for a shift in δ60/58Ni over time that correlates with the decrease in BIF Ni/Fe ratios documented previously [1,2] and that possibly reflects a dramatic change in methanogen Ni status over that same time interval (2.7-2.4 Ga). Our preliminary results indicate that the ocean's Ni isotope composition has varied considerably over geologic time. Using results from an accompanying experimental study of Ni fractionation during incorporation into ferric oxyhydroxides/oxides, we can reconstruct the Ni isotope compositions of seawater from which BIF precipitated. We observe that Precambrian seawater was generally considerably enriched in light isotopes of Ni relative to modern seawater. So far we observe the widest range of δ60/58Ni values in those BIF samples aged 2.7-2.4 Ga, implying significant changes in the controls on δ60/58Ni in the Late Archean Eon and possibly much greater sensitivity of the biogeochemical cycle of Ni to perturbations in Ni sources, such as oxidative weathering of sulfides, input/output fluxes, or biological uptake. [1] Konhauser et al. (2009) Nature 458,750; [2] Konhauser et al. (2015) Astrobiology 15,804.

The GENESIS Mission: Solar Wind Isotopic and Elemental Compositions and Their Implications

NASA Astrophysics Data System (ADS)

Wiens, R. C.; Burnett, D. S.; McKeegan, K. D.; Kallio, A. P.; Mao, P. H.; Heber, V. S.; Wieler, R.; Meshik, A.; Hohenberg, C. M.; Mabry, J. C.; Gilmour, J.; Crowther, S. A.; Reisenfeld, D. B.; Jurewicz, A.; Marty, B.; Pepin, R. O.; Barraclough, B. L.; Nordholt, J. E.; Olinger, C. T.; Steinberg, J. T.

2008-12-01

The GENESIS mission was a novel NASA experiment to collect solar wind at the Earth's L1 point for two years and return it for analysis. The capsule crashed upon re-entry in 2004, but many of the solar-wind collectors were recovered, including separate samples of coronal hole, interstream, and CME material. Laboratory analyses of these materials have allowed higher isotopic precision than possible with current in-situ detectors. To date GENESIS results have been obtained on isotopes of O, He, Ne, Ar, Kr, and Xe on the order of 1% accuracy and precision, with poorer uncertainty on Xe isotopes and significantly better uncertainties on the lighter noble gases. Elemental abundances are available for the above elements as well as Mg, Si, and Fe. When elemental abundances are compared with other in situ solar wind measurements, agreement is generally quite good. One exception is the Ne elemental abundance, which agrees with Ulysses and Apollo SWC results, but not with ACE. Neon is of particular interest because of the uncertainty in the solar Ne abundance, which has significant implications for the standard solar model. Helium isotopic results of material from the different solar wind regimes collected by GENESIS is consistent with isotopic fractionation predictions of the Coulomb drag model, suggesting that isotopic fractionation corrections need to be applied to heavier elements as well when extrapolating solar wind to solar compositions. Noble gas isotopic compositions from GENESIS are consistent with those obtained for solar wind trapped in lunar grains, but have for the first time yielded a very precise Ar isotopic result. Most interesting for cosmochemistry is a preliminary oxygen isotopic result from GENESIS which indicates a solar enrichment of ~4% in 16O relative to the planets, consistent with a photolytic self-shielding phenomenon during solar system formation. Analyses of solar wind N and C isotopes may further elucidate this phenomenon. Preliminary results from GENESIS have been reported for N, and results are still pending for C.

Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oerter, Erik; Singleton, Michael; Davisson, Lee

The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

DOE PAGES

Oerter, Erik; Singleton, Michael; Davisson, Lee

2017-10-22

The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

Spatial evolution of Zn-Fe-Pb isotopes of sphalerite within a single ore body: A case study from the Dongshengmiao ore deposit, Inner Mongolia, China

NASA Astrophysics Data System (ADS)

Gao, Zhaofu; Zhu, Xiangkun; Sun, Jian; Luo, Zhaohua; Bao, Chuang; Tang, Chao; Ma, Jianxiong

2018-01-01

Analyses of sphalerite minerals from the characteristic brecciated Zn-Pb ores of the main ore body in the giant Dongshengmiao deposit have revealed variations in δ66Zn from 0.17 to 0.40‰ and in δ56Fe from -1.78 to -0.35‰. Further, the investigated pyrrhotite samples have iron that is isotopically similar to that of associated sphalerite minerals. The most distinctive pattern revealed by the zinc and iron isotope data is the lateral trend of increasing δ66Zn and δ56Fe values from southwest to northeast within the main ore body. The lead isotopic homogeneity of ore sulfides from the main ore body suggests that there is only one significant source for metal, thus precluding the mixing of multiple metal sources as the key factor controlling spatial variations of zinc and iron isotopes. The most likely control on spatial variations is Rayleigh fractionation during hydrothermal fluid flow, with lighter Zn and Fe isotopes preferentially incorporated into the earliest sulfides to precipitate from fluids. Precipitations of sphalerite and pyrrhotite have played vital roles in the Zn and Fe isotopic variations, respectively, of the ore-forming system. Accordingly, the larger isotopic variability for Fe than Zn within the same hydrothermal system perhaps resulted from a larger proportion of precipitation for pyrrhotite than for sphalerite. The lateral trend pattern revealed by the zinc and iron isotope data is consistent with the occurrence of a cystic-shaped breccia zone, which is characterized by marked elevation in Cu. The results further confirm that Zn and Fe isotopes can be used as a vectoring tool for mineral prospecting.

Anoxic groundwaters as a source of CO2 and PO4 for the coastal southern Baltic Sea: The role of an iron curtain

NASA Astrophysics Data System (ADS)

Lipka, Marko; Schneider, Jonas; Schmiedinger, Iris; Westphal, Julia; Escher, Peter; Sültenfuß, Jürgen; Dellwig, Olaf; Winde, Vera; Böttcher, Michael E.

2017-04-01

Submarine ground water discharge (SGD) into coastal ecosystems is perceived as an important source of fresh water and solutes (nutrients, metabolites, trace elements) in marine biogeochemical cycles. Less is known about its significance for the German coastal zone. We present here the results of hydrogeochemical and stable isotope geochemical studies in an area that is affected by SGD into the southern Baltic Sea. Anoxic groundwaters emerging as springs at the shore zone of the southern Baltic Sea are windows into the composition of subterrestrial ground water composition. They were investigated on a seasonal base for about five years. Water samples were analyzed for the concentrations of major and trace elements, pH, and the stable isotope ratios of water, DIC and sulfate. Newly formed precipitates in the stream bed were characterized via SEM-EDX and the stable isotope composition, as well as chemically extracted for the determination of the solid composition. The springs emerge in small pits yielding discharges of about 10 l/min each. Surrounding sediments are sandy with gravels found at depth and corresponding high permeabilities. The positions of different springs on the shore zone were geostationary during the investigation period while their shape varied due to wind- and wave action. The 2H and 18O contents of the spring waters indicate the ground water to originate from relatively young mixed meteoric waters. Dating by means of tritium and noble gases (3H, 3He, 4He, Ne) yields an age of the spring waters of about 25-32 years, with different mixing proportions of tritium-free waters. The springs are hydrogeochemically characterized by dissolved Ca, Mg, Na, bicarbonate, and sulfate, mainly reflecting the water-rock interaction with aquifer material in the recharge area. The isotope signature of DIC indicates the uptake of biogenic CO2 in the soil zone followed by the dissolution of carbonate minerals in the soil/ aquifer system. The oxygen-free ground water is rich in dissolved iron (Fe) and phosphorous (P). Iron(oxyhydr)oxide precipitates in the stream beds acting as a sink for dissolved PO4 and minor Ca. The investigation reveals that the surface precipitation on the beach leads to the formation of submarine groundwater discharge essentially free of dissolved Fe and PO4. The formation of Fe-phases in the subterranean estuary is supposed at depth influencing the release of nutrients and metals into the coastal ecosystem. Before the water passes to underground drainage into a subterranean mixing zone with brackish Baltic Sea waters, the above ground draining streams degas carbon dioxide and take up oxygen in contact with the atmosphere. Iron(oxyhydr)oxide precipitates in the stream beds acting as a sink for dissolved phosphate. Residues of Fe- oxidizing bacteria were found in the stream bed rust indicating an involvement of microbes to catalyze the dissolved Fe removal. The investigation reveals that the surface precipitation on the beach leads to the formation of submarine groundwater discharge essentially free of dissolved iron and phosphate. The formation of Fe-phases in the subterranean estuary is also supposed to take place at depth thereby influencing the release of nutrients and metals into the Baltic Sea coastal ecosystem. This work was supported by the BONUS+ project AMBER, the Leibniz IOW and the Graduiertenkolleg BALTIC TRANSCOAST.

Containing arsenic-enriched groundwater tracing lead isotopic compositions of common arsenical pesticides in a coastal Maine watershed

USGS Publications Warehouse

Ayuso, Robert A.; Foley, Nora K.; Robinson, Glipin R.; Colvin, A.S.; Lipfert, G.; Reeve, A.S.

2006-01-01

Arsenical pesticides and herbicides were extensively used on apple, blueberry, and potato crops in New England during the first half of the twentieth century. Lead arsenate was the most heavily used arsenical pesticide until it was officially banned. Lead arsenate, calcium arsenate, and sodium arsenate have similar Pb isotope compositions: 208Pb207Pb = 2.3839-2.4722, and 206Pb207Pb = 1.1035-1.2010. Other arsenical pesticides such as copper acetoarsenite (Paris green), methyl arsonic acid and methane arsonic acid, as well as arsanilic acid are widely variable in isotope composition. Although a complete understanding of the effects of historical use of arsenical pesticides is not available, initial studies indicate that arsenic and lead concentrations in stream sediments in New England are higher in agricultural areas that intensely used arsenical pesticides than in other areas. The Pb isotope compositions of pesticides partially overlap values of stream sediments from areas with the most extensive agricultural use. The lingering effects of arsenical pesticide use were tested in a detailed geochemical and isotopic study of soil profiles from a watershed containing arsenic-enriched ground water in coastal Maine. Acid-leach compositions of the soils represent lead adsorbed to mineral surfaces or held in soluble minerals (Fe- and Mn-hydroxides, carbonate, and some micaceous minerals), whereas residue compositions likely reflect bedrock compositions. The soil profiles contain labile Pb (acid-leach) showing a moderate range in 206Pb 207Pb (1.1870-1.2069), and 208Pb207Pb (2.4519-2.4876). Isotope values vary as a function of depth: the lowest Pb isotope ratios (e.g.,208Pb206Pb) representing labile lead are in the uppermost soil horizons. Lead contents decrease with depth in the soil profiles. Arsenic contents show no clear trend with depth. A multi-component mixing scheme that included lead from the local parent rock (Penobscot Formation), lead derived from combustion of fossil fuels, and possibly lead from other anthropogenic sources (e.g., pesticides), could account for Pb isotope variations in the soil profiles. In agricultural regions, our preliminary data show that the extensive use of arsenical pesticides and herbicides can be a significant anthropogenic source of arsenic and lead to stream sediments and soils.

Isotopically Heavy Low-Spin Iron in Ferropericlase at the Core-Mantle Boundary

NASA Astrophysics Data System (ADS)

Yang, H.; Lin, J. F.; Dauphas, N.; Bi, W.; Zhao, J.

2016-12-01

The iron isotope fractionation between metal and silicate at high pressure is of great interest for it is potentially responsible for the iron isotopic difference between the 2 main iron reservoir —the mantle and the core and therefore vital for estimating the bulk iron isotopic composition of the Earth. In 2009, Polyakov pioneered the use of NRIXS(Nuclear Resonant Inelastic X-ray Scat- tering) technique to investigate iron isotope fractionation at core-mantle boundary. This synchr- otron-based technique is excellent in that it can be applied to samples loaded in DACs with tens of um in size and one doesn't needs to put minerals together to reach isotope exchange equilib- rium. However, the NRIXS data used in Polyakov(2009) was scanned over a limited energy range and thus is not suitable for isotope fractionation at high pressure: the phonon modes shift with increasing pressure and a scanned energy range over 100meV is necessary. Recently, Shahar and co-workers(2016) used NRIXS with a wider energy scan range and DFT simulation to estimate the light element alloying effect on iron bonding environment at high pressure. They found that C or H may not be a major light element in the core considering only bridgmanite as a proxy of the mantle, but another lower mantle mineral ferropericlase was not taken into account. Here we report newly collected NRIXS data at sector-3 of the Advanced Photon Source. >95% 57Fe enriched powder ferropericlase((Fe0.25,Mg0.75)O) was loaded in 3-fold panoramic DACs us- ing Be gasket and c-BN insert as windows for X-ray fluorescence. The NRIXS spectra of ferroperic- lase were measured up to 94GPa across the spin transition zone. We found that the spin state of iron dramatically influences its force constants at high pressure. Low-spin iron force constants incr- ease 3 times faster than high-spin iron with pressure. Assuming linear relationship between force constants and pressure, this will lead to a fractionation of 0.147 (delta57Fe/54Fe) between ferrop- ericlase and iron metal at the core-mantle boundary conditions (4000K and 135GPa). The partition coefficient KD of Fe/Mg between bridgmanite and ferropericlase decreases with the spin transition of iron, therefore the ferropericlase would be a major iron carrier at the core-mantle boundary and fur- ther emphasize the results here.

Speciation of strontium in particulates and sediments from the Mississippi River mixing zone

NASA Astrophysics Data System (ADS)

Xu, Yingfeng; Marcantonio, Franco

2004-06-01

Sequential extractions were performed on small amounts of particulate and sediment samples (6 to10 mg) from the Mississippi River mixing zone. The leachates were analyzed for Sr concentration and 87Sr/ 86Sr isotope ratio. Mn and Fe contents were also measured as their oxyhydroxides are potential carrier phases for Sr. The largest fraction of Sr in the solid phase (particulates and sediments) was found to be present in the residual, refractory fraction (>70% of total). By comparison with the corresponding sediment, particulates appear to have higher concentrations of nonresidual, labile Sr (30% vs. 15%). Carbonate components seem to play an important role as carriers for labile Sr in particulates and sediments. Changes in the composition and content of the solid phase may significantly modify both the 87Sr/ 86Sr isotope ratio of the total labile fractions and that of the bulk components. However, such modifications, under normal conditions, exert little measurable influence on the Sr isotope composition of the dissolved phase.

Extrinsic labeling method may not accurately measure Fe absorption from cooked pinto beans (Phaseolus vulgaris): comparison of extrinsic and intrinsic labeling of beans.

PubMed

Jin, Fuxia; Cheng, Zhiqiang; Rutzke, Michael A; Welch, Ross M; Glahn, Raymond P

2008-08-27

Isotopic labeling of food has been widely used for the measurement of Fe absorption in determining requirements and evaluating the factors involved in Fe bioavailability. An extrinsic labeling technique will not accurately predict the total Fe absorption from foods unless complete isotopic exchange takes place between an extrinsically added isotope label and the intrinsic Fe of the food. We examined isotopic exchange in the case of both white beans and colored beans (Phaseolus vulgaris) with an in vitro digestion model. There are significant differences in (58)Fe/(56)Fe ratios between the sample digest supernatant and the pellet of extrinsically labeled pinto bean. The white bean digest shows significantly better equilibration of the extrinsic (58)Fe with the intrinsic (56)Fe. In contrast to the extrinsically labeled samples, both white and red beans labeled intrinsically with (58)Fe demonstrated consistent ratios of (58)Fe/(56)Fe in the bean meal, digest, supernatant, and pellet. It is possible that the polyphenolics in the bean seed coat may bind Fe and thus interfere with extrinsic labeling of the bean meals. These observations raise questions on the accuracy of studies that used extrinsic tags to measure Fe absorption from beans. Intrinsic labeling appears necessary to accurately measure Fe bioavailability from beans.

Revisiting the Si Isotope Record of Precambrian Cherts and Banded Iron Formations Using New Experimental Results

NASA Astrophysics Data System (ADS)

Zheng, X. Y.; Satkoski, A.; Beard, B. L.; Reddy, T. R.; Beukes, N. J.; Johnson, C.

2017-12-01

Precambrian Banded iron formations (BIFs) and cherts provide a record of Fe and Si biogeochemical cycling in early Earth marine environments. Much of the focus on BIFs has been the origin and pathways for Fe, but Si is intimately tied to BIF genesis through its connection to Fe minerals, either through direct structural bonding or through sorption. In the Precambrian ocean, aqueous Si contents were high, and it is increasingly recognized that Fe(III)-Si gels were the most likely precursor to BIFs [1]. It is known that Fe-Si bonding affects stable Fe isotope fractionations [2], and our recent experimental work shows this to be true for stable Si isotope fractionations [3, 4]. Silicon isotope fractionations in the Fe-Si system vary from 0‰ to nearly 4‰ in 30Si/28Si ratios with the solid phase being isotopically light depending on Fe:Si ratio [3, 4, and this study], a range far larger than that of 56Fe/54Fe ratios, highlighting the fact that Si isotopes are a highly sensitive tracer of the Fe-Si cycle. This range in Si isotope fractionation factors for the Fe-Si system can explain the full range of δ30Si values measured in Precambrian BIFs, providing a new framework to interpret Precambrian δ30Si records. Our results provide strong support for a model where Fe(III)-Si gels are the precursor phase for BIFs, which in turn affects estimates for the aqueous Fe and Si contents of the Precambrian oceans through changes in Fe-Si gel solubility. Our experiments also showed that microbial dissimilatory iron reduction (DIR) of Fe(III)-Si gel can easily produce a solid with Fe(II)-Fe(III) stoichiometry equal to magnetite, in marked contrast to abiotic incorporation of Fe(II) into Fe(III)-Si gel that resulted in a solid with Fe(II)-Fe(III) stoichiometry much lower than magnetite. Moreover, this DIR process produces a unique, negative δ30Si signature that should be eventually preserved in quartz closely associated with magnetite upon phase transformation of Fe-Si gel, and serve as a bio-signature. This experimental finding well explains the tendency of magnetite-rich BIFs to have lower δ30Si values than hematite-rich BIFs. [1] Konhauser et al., Earth-Science Rev, 2017 [2] Wu et al., GCA, 2012 [3] Zheng et al., GCA, 2016 [4] Reddy et al., GCA, 2016

Neodymium Isotope associated with planktonic foraminifera as a proxy of deglacial changes in Pacific ocean circulation

NASA Astrophysics Data System (ADS)

Hu, R.

2015-12-01

Neodymium isotopes of ferromanganese oxide coatings precipitated on planktonic foraminifera have been intensively used as a proxy for water mass reconstruction in the deep Atlantic and Indian Ocean, but their suitability is not well constrained in the Pacific and may be affected by enhanced inputs and scavenging relative to advection. In this study, Nd isotopes and Rare Earth Element (REE) concentrations of planktonic foraminifera from ~60 sites widely distributed throughout the Pacific are presented. We found that the REE pattern associated with planktonic foraminifera in our study and Fe-Mn oxides/coatings in the global ocean have a common heavy REE depleted pattern when normalized to their ambient seawater due to preferential removal of light REEs onto particles relative to heavy REEs during scavenging. The core-top ɛNd results agree with the proximal seawater compositions, indicating that planktonic foraminiferal coatings can give a reliable record of past changes in bottom water Nd isotopes in the Pacific. A good correlation between foraminifera Nd isotopes and seawater phosphate suggests that Nd with a predominantly radiogenic isotopic composition was probably added gradually along continental boundaries so that the Nd isotopic composition change paralleled the accumulation of nutrients in the deep Pacific. By confirming Nd isotopes as a reliable water mass tracer in the Pacific Ocean, this proxy is then applied to reconstruct how the water mass circulation changes during the Last Glacial Maximum (LGM). Most of the cores in deep North Pacific show essentially invariant Nd isotopic compositions during the LGM compared with core-top values, suggesting that Nd isotope of Pacific end-member did not change during glacial times. However, the LGM Southwest Pacific cores have more radiogenic ɛNd than core-tops corroborating the previous findings of reduced inflow of North Atlantic Deep Water. The Eastern Equatorial Pacific cores above ~2 km showed consistently lower LGM ɛNd values, which might suggest a reduced influence of more radiogenic North Pacific Deep Water return flow. Taken together, our results indicate a slower Pacific overturning circulation during the glacial times, and the inflow and return flow of the Pacific meridional overturning were closely linked in the glacial-interglacial cycles.

Crystal Structure and Chemical Composition of a Presolar Silicate from the Queen Elizabeth Range 99177 Meteorite

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Keller, L. P.; Rahman, Z.; Messenger, S.

2013-01-01

Mineral characterization of presolar silicate grains, the most abundant stardust phase, has provided valuable information about the formation conditions in circumstellar environments and in super-nova (SN) outflows. Spectroscopic observations of dust around evolved stars suggest a majority of amor-phous, Mg-rich olivine grains, but crystalline silicates, most of which are pyroxene, have also been observed [1]. The chemical compositions of hundreds of presolar silicates have been determined by Auger spectroscopy and reveal high Fe contents and nonstoichiometric compositions intermediate to olivine and pyroxene [2-6]. The unexpectedly high Fe contents can partly be attributed to secondary alteration on the meteorite parent bodies, as some grains have Fe isotopic anomalies from their parent stellar source [7]. Only about 35 presolar silicates have been studied for their mineral structures and chemical compositions by transmission electron microscopy (TEM). These grains display a wide range of compositions and structures, including crystalline forsterite, crystalline pyroxene, nanocrystalline grains, and a majority of amorphous nonstoichiometric grains. Most of these grains were identified in the primitive Acfer 094 meteorite. Presolar silicates from this meteorite show a wide range of Fe-contents, suggestive of secondary processing on the meteorite parent body. The CR chondrite QUE 99177 has not suffered as much alteration [8] and displays the highest presolar silicate abundance to date among carbonaceous chondrites [3, 6]. However, no mineralogical studies of presolar silicates from this meteorite have been performed. Here we examine the mineralogy of a presolar silicate from QUE 99177.

Separation of copper, iron, and zinc from complex aqueous solutions for isotopic measurement

USGS Publications Warehouse

Borrok, D.M.; Wanty, R.B.; Ridley, W.I.; Wolf, R.; Lamothe, P.J.; Adams, M.

2007-01-01

The measurement of Cu, Fe, and Zn isotopes in natural samples may provide valuable information about biogeochemical processes in the environment. However, the widespread application of stable Cu, Fe, and Zn isotope chemistry to natural water systems remains limited by our ability to efficiently separate these trace elements from the greater concentrations of matrix elements. In this study, we present a new method for the isolation of Cu, Fe, and Zn from complex aqueous solutions using a single anion-exchange column with hydrochloric acid media. Using this method we are able to quantitatively separate Cu, Fe, and Zn from each other and from matrix elements in a single column elution. Elution of the elements of interest, as well as all other elements, through the anion-exchange column is a function of the speciation of each element in the various concentrations of HCl. We highlight the column chemistry by comparing our observations with published studies that have investigated the speciation of Cu, Fe, and Zn in chloride solutions. The functionality of the column procedure was tested by measuring Cu, Fe, and Zn isotopes in a variety of stream water samples impacted by acid mine drainage. The accuracy and precision of Zn isotopic measurements was tested by doping Zn-free stream water with the Zn isotopic standard. The reproducibility of the entire column separation process and the overall precision of the isotopic measurements were also evaluated. The isotopic results demonstrate that the Cu, Fe, and Zn column separates from the tested stream waters are of sufficient purity to be analyzed directly using a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), and that the measurements are fully-reproducible, accurate, and precise. Although limited in scope, these isotopic measurements reveal significant variations in ??65Cu (- 1.41 to + 0.30???), ??56Fe (- 0.56 to + 0.34???), and ??66Zn (0.31 to 0.49???) among samples collected from different abandoned mines within a single watershed. Hence, Cu, Fe, and Zn isotopic measurements may be a powerful tool for fingerprinting specific metal sources and/or examining biogeochemical reactions within fresh water systems.

Nickel distribution and isotopic fractionation in a Brazilian lateritic regolith: Coupling Ni isotopes and Ni K-edge XANES

NASA Astrophysics Data System (ADS)

Ratié, G.; Garnier, J.; Calmels, D.; Vantelon, D.; Guimarães, E.; Monvoisin, G.; Nouet, J.; Ponzevera, E.; Quantin, C.

2018-06-01

Ultramafic (UM) rocks are known to be nickel (Ni) rich and to weather quickly, which makes them a good candidate to look at the Ni isotope systematics during weathering processes at the Earth's surface. The present study aims at identifying the Ni solid speciation and discussing the weathering processes that produce Ni isotope fractionation in two deep laterite profiles under tropical conditions (Barro Alto, Goiás State, Brazil). While phyllosilicates and to a lower extent goethite are the main Ni-bearing phases in the saprolitic part of the profile, iron (Fe) oxides dominate the Ni budget in the lateritic unit. Nickel isotopic composition (δ60Ni values) has been measured in each unit of the regolith, i.e., rock, saprock, saprolite and laterite (n = 52). δ60Ni varies widely within the two laterite profiles, from -0.10 ± 0.05‰ to 1.43 ± 0.05‰, showing that significant Ni isotope fractionation occurs during the weathering of UM rocks. Overall, our results show that during weathering, the solid phase is depleted in heavy Ni isotopes due to the preferential sorption and incorporation of light Ni isotopes into Fe oxides; the same mechanisms likely apply to the incorporation of Ni into phyllosilicates (type 2:1). However, an isotopically heavy Ni pool is observed in the solid phase at the bottom of the saprolitic unit. This feature can be explained by two hypotheses that are not mutually exclusive: (i) a depletion in light Ni isotopes during the first stage of weathering due to the preferential dissolution of light Ni-containing minerals, and (ii) the sorption or incorporation of isotopically heavy Ni carried by percolating waters (groundwater samples have δ60Ni of 2.20 and 2.27‰), that were enriched in heavy Ni isotopes due to successive weathering processes in the overlying soil and laterite units.

Characterization of Minerals of Geochronological Interest by EPMA and Atom Probe Tomography

NASA Astrophysics Data System (ADS)

Snoeyenbos, D.; Jercinovic, M. J.; Reinhard, D. A.; Hombourger, C.

2012-12-01

Isotopic and chemical dating techniques for zircon and monazite rely on several assumptions: that initial common Pb is low to nonexistent, that the analyzed domain is chronologically homogeneous, and that any relative migration of radiogenic Pb and its parent isotopes has not exceeded the analyzed domain. Yet, both zircon and monazite commonly contain significant submicron heterogeneities that may challenge these assumptions and can complicate the interpretation of chemical and isotopic data. Compositional mapping and submicron quantitative analysis by EPMA and FE-EPMA have been found to be useful techniques both for the characterization of these heterogeneities, and for quantitative geochronological determinations within the analytical limits of these techniques and the statistics of submicron sampling. Complementary to high-resolution EPMA techniques is Atom Probe Tomography (APT), wherein a specimen with dimensions of a few hundreds of nanometers is field evaporated atom by atom. The original position of each atom is identified, along with its atomic species and isotope. The result is a reconstruction allowing quantitative three-dimensional study of the specimen at the atomic scale, with low detection limits and high mass resolution. With the introduction of laser-induced thermal pulsing to achieve field evaporation, the technique is no longer limited to conductive specimens. There exists the capability to explore the compositional and isotopic structure of insulating materials at sub-nanometer resolution. Minerals of geochronological interest have been studied by an analytical method involving first compositional mapping and submicron quantitative analysis by EPMA and FE-EPMA, and subsequent use of these data to select specific sites for APT specimen extraction by FIB. Examples presented include 1) zircon from the Taconian of New England, USA, containing a fossil resorption front included between an unmodified igneous core, and a subsequent metamorphic overgrowth, with significant redistribution of U, Th, P and Y along microfracture arrays extending into the overgrowth, and 2) Paleoproterozoic monazite in thin bands <1μm wide along cleavage planes within much older (Neoarchean) monazite from the Boothia mainland of the Western Churchill Province, Canada.

Distribution of 26Al in the CR chondrite chondrule-forming region of the protoplanetary disk

NASA Astrophysics Data System (ADS)

Schrader, Devin L.; Nagashima, Kazuhide; Krot, Alexander N.; Ogliore, Ryan C.; Yin, Qing-Zhu; Amelin, Yuri; Stirling, Claudine H.; Kaltenbach, Angela

2017-03-01

We report on the mineralogy, petrography, and in situ measured oxygen- and magnesium-isotope compositions of eight porphyritic chondrules (seven FeO-poor and one FeO-rich) from the Renazzo-like carbonaceous (CR) chondrites Graves Nunataks 95229, Grosvenor Mountains 03116, Pecora Escarpment 91082, and Queen Alexandra Range 99177, which experienced minor aqueous alteration and very mild thermal metamorphism. We find no evidence that these processes modified the oxygen- or Al-Mg isotope systematics of chondrules in these meteorites. Olivine, low-Ca pyroxene, and plagioclase within an individual chondrule have similar O-isotope compositions, suggesting crystallization from isotopically uniform melts. The only exceptions are relict grains in two of the chondrules; these grains are 16O-enriched relative to phenocrysts of the host chondrules. Only the FeO-rich chondrule shows a resolvable excesses of 26Mg, corresponding to an inferred initial 26Al/27Al ratio [(26Al/27Al)0] of (2.5 ± 1.6) × 10-6 (±2SE). Combining these results with the previously reported Al-Mg isotope systematics of CR chondrules (Nagashima et al., 2014, Geochem. J. 48, 561), 7 of 22 chondrules (32%) measured show resolvable excesses of 26Mg; the presence of excess 26Mg does not correlate with the FeO content of chondrule silicates. In contrast, virtually all chondrules in weakly metamorphosed (petrologic type 3.0-3.1) unequilibrated ordinary chondrites (UOCs), Ornans-like carbonaceous (CO) chondrites, and the ungrouped carbonaceous chondrite Acfer 094 show resolvable excesses of 26Mg. The inferred (26Al/27Al)0 in CR chondrules with resolvable excesses of 26Mg range from (1.0 ± 0.4) × 10-6 to (6.3 ± 0.9) × 10-6, which is typically lower than (26Al/27Al)0 in the majority of chondrules from UOCs, COs, and Acfer 094. Based on the inferred (26Al/27Al)0, three populations of CR chondrules are recognized; the population characterized by low (26Al/27Al)0 (<3 × 10-6) is dominant. There are no noticeable trends with major and minor element or O-isotope compositions between these populations. The weighted mean (26Al/27Al)0 of 22 CR chondrules measured is (1.8 ± 0.3) × 10-6. An apparent agreement between the 26Al-26Mg ages (using weighted mean value) and the revised (using 238U/235U ratio for bulk CR chondrites of 137.7789 ± 0.0085) 207Pb-206Pb age of a set of chondrules from CR chondrites (Amelin et al., 2002, Science297, 1678) is consistent with the initial 26Al/27Al ratio in the CR chondrite chondrule-forming region at the canonical level (∼5.2 × 10-5), allowing the use of 26Al-26Mg systematics as a chronometer for CR chondrules. To prove chronological significance of 26Al for CR chondrules, measurements of Al-Mg and U-Pb isotope systematics on individual chondrules are required. The presence of several generations among CR chondrules indicates some chondrules that accreted into the CR chondrite parent asteroid avoided melting by later chondrule-forming events, suggesting chondrule-forming processes may have occurred on relatively limited spatial scales. Accretion of the CR chondrite parent body occurred at >4.0-0.3+0.5 Ma after the formation of CAIs with the canonical 26Al/27Al ratio, although rapid accretion after formation of the major population of CR chondrules is not required by our data.

Origin and Properties of Quiet-time 0.11–1.28 MeV Nucleon{sup −1} Heavy-ion Population Near 1 au

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dayeh, M. A.; Desai, M. I.; Ebert, R. W.

Using measurements from the Advanced Composition Explorer /Ultra-Low Energy Isotope Spectrometer near 1 au, we surveyed the composition and spectra of heavy ions (He-through-Fe) during quiet times from 1998 January 1 to 2015 December 31 at suprathermal energies between ∼0.11 and ∼1.28 MeV nucleon{sup −1}. The selected time period covers the maxima of solar cycles 23 and 24 and the extended solar minimum in between. We find the following. (1) The number of quiet hours in each year correlates well with the sunspot number, year 2009 was the quietest for about 82% of the time. (2) The composition of themore » quiet-time suprathermal heavy-ion population ({sup 3}He, C-through-Fe) correlates well with the level of solar activity, exhibiting SEP-like composition signatures during solar maximum, and CIR- or solar wind-like composition during solar minimum. (3) The heavy-ion (C–Fe) spectra exhibit suprathermal tails at energies of 0.11–0.32 MeV nucleon{sup −1} with power-law spectral indices ranging from 1.40 to 2.97. Fe spectra soften (steepen, i.e., spectral index increases) smoothly with increasing energies compared with Fe, indicating a rollover behavior of Fe at higher energies (0.45–1.28 MeV nucleon{sup −1}). (4) Spectral indices of Fe and O do not appear to exhibit clear solar cycle dependence. (2) and (3) imply that during IP quiet times and at energies above ∼0.1 MeV nucleon{sup −1}, the IP medium is dominated by material from prior solar and interplanetary events. We discuss the implications of these extended observations in the context of the current understanding of the suprathermal ion population near 1 au.« less

Ion probe measurements of carbon and nitrogen in iron meteorites

NASA Astrophysics Data System (ADS)

Sugiura, Naoji

1998-05-01

Carbon and nitrogen distributions in iron meteorites, their concentrations in various phases, and their isotopic compositions in certain phases were measured by secondary ion mass spectrometry (SIMS). Taenite (and its decomposition products) is the main carrier of carbon except for IAB irons where graphite and/or carbide (cohenite) may be the main carrier. Taenite is also the main carrier of nitrogen in most iron meteorites unless nitrides (carlsbergite CrN or roaldite (Fe,Ni)4N) are present. Carbon and nitrogen distributions in taenite are well correlated, unless carbides and/or nitrides are exsolved. There seem to be three types of C and N distributions within taenite. 1) These elements are enriched at the center of taenite (convex type). 2) They are enriched at the edge of taenite (concave type). 3) They are enriched near but some distance away from the edge of taenite (complex type). The case 1) is explained as equilibrium distribution of C and N in Fe-Ni alloy with M- shape nickel concentration profile. The case 2) seems to be best explained as diffusion controlled C and N distributions. In the case 3), the interior of taenite has been transformed to the a phase (kamacite or martensite). C and N were expelled from the a phase and enriched near the inner border of the remaining g phase. Such differences in the C and N distributions in taenite may reflect different cooling rates of iron meteorites. Nitrogen concentrations in taenite are quite high approaching 1 wt.% in some irons. Nitride (carlsbergite and roaldite) is present in meteorites with high nitrogen concentrations in taenite, suggesting that the nitride was formed due to supersaturation of the metallic phases with nitrogen. The same tendency is generally observed for carbon, i.e. high C concentrations in taenite correlate with the presence of carbide and/or graphite. Concentrations of C and N in kamacite are generally below detection limits. Isotopic compositions of C and N in taenite can be measured with a precision of several permil. Isotopic analysis in kamacite in most iron meteorites is not possible, because of the low concentrations. The C isotopic compositions seem to be somewhat fractionated among various phases, reflecting closure of carbon transport at low temperatures. A remarkable isotopic anomaly was observed for the Mundrabilla (IIICD anomalous) meteorite. Nitrogen isotopic compositions of taenite measured by SIMS agree very well with those of the bulk samples measured by conventional mass-spectrometry.

Subducted slab-plume interaction traced by magnesium isotopes in the northern margin of the Tarim Large Igneous Province

NASA Astrophysics Data System (ADS)

Cheng, Zhiguo; Zhang, Zhaochong; Xie, Qiuhong; Hou, Tong; Ke, Shan

2018-05-01

Incorporation of subducted slabs may account for the geochemical and isotopic variations of large igneous provinces (LIPs). However, the mechanism and process by which subducted slabs are involved into magmas is still highly debated. Here, we report a set of high resolution Mg isotopes for a suite of alkaline and Fe-rich rocks (including basalts, mafic-ultramafic layered intrusions, diabase dykes and mantle xenoliths in the kimberlitic rocks) from Tarim Large Igneous Province (TLIP). We observed that δ26 Mg values of basalts range from -0.29 to - 0.45 ‰, -0.31 to - 0.42 ‰ for mafic-ultramafic layered intrusions, -0.28 to - 0.31 ‰ for diabase dykes and -0.29 to - 0.44 ‰ for pyroxenite xenoliths from the kimberlitic rocks, typically lighter than the normal mantle source (- 0.25 ‰ ± 0.04, 2 SD). After carefully precluding other possibilities, we propose that the light Mg isotopic compositions and high FeO contents should be ascribed to the involvement of recycled sedimentary carbonate rocks and pyroxenite/eclogite. Moreover, from basalts, through layered intrusions to diabase dykes, (87Sr/86Sr)i values and δ18OV-SMOW declined, whereas ε (Nd) t and δ26 Mg values increased with progressive partial melting of mantle, indicating that components of carbonate rock and pyroxenite/eclogite in the mantle sources were waning over time. In combination with the previous reported Mg isotopes for carbonatite, nephelinite and kimberlitic rocks in TLIP, two distinct mantle domains are recognized for this province: 1) a lithospheric mantle source for basalts and mafic-ultramafic layered intrusions which were modified by calcite/dolomite and eclogite-derived high-Si melts, as evidenced by enriched Sr-Nd-O and light Mg isotopic compositions; 2) a plume source for carbonatite, nephelinite and kimberlitic rocks which were related to magnesite or periclase/perovskite involvement as reflected by depleted Sr-Nd-O and extremely light Mg isotopes. Ultimately, our study suggests that subducted slabs could make important contributions to LIP generation, and establishes a potential linkage between plate tectonics and mantle plume.

A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

NASA Astrophysics Data System (ADS)

Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

2014-12-01

Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar experiments were performed with bacterial nitric oxide reductase from Paracoccus denitrificans (cNOR). In this case both Nα and Nβ exhibited inverse isotope effects, while O had a normal isotope effect. Together, these data highlight the utility in using stable isotopes as both tracers and mechanistic probes when studying metabolic processes.

Studies on hydrogenase

PubMed Central

YAGI, Tatsuhiko; HIGUCHI, Yoshiki

2013-01-01

Hydrogenases are microbial enzymes which catalyze uptake and production of H2. Hydrogenases are classified into 10 classes based on the electron carrier specificity, or into 3 families, [NiFe]-family (including [NiFeSe]-subfamily), [FeFe]-family and [Fe]-family, based on the metal composition of the active site. H2 is heterolytically cleaved on the enzyme (E) to produce EHaHb, where Ha and Hb have different rate constants for exchange with the medium hydron. X-ray crystallography unveiled the three-dimensional structures of hydrogenases. The simplest [NiFe]-hydrogenase is a heterodimer, in which the large subunit bears the Ni-Fe center buried deep in the protein, and the small subunit bears iron-sulfur clusters, which mediate electron transfer between the Ni-Fe center and the protein surface. Some hydrogenases have additional subunit(s) for interaction with their electron carriers. Various redox states of the enzyme were characterized by EPR, FTIR, etc. Based on the kinetic, structural and spectroscopic studies, the catalytic mechanism of [NiFe]-hydrogenase was proposed to explain H2-uptake, H2-production and isotopic exchange reactions. PMID:23318679

The Oxidation State of Fe in Glasses from the Galapagos Archipelago: Variable Oxygen Fugacity as a Function of Mantle Source

NASA Astrophysics Data System (ADS)

Peterson, M. E.; Kelley, K. A.; Cottrell, E.; Saal, A. E.; Kurz, M. D.

2015-12-01

The oxidation state of the mantle plays an intrinsic role in the magmatic evolution of the Earth. Here we present new μ-XANES measurements of Fe3+/ΣFe ratios (a proxy for ƒO2) in a suite of submarine glasses from the Galapagos Archipelago. Using previously presented major, trace, and volatile elements and isotopic data for 4 groups of glass that come from distinct mantle sources (depleted upper mantle, 2 recycled, and a primitive mantle source) we show that Fe3+/ΣFe ratios vary both with the influence of shallow level processes and with variations in mantle source. Fe3+/ΣFe ratios increase with differentiation (i.e. decreasing MgO), but show a large variation at a given MgO. Progressive degassing of sulfur accompanies decreasing Fe3+/ΣFe ratios, while assimilation of hydrothermally altered crust (as indicated by increasing Sr/Sr*) is shown to increase Fe3+/ΣFe ratios. After taking these processes into account, there is still variability in the Fe3+/ΣFe ratios of the isotopically distinct sample suites studied, yielding a magmatic ƒO2 that ranges from ΔQFM = +0.16 to +0.74 (error < 0.5 log units) and showing that oxidation state varies as a function of mantle source composition in the Galapagos hotspot system. After correcting back to a common MgO content = 8.0 wt%, the trace element depleted group similar to MORB (ITD), and the group similar to Pinta (WD = high Th/La, Δ7/4, Δ8/4 ratios) show Fe3+/ΣFe ratios within the range of MORB (average ITD = 0.162 ± 0.003 and WD = 0.164 ± 0.006). Another trace element enriched group similar to Sierra Negra and Cerro Azul (ITE = enriched Sr and Pb isotopes) shows evidence of mixing between oxidized and reduced sources (ITE oxidized end-member = 0.177). This suggests that mantle sources in the Galapagos that are thought to contain recycled components (i.e., WD and ITE groups) have distinct oxidation states. The high 3He/4He Fernandina samples (HHe group) are shown to be the most oxidized (ave. 0.175 ± 0.006). With C/3He ratios an order of magnitude greater than MORB this suggests that the primitive mantle is a more carbonated and oxidized source than the depleted upper mantle.

Using trace element content and lead isotopic composition to assess sources of PM in Tijuana, Mexico

NASA Astrophysics Data System (ADS)

Salcedo, D.; Castro, T.; Bernal, J. P.; Almanza-Veloz, V.; Zavala, M.; González-Castillo, E.; Saavedra, M. I.; Perez-Arvízu, O.; Díaz-Trujillo, G. C.; Molina, L. T.

2016-05-01

PM2.5 samples were collected at two urban sites (Parque Morelos (PQM) and CECyTE (CEC)) in Tijuana during the Cal-Mex campaign from May 24 to June 5, 2010. Concentration of trace elements (Mg, Al, Ti, V, Mn, Fe, Co, Ni, Zn, Cu, Ga, As, Se, Rb, Sr, Mo, Cd, Sn, Sb, Ba, La, Ce, and Pb), and Pb isotopic composition were determined in order to study the sources of PM impacting each site. Other chemical analysis (gravimetric, elemental and organic carbon (EC/OC), and polycyclic aromatic hydrocarbons (PAHs)), were also performed. Finally, back-trajectories were calculated to facilitate the interpretation of the chemical data. Trace elements results show that CEC is a receptor site affected by mixed regional sources: sea salt, mineral, urban, and industrial. On the other hand, PQM seems to be impacted mainly by local sources. In particular, Pb at CEC is of anthropogenic, as well as crustal origin. This conclusion is supported by the lead isotopic composition, whose values are consistent with a combination of lead extracted from US mines, and lead from bedrocks in the Mexican Sierras. Some of the time variability observed can be explained using the back-trajectories.

[Determination of 235U/238U isotope ratios in camphor tree bark samples by MC-ICP-MS after separation of uranium from matrix elements].

PubMed

Wang, Xiao-Ping; Zhang, Ji-Long

2007-07-01

Twelve camphor (cinnamomum camphora) tree bark samples were collected from Hiroshima and Kyoto, and the matrix element composition and morphology of the outer surface of these camphor tree bark samples were studied by EDXS and SEM respectively. After a dry decomposition, DOWEX 1-X8 anion exchange resin was used to separate uranium from matrix elements in these camphor tree bark samples. Finally, 235U/238 U isotope ratios in purified uranium solutions were determined by MC-ICP-MS. It was demonstrated that the outer surface of these camphor tree bark samples is porous and rough, with Al, Ca, Fe, K, Mg, Si, C, O and S as its matrix element composition. Uranium in these camphor tree bark samples can be efficiently separated and quantitatively recovered from the matrix element composition. Compared with those collected from Kyoto, the camphor tree bark samples collected from Hiroshima have significantly higher uranium contents, which may be due to the increased aerosol mass concentration during the city reconstruction. Moreover, the 235 U/23.U isotope ratios in a few camphor tree bark samples collected from Hiroshima are slightly higher than 0.007 25.

Ibitira: A basaltic achondrite from a distinct parent asteroid

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.

2004-01-01

I have done detailed petrologic study of Ibitira, nominally classified as a basaltic eucrite. The Fe/Mn ratio of Ibitira pyroxenes with <10 mole % wollastonite component is 36.4 0.4, and is well-resolved from those of five basaltic eucrites studied for comparison; 31.2-32.2. Data for the latter completely overlap. Ibitira pyroxenes have lower Fe/Mg than the basaltic eucrite pyroxenes. Thus, the higher Fe/Mn ratio does not reflect a simple difference in oxidation state. Ibitira also has an oxygen isotopic composition, alkali element contents and a Ti/Hf ratio that distinguish it from basaltic eucrites. These differences support derivation from a distinct parent asteroid. Ibitira is the first recognized representative of the fifth known asteroidal basaltic crust.

Vapor pressures and evaporation coefficients for melts of ferromagnesian chondrule-like compositions

NASA Astrophysics Data System (ADS)

Fedkin, A. V.; Grossman, L.; Ghiorso, M. S.

2006-01-01

To determine evaporation coefficients for the major gaseous species that evaporate from silicate melts, the Hertz-Knudsen equation was used to model the compositions of residues of chondrule analogs produced by evaporation in vacuum by Hashimoto [Hashimoto A. (1983) Evaporation metamorphism in the early solar nebula-evaporation experiments on the melt FeO-MgO-SiO 2-CaO-Al 2O 3 and chemical fractionations of primitive materials. Geochem. J. 17, 111-145] and Wang et al. [Wang J., Davis A. M., Clayton R. N., Mayeda T. K., Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO-MgO-SiO 2-CaO-Al 2O 3-TiO 2 rare earth element melt system. Geochim. Cosmochim. Acta 65, 479-494], in vacuum and in H 2 by Yu et al. [Yu Y., Hewins R. H., Alexander C. M. O'D., Wang J. (2003) Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts. Geochim. Cosmochim. Acta 67, 773-786], and in H 2 by Cohen et al. [Cohen B. A., Hewins R. H., Alexander C. M. O'D. (2004) The formation of chondrules by open-system melting of nebular condensates. Geochim. Cosmochim. Acta 68, 1661-1675]. Vapor pressures were calculated using the thermodynamic model of Ghiorso and Sack [Ghiorso M. S., Sack R. O. (1995) Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures. Contrib. Mineral. Petrol. 119, 197-212], except for the late, FeO-free stages of the Wang et al. (2001) and Cohen et al. (2004) experiments, where the CMAS activity model of Berman [Berman R. G. (1983) A thermodynamic model for multicomponent melts, with application to the system CaO-MgO-Al 2O 3-SiO 2. Ph.D. thesis, University of British Columbia] was used. From these vapor pressures, evaporation coefficients ( α) were obtained that give the best fits to the time variation of the residue compositions. Evaporation coefficients derived for Fe (g), Mg (g), and SiO (g) from the Hashimoto (1983) experiments are similar to those found by Alexander [Alexander C. M. O'D. (2004) Erratum. Meteoritics Planet. Sci. 39, 163] in his EQR treatment of the same data and also adequately describe the FeO-bearing stages of the Wang et al. (2001) experiments. From the Yu et al. (2003) experiments at 1723 K, αNa = 0.26 ± 0.05, and αK = 0.13 ± 0.02 in vacuum, and αNa = 0.042 ± 0.020, and αK = 0.017 ± 0.002 in 9 × 10 -5 bar H 2. In the FeO-free stages of the Wang et al. (2001) experiments, αMg and αSiO are significantly different from their respective values in the FeO-bearing portions of the same experiments and from the vacuum values obtained at the same temperature by Richter [Richter F. M., Davis A. M., Ebel D. S., Hashimoto A. (2002) Elemental and isotopic fractionation of Type B calcium-, aluminum-rich inclusions: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta 66, 521-540] for CMAS compositions much lower in MgO. When corrected for temperature, the values of αMg and αSiO that best describe the FeO-free stages of the Wang et al. (2001) experiments also adequately describe the FeO-free stage of the Cohen et al. (2004) H 2 experiments, but αFe that best describes the FeO-bearing stage of the latter experiment differs significantly from the temperature-corrected value derived from the Hashimoto (1983) vacuum data.

Non-traditional stable isotope behaviors in immiscible silica-melts in a mafic magma chamber.

PubMed

Zhu, Dan; Bao, Huiming; Liu, Yun

2015-12-01

Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ(57)Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ(57)Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ(57)Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted.

Variations in Fe and S redox states in ocean island basalts

NASA Astrophysics Data System (ADS)

Brounce, M. N.; Peterson, M. E.; Stolper, E. M.; Eiler, J. M.

2016-12-01

The chemical and isotopic compositions of ocean island basalts (OIB) suggest that their mantle sources contain imprints of subducted sediments, altered oceanic crust, undegassed mantle, and/or residues of continental crust formation. By comparing the oxygen fugacities (fO2) of OIBs to the extent to which they contain these imprints, it may be possible to relate specific compositions to spatial and temporal variations in source fO2. To explore this, we present µ-XANES measurements of the oxidation states of Fe and S from pillow glass and olivine-hosted melt inclusions from the Reykjanes Ridge, Mauna Kea, Kilauea, Loihi, Hawaiian South Arch, Reunion Island, and the Ontong Java Plateau; we then compare these measurements with previous determinations of the chemical and isotopic compositions of these OIBs. Reykjanes Ridge and Ontong Java glasses have Fe and S redox states that are similar to MORBs; although these glasses show evidence for assimilation of seawater or crustal components, there is no relationship between indices of assimilation (18O/16O, Cl) and Fe or S redox states. This indicates that assimilation in these settings does not have a major effect on magmatic fO2. Mauna Kea and Kilauea glasses affected by S+H2O degassing have decreased Fe and S redox states, but the least degassed samples from both volcanoes are similar to each other and more oxidized than MORB, Reykjanes Ridge, and Ontong Java glasses. Loihi and South Arch glasses have not lost significant S and H2O to degassing, and they record fO2s similar to the least degassed Mauna Kea and Kilauea glasses. Olivine-hosted melt inclusions from Reunion range in Fe redox from similar to MORBs to more oxidized than Hawaiian volcanoes. These data demonstrate that OIBs are heterogeneous in Fe and S redox states. Although more data are needed for the various OIB end members, with the exception of the two most reduced glasses from Reunion, the data thus far suggest a rough positive correlation between 87Sr/86Sr ratios and Fe and S redox states. If this correlation holds up, it would be consistent with EMI and/or EMII end members having fO2s more oxidized than the upper mantle sources of MORBs, perhaps because these end members contain subducted sediments and/or oceanic crust that were previously oxidized during exposure to the H2O- and O2-rich conditions at Earth's surface.

Constraining mechanisms of quartz precipitation in the Archean ocean using silicon isotopes

NASA Astrophysics Data System (ADS)

Brengman, L. A.; Fedo, C.; Martin, W.

2017-12-01

To constrain reservoir values for the Archean silica cycle we measured silicon isotope compositions (δ30Si) of 28 igneous, siliciclastic sedimentary, hydrothermal, and chemical sedimentary rock samples from three Archean greenstone belts representing different times (>3.7 - 2.7 Ga) and tectonic regimes. We posit that silicon isotope compositions of quartz (746 analyses measured in situ by secondary ion mass spectrometry at the NORDSIM facility) are linked to changes in key geochemical parameters that vary within local depositional environments, coupled with a dependency on size and δ30Si composition of the source reservoir. Collectively, siliceous precipitates from even a single basin span a 7‰ range in δ30Si values. Such heterogeneity, regardless of basinal position or presence of Fe-phases demonstrates that δ30Si values of chemical sediments are linked to neither a well-mixed water column representative of a single ocean composition, nor a specific time in Earth history. Combining data from all three greenstone belts we discern that all measured Algoma-type iron formation (IF) and about 50% of associated chert samples possess δ30Si values <0‰, while the majority of silicified volcanic rocks and the remaining 50% of chert samples have δ30Si values >0‰. Negative values of Algoma-type IF can be explained by rate-dependent fractionation during precipitation and/or adsorption to Fe/Al. Combined experimental and natural data for quartz precipitates suggest slow precipitation rates coupled with closed system, Rayleigh type distillation could produce the isotopically heavy values. Such results suggest the quartz-precipitating fluid for these rocks evolves from an open system in disequilibrium, to one that is closed, and in equilibrium with the host rock. In contrast to the static range of values through time for Algoma-type IF, associated cherts and silicified rocks, compiled data for Superior-type IF from 3 - 1.8 Ga record a systematic increasing trend from dominantly 30Si-depleted to 30Si-enriched values over the Archean-Paleoproterozoic transition. Interpreted in the context of our provisional, mass-balance based flux model for the Precambrian silicon cycle, we conclude the 30Si-enrichment to reflect the evolving δ30Si composition of the ocean due to the addition of continentally derived silica.

C Diffusion in Fe: Isotope Effects and Other Complexities

NASA Astrophysics Data System (ADS)

Watson, E. B.; Muller, T.; Trail, D.; Van Orman, J. A.; Papineau, D.

2011-12-01

Carbon is a minor but significant component of iron meteorites, and probably also of planetary cores, including that of Earth. Given the dynamical nature of core-forming processes, C diffusion in the metal phase may play a role in C equilibration between Fe-Ni metal and silicate, carbide or oxide at some stage. Despite its relevance to steel-making, C diffusion in Fe is not well characterized over the range of conditions of interest in planetary bodies, and the likelihood of an isotope mass effect on C diffusion has not been explored. The prospect of incomplete diffusive equilibration of carbon in Fe-Ni raises the possibility that carbon isotopes might be fractionated by diffusion during core formation and evolution-perhaps to an extent that could affect the C isotope ratio of the bulk silicate Earth. Here we report results of preliminary experiments addressing the isotopic mass effect on C diffusion in Fe. Initial low-pressure experiments were conducted by placing a layer of ^{13}C-enriched graphite ( 20% ^{13}C) at the end of a high-purity, polycrystalline Fe cylinder in a silica glass container. These diffusion couples were run in a piston-cylinder apparatus at 1.5 GPa and 1000-1100^{o}C for several hours, and the resulting C-uptake profiles in the Fe cylinders were measured by EPMA and SIMS. In traverses moving away from the original C-Fe interface, total carbon decreases monotonically and becomes significantly lighter, indicating that ^{12}C diffuses faster than ^{13}C. Preliminary estimates of β in the relative isotope diffusivity relation D_{1}/D_{2} = [M_{2}/M_{1}]^{β} (where D is diffusivity and M is mass of isotopes 1 and 2) suggest values as high as 0.5, corresponding to predictions for gaseous diffusion. Isotope mass effects approaching this magnitude have been observed previously for diffusion in metals, and are expected to be highest for interstitial diffusion. Such a high β value will lead to major C isotope fractionation in some partial equilibration scenarios in planets and meteorite parent bodies. Caution is warranted at this point, however, because D_{carbon} is sensitive to carbon concentration, complicating quantification of the isotope effect.

Kinetically Relevant Steps and H2/D2 Isotope Effects in Fischer-Tropsch Synthesis on Fe and Co Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ojeda, Manuel; Li, Anwu; Nabar, Rahul P.

2010-11-25

H2/D2 isotope effects on Fischer-Tropsch synthesis (FTS) rate and selectivity are examined here by combining measured values on Fe and Co at conditions leading to high C5+ yields with theoretical estimates on model Fe(110) and Co(0001) surfaces with high coverages of chemisorbed CO (CO*). Inverse isotope effects (rH/rD < 1) are observed on Co and Fe catalysts as a result of compensating thermodynamic (H2 dissociation to H*; H* addition to CO* species to form HCO*) and kinetic (H* reaction with HCO*) isotope effects. These isotopic effects and their rigorous mechanistic interpretation confirm the prevalence of H-assisted CO dissociation routes onmore » both Fe and Co catalysts, instead of unassisted pathways that would lead to similar rates with H2 and D2 reactants. The small contributions from unassisted pathways to CO conversion rates on Fe are indeed independent of the dihydrogen isotope, as is also the case for the rates of primary reactions that form CO2 as the sole oxygen rejection route in unassisted CO dissociation paths. Isotopic effects on the selectivity to C5+ and CH4 products are small, and D2 leads to a more paraffinic product than does H2, apparently because it leads to preference for chain termination via hydrogen addition over abstraction. These results are consistent with FTS pathways limited by H-assisted CO dissociation on both Fe and Co and illustrate the importance of thermodynamic contributions to inverse isotope effects for reactions involving quasi-equilibrated H2 dissociation and the subsequent addition of H* in hydrogenation catalysis, as illustrated here by theory and experiment for the specific case of CO hydrogenation.« less

Iron Isotope Variations in Reduced Groundwater and in Drinking Water Supplies: A Case Study of Hanoi, Vietnam

NASA Astrophysics Data System (ADS)

Teutsch, N.; Berg, M.; von Gunten, U.; Halliday, A.

2004-12-01

In reduced groundwater iron is involved in biotic and abiotic transformation processes, both of which could lead to iron isotope fractionation. The reduced groundwater aquifers in the area of the Vietnamese capital of Hanoi are the main drinking water sources for the city. These groundwaters contain arsenic, which imposes a serious health threat to millions of people. Dissolved arsenic is related to the reducing conditions prevalent in the groundwater, and iron and arsenic contents are correlated in the sediments. We are employing iron isotope composition as a tool to better understand the processes leading to the transformation of iron in the groundwater and its role in various biogeochemical processes in reduced environments. Drinking water is supplied to the city of Hanoi from several water treatment plants (WTP) which pump the raw groundwater from a lower aquifer, while the rural surroundings pump untreated groundwater from an upper aquifer by private tubewells. Surface water from the Red River delta is the main source of recharge to these two aquifers. Due to high content of particulate natural organic matter (NOM) in the sediment leading to extensive microbial activity, the groundwaters are anoxic and rich in dissolved iron(II). The iron(II) removal in the WTPs is carried by a multi-step treatment including aeration, settling, filtration, and chlorination. We have collected natural groundwater samples for isotopic analysis from two aquifers at several locations, a groundwater depth profile and its corresponding sediment phases from the upper aquifer and the underlying aquitard, raw and treated water from several WTPs, as well as the corresponding iron(III) precipitates. The iron concentrations of groundwaters analysed in this study range from 3 to 28 mg/L and δ 57Fe (57/54 deviation from IRMM 014) values vary between -1.2 and +1.5 ‰ . The sediment depth profile has a δ 57Fe around +0.3 ‰ , which implies that the high values obtained in the groundwater nearby (+0.9 - +1.2 ‰ ) cannot be explained by a simple reductive dissolution process, which would be expected to favour the lighter Fe isotopes. Removal of iron in the WTP is followed by a strong decrease of δ 57Fe, probably due to formation of heavier Fe(III) phases. High δ 57Fe values are found in both aquifers and correspond to high concentrations of iron in the groundwater. We hypothesize that the iron isotopic variations observed so far are an indication for iron sources and transformation processes that could not be detected by only measuring dissolved iron concentrations. Current investigations will further explore this hypothesis.

Evidences for Cu and Zn Isotope Fractionation in Sediments and Particulate Suspended Matter of the Scheldt Estuary

NASA Astrophysics Data System (ADS)

Petit, J.; Mattielli, N.; de Jong, J.; Chou, L.

2004-05-01

Recent developments in MC-ICP-MS technology allow high precision measurements of heavy stable isotopes, such as Cu and Zn isotopes, which have been shown to undergo biotic or abiotic fractionation (1). Application of Zn isotopes to the study of aquatic ecosystems has already shown some interesting perspectives in their potential use as biogeochemical tracers in deep ocean carbonates (2) or Fe-Mn nodules (3). However, until now no investigation of possible Cu and Zn isotopic fractionation has been carried out within estuaries that are important pathways for hydrological and geochemical cycling of metals. Cu and Zn isotope geochemistry has been studied in sandy to loamy surface sediments (top 20 cm) and in suspended particulate matter (SPM) along a transect in a strong tidal estuary, the Scheldt estuary situated in Belgium and the Netherlands (November 2002). Further to separation of Cu, Fe and Zn by one step ion-exchange chromatography, Cu and Zn isotopic ratios are measured with a "Nu-Plasma" MC-ICP-MS. Instrumental mass bias is corrected using reference materials (Zn JMC, Cu NIST SRM 976 and Ga JMC standard) by simultaneous standard-sample bracketing and external normalization (500 ppb Zn doping for Cu isotopic analyses in static mode and 250 ppb Ga doping for Zn isotopic analyses in dynamic mode), together with a Ni correction. These methods lead to long-term reproducibility (2σ at 95 % confidence level) of ± 0.07 per mil for δ 66Zn (n=100 over 7 analysis sessions) and ± 0.06 per mil for δ 65Cu (n=120 over 8 analysis sessions) for 500 ppb of reference material. Average beam intensities are 6 V/ppm. Precise and reproducible results are obtained for concentration as low as 100 ppb for Cu and Zn. Expected Cu and Zn enrichment in SPM (120 ppm and 1200 ppm respectively) and sediments (being 6 to 10 times lower than SPM) in the upper estuary and progressive decrease in metal content by mixing downstream of the maximum turbidity zone (MTZ, around 5 psu) are observed. Results show that variations in Cu and Zn isotopic composition are smaller in SPM (δ 66Zn varying from 0.35 to 0.17 and δ 65Cu from -0.13 to 0.18) than in sediments. Cu and Zn isotopic signatures of sediments show a clear trend of lighter isotopes removal from the MTZ seaward with δ 66Zn varying from 0.21 at 2 psu to 1.11 per mil at 33 psu (and δ 65Cu = -0.37 to 0.24). In contrast, Zn isotopic compositions in SPM are more homogeneous with average δ 66Zn of 0.24 ± 0.18 over all the transect. Cu isotopic composition in SPM are very constant downstream of the MTZ with average δ 65Cu =-0.06 ± 0.08 but become more scattered within MTZ (varying from -0.04 to 0.18). These preliminary results pinpoint important variations in Cu and Zn isotopic compositions within estuarine systems and contrasted isotopic signatures in Cu and Zn between SPM and sediments. Results suggest the important role of early diagenesis in the isotope geochemistry of heavy metals in estuarine environment. This study provides a stepping stone for further investigation of interacting processes involved in controlling the cycling of metals in the Scheldt estuary. (1) Zhu et al., Earth Planet. Sci. Lett. 200 (2002), 47-62 (2) Pichat et al., Earth Planet. Sci. Lett. 6598 (2003), 1-12 (3) Maréchal et al., Geochem. Geophys. Geosyt., 1 (2000), GC000029

How to explain Si isotopes of chert?

NASA Astrophysics Data System (ADS)

Liu, Y.

2016-12-01

The variations of d30Si values in diagenetic chert and chert- associated BIFs over time can be used to reconstruct the environmental conditions of the early Earth, and become a hot topic in the Si isotope society. However, there are several different views of explaining the variation of d30Si values over time. Moreover, there are disputes in explaining the distribution of Si isotope in several main reservoirs in surface systems. Those disagreements are caused by lacking key Si isotope fractionation factors associated with the formation processes of chert and its altered products. There are many unexplained observations about Si isotope distributions in Earth's surface systems (Opfergelt and Delmelle, 2012). For example, the deduced Si isotope equilibrium fractionation factors by Rayleigh model at ambient temperature between clay and the solution D30Siclay-solution = -1.5 ‰ and -2.05 ‰ (Hughes et al., 2013) obviously disagree with common sense, which dictates that stiffer chemical bonds will enrich heavier isotopes, i.e., the precipitated minerals will preferentially incorporate heavy isotopes relative to aqueous H4SiO4 due to their shorter Si-O bonds. Another similar case is the fractionation between quartz and solution. Most field observations suggested that solution will be enriched with heavier Si isotope compared to quartz, conflicting to the fact that quartz is the one with much shorter Si-O bonds than aqueous H4SiO4 (ca. 1.610Å vs. 1.639Å). Here we provide equilibrium and kinetic Si isotope fractionation factors associated with the formation of amorphous quartz and other secondary minerals in polymerization, co-precipitation and adsorption processes. The adsorption processes of silica gel to Fe-hydroxides have been carefully examined. The Si isotope fractionations due to the formation of mono-dentate to quadru-dentate adsorbed Fe-Si complexes have been calculated. These data can explain well the experimental observations (e.g., Zheng et al., 2016) and provide further insights into such processes. With the knowledge of Si isotope fractionations of those processes, we can quantitatively evaluate the net Si isotope fractionation during the chert formation processes and can link the Si isotope composition of chert to that of seawater from now to early Archean.

Nd and Pb isotopic Mediterranean overflow water signature in the Gulf of Cadiz over the Mio-Pliocene boundary.

NASA Astrophysics Data System (ADS)

van der Schee, Marlies; Gutjahr, Marcus; Sierro, Francisco Javier; Flecker, Rachel; Jiménez Espejo, Francisco; Hodell, David; Abel Flores, Jose

2014-05-01

Marine gateways play a major role in ocean circulation and therefore climate. Currently, it is thought that there was no significant Mediterranean Overflow Water (MOW) in the Gulf of Cadiz during the Messinian Salinity Crisis (MSC) in the Late Miocene. However, a connection has supplied the Mediterranean with enough salt to precipitate the extensive evaporates preserved across the basin. After the MSC, the Mediterranean overflow was re-established through the Straits of Gibraltar. Today, MOW follows the continental slope of the Iberian Peninsula at a depth of 500-800 m in the Gulf of Cadiz northwards. In this study, lead and neodymium isotopes are used as water mass tracers for Mio-Pliocene MOW and NE Atlantic water in the Gulf of Cadiz. Complementary biostratigraphic data, carbon and oxygen isotopes and trace elements are presented alongside to corroborate our findings. Here we present a detailed authigenic Fe-Mn oxyhydroxide-derived Pb and Nd isotope records extracted from ~5.85 - 4.0 million year old bulk sediments recovered in IODP Core U1387C in the Gulf of Cadiz (current water depth 559 m). MOW and NE Atlantic waters have different Nd and Pb isotopic characteristics allowing for the identification of bottom water mass provenance changes and mixing proportions at the core site. The properties of the water bodies during the given time period are defined by Fe-Mn crust and marine sediment signatures. We also examine the natural variability within a single precession cycle. In order to confirm that the bulk sediment data indeed reliably reflects the primary composition of the bottom water masses, several bulk sediment samples are compared to foraminifera-derived Nd isotopic compositions. Results from the Messinian show a trend from isotope compositions that are more typical for MOW towards compositions more typical for the NE Atlantic. Subsequently, this trend reverses. After this, around 5.6 Ma an abrupt shift from MOW to more NE Atlantic characteristics is visible. The last abrupt switch is mainly visible in the lead isotopic record. The first trend may bear evidence for the presence of Mediterranean water in the Gulf of Cadiz at the same time of the deposition of the Lower Evaporites precipitation in the Mediterranean basin. The abrupt change to more Atlantic values around 5.6 Ma, during the deposition of the Upper Evaporites in the Mediterranean, could reflect a change from a two-layer flow gateway system with a MOW to a one layer inflow of Atlantic water in the Mediterranean. Mediterranean-Atlantic exchange through the Straits of Gibraltar, is thought to have been established after the MSC. No geochemical record of MOW is known immediately after the opening of the Straits. The radiogenic records may reveal the timing of Pliocene MOW and a strengthening at ~4.2-4.5 Ma at the same time of the onset of the contourite depositional system in the Gulf of Cadiz.

Coordinated Isotopic and Mineral Characterization of Highly Fractionated 18O-Rich Silicates in the Queen Alexandra Range 99177 CR3 Chondrite

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Keller, L. P.; Messenger, S.; Rahman, Z.

2016-01-01

Carbonaceous chondrites contain a mixture of solar system condensates, pre-solar grains, and primitive organic matter. Each of these materials record conditions and processes in different regions of the solar nebula, on the meteorite parent body, and beyond the solar system. Oxygen isotopic studies of meteorite components can trace interactions of distinct oxygen isotopic reservoirs in the early solar system and secondary alteration processes. The O isotopic compositions of the earliest solar system condensates fall along a carbonaceous chondrite anhydrous mineral (CCAM) line of slope approximately 1 in a plot of delta 17O against delta 18O. This trend is attributed to mixing of material from 16O-poor and 16O-rich reservoirs. Secondary processing can induce mass-dependent fractionation of the O isotopes, shifting these compositions along a line of slope approximately 0.52. Substantial mass-dependent fractionation of O isotopes has been observed in secondary minerals in CAIs, calcite, and FUN inclusions. These fractionations were caused by significant thermal or aqueous alteration. We recently reported the identification of four silicate grains with extremely fractionated O isotopic ratios (delta 18O equals 37 - 55 per mille) in the minimally altered CR3 chondrite QUE 99177. TEM analysis of one grain indicates it is a nebular condensate that did not experience substantial alteration. The history of these grains is thus distinct from those of the aforementioned fractionated materials. To constrain the origin of the silicate grains, we conducted further Mg and Fe isotopic studies and TEM analyses of two grains.

Equilibrium carbon and hydrogen isotope fractionation in iron

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2009-12-01

Recent theoretical and experimental studies (e.g., [1-3]) have suggested that Si- and Fe-isotopic signatures can be used to characterize the compositions and conditions of segregation of metallic cores in planetary interiors. This study expands the theoretical framework to include carbon and hydrogen, which may also be alloying elements. Hydrogen (D/H) and carbon (13C/12C) fractionations in iron-rich metallic melts are estimated by modeling analogous iron-rich crystals, i.e., dhcp-FeH and η-Fe2C. C- and H-atoms in these crystals are completely coordinated by iron. The driving energy for equilibrium fractionation is assumed to come from the reduction of vibrational frequencies when heavy isotopes are substituted for light ones; vibrations are assumed to be harmonic. This treatment is crude at high temperature, and for the relatively anharmonic vibrations typical of hydrogen-bearing substances, but may provide a reasonably accurate, semi-quantitative approximation of real fractionation behavior. Vibrational frequencies of all crystals are modeled with density functional theory, using gradient-corrected functionals and ultrasoft pseudopotentials. For both carbon and hydrogen, the models suggest that the metal phase will be strongly depleted in heavy isotopes. At 2000 K, 1 atm, η-Fe2C will have 3‰ lower 13C/12C than coexisting diamond. Combining this result with previous high-temperature theoretical and experimental studies (e.g., [4]), metal-graphite fractionation is expected to be very similar, while metal-CO2 fractionation will be almost twice as large, ca. -5‰. Deuterium/hydrogen fractionations are expected to be an order of magnitude larger, with 50-70‰ lower D/H in dhcp-FeH than in coexisting H2 gas at 2000 K, and approximately 100‰ lower D/H than water vapor. These fractionations are much larger than those inferred for silicon and iron, as expected given the differences in atomic mass. References: 1. Georg et al. (2007) Nature 447:1102; 2. Rustad & Yin (2009) Nature Geoscience doi:10.1038/ngeo546; 3. Polyakov (2009) Science 323:912; 4. Polyakov & Kharlashina (1995) GCA 59:2561.

Ion-beam mixing at Fe:metallic-glass (Fe67Co18B14Si1) interface: A conversion-electron Mössbauer spectroscopic study

NASA Astrophysics Data System (ADS)

Bhandarkar, Y. V.; Ghaisas, S. V.; Ogale, S. B.

1988-07-01

Ion-beam mixing at an Fe:metallic glass (Fe67Co18B14Si1) interface is studied by employing the technique of conversion electron Mössbauer spectroscopy (CEMS). A 230-Å-thick overlayer of iron (enriched to 33% in the concentration of 57Fe Mössbauer isotope) was deposited on the shiny surface of metallic glass and such composites were bombarded with 100-keV Kr+ ions at dose values in the range between 1×1015 and 2×1016 ions/cm2. The transformations in the local atomic arrangements across the interface were investigated by monitoring the changes in the hyperfine-interaction parameters. It is shown that mixing leads to significant changes in the composition, in the vicinity of the interface as a function of the ion dose. At low dose (1×1015 ions/cm2) the local atomic coordination is found to be rich in the transition-metal concentration, while at a higher dose (2×1016 ions/cm2) it is observed to be rich in the boron concentration. Interestingly, at an intermediate dose 1×1016 ions/cm2 the composite near the interface region partially crystallizes and this structural state is found to revert back to the amorphous state upon thermal annealing at 300 °C. The observations made on the basis of CEMS are well supported by x-ray diffraction measurements.

Oxygen isotopes in crystalline silicates of comet Wild 2: A comparison of oxygen isotope systematics between Wild 2 particles and chondritic materials

NASA Astrophysics Data System (ADS)

Nakashima, Daisuke; Ushikubo, Takayuki; Joswiak, David J.; Brownlee, Donald E.; Matrajt, Graciela; Weisberg, Michael K.; Zolensky, Michael E.; Kita, Noriko T.

2012-12-01

Oxygen three-isotope ratios of nine crystalline silicate particles from comet Wild 2 were measured to investigate oxygen isotope systematics of cometary materials. We are able to analyze particles as small as 4 μm using an ion microprobe with a˜1×2 μm beam by locating the analysis spots with an accuracy of ±0.4 μm. Three particles of Mn-rich forsterite, known as low-iron, manganese-enriched (LIME) olivine, showed extremely 16O-rich signatures (δ18O, δ17O˜-50‰), similar to refractory inclusions in chondrites. The three Mn-rich forsterite particles may have formed by condensation from an 16O-rich solar nebula gas. Other particles consist of olivine and/or pyroxene with a wide range of Mg# [=molar MgO/(FeO+MgO) %] from 60 to 96. Their oxygen isotope ratios plot nearly along the carbonaceous chondrite anhydrous mineral (CCAM) and Young and Russell lines with Δ17O(=δ17O-0.52×δ18O) values of -3.0‰ to +2.5‰. These data are similar to the range observed from previous analyses of Wild 2 crystalline silicates and those of chondrules in carbonaceous chondrites. Six particles extracted from Stardust track 77 show diverse chemical compositions and isotope ratios; two Mn-rich forsterites, FeO-poor pigeonite, and three FeO-rich olivines with a wide range of Δ17O values from -24‰ to +1.6‰. These results confirmed that the original projectile that formed track 77 was an aggregate (>6 μm) of silicate particles that formed in various environments. The Δ17O values of ferromagnesian Wild 2 particles (including data from previous studies) increase from ˜-23‰ to+2.5‰ with decreasing Mg#: Δ17O values of Mn-rich forsterite particles (Mg#=98-99.8) cluster at -23‰, those of FeO-poor particles (Mg#=95-97) cluster at -2‰, and those of FeO-rich particles (Mg#≤90) scatter mainly from -1.5‰ to+2.5‰. Compared to chondrules in primitive chondrites, the systematic trend between Mg# and Δ17O among the Wild 2 particles is most similar to that reported for CR chondrite chondrules. We argue that CR chondrites and some cometary materials share multiple common chemical and isotope characteristics. We suggest that many of the crystalline silicate particles formed in the outer regions of the asteroid belt, or regions that share the common properties, and were transported to comet-forming regions and accreted into comet Wild 2.

Lunar and Planetary Science XXXVI, Part 1

NASA Technical Reports Server (NTRS)

2005-01-01

Contents include the following: Observations with Near Infrared Spectrometer for Hayabusa Mission in the Cruising Phase. First Results of Quadrantid Meteor Spectrum. Compositional Investigation of Binary Near-Earth Asteroid 66063 (1998 RO1): A Potentially Undifferentiated Assemblage. Impact-induced Hydrothermal Activity on Early Mars. HRTEM and EFTEM Studies of Phyllosilicate-Organic Matter Associations in Matrix and Dark Inclusions in the EET92042 CR2 Carbonaceous Chondrite. Volumetric Analysis of Martian Rampart Craters. High Pressure Melting of H-Chondrite: A Match for the Martian Basalt Source Mantle. MERView: A New Computer Program for Easy Display of MER-acquired M ssbauer Data. Distribution, Exchange, and Topographic Control of Subsurface Ice on Mars. Shock-induced Damage Beneath Normal and Oblique Impact Craters. Amphitrites Patera Studied from the Mars Express HRSC Data. Oxygen Isotope Microanalysis of Enveloping Compound Chondrules in CV3 and LL3 Chondrites. Gamma-Ray Irradiation in the Early Solar System and the Conundrum of the Lu-176 Decay Constant. Magnesium Isotope Mapping of Silica-rich Grains Having. Extreme Oxygen Isotope Anomalies Extreme Oxygen Isotopic Anomalies from Irradiation in the Early Solar System, Re-Examining the Role of Chondrules in Producing the Elemental Fractionations in Chondrites. Meteorite Data on the Solar Modulation of Galactic Cosmic Rays and an Inference on the Solar Activity Influence on Climate of the Earth. Volatiles Enrichments and Composition of Jupiter. Thinking Like a Wildcatter Prospecting for Methane in Arabia Terra, Mars. Size Distribution of Genesis Solar Wind Array Collector Fragments. Initial Subdivision of Genesis Early Science Polished Aluminum Collector. Presolar Graphite and Its Noble Gases. Young Pb-Isotopic Ages of Chondrules in CB Carbonaceous Chondrites. Fe Isotopic Composition of Martian Meteorites. Petrology and Geochemistry of Nakhlite MIL 03346: A New Martian Meteorite from Antarctica.

Use of Zn isotopes as a probe of anthropogenic contamination and biogeochemical processes in the Seine River, France

NASA Astrophysics Data System (ADS)

Chen, J.; Gaillardet, J.; Louvat, P.; Birck, J.

2009-05-01

Metal contamination is a major issue of human impact on the aqueous environment. River water is particularly susceptible to contamination for both dissolved and particulate loads, displaying a major challenge in understanding the dominant sources and pathways of metals in polluted drainage basins. Recent improvements in mass spectrometry allow isotopic measurements of "non-traditional" metals (Zn, Cu, Fe, etc.), making their isotopes a new potential device to investigate contamination of metals under dissolved and particulate forms in rivers. We focus here on Zn isotope geochemistry in the largely anthropized Seine River (France). A new protocol of two-column separation of Zn from dilute aqueous solution has been developed and proven to be reproducible and satisfactory for accurate measurement of Zn isotopic ratios in water samples by MC-ICP-MS (2σ = 0.04‰). Preliminary results show a total variation of 0.65‰ for δ66Zn in dissolved phases of the Seine basin, and a light isotope enrichment in anthropogenic sources compared to other water samples. The determined conservative behavior of Zn in river water makes its isotopes an effective probe of anthropogenic contamination. The natural and anthropogenic inputs were clearly identified and calculated based on Zn isotope compositions for dissolved loads. Suspended particular matters (SPM) display different Zn isotope compositions compared to dissolved loads, with a total δ66Zn variation of 0.22‰. Zn concentrations and its isotope compositions in SPM reveal inverse relationships as function of the distance from the headwater and the SPM content for geographical and temporal samples, respectively. The δ66Zn data in SPM are interpreted as reflecting the mixture of natural and anthropogenic particles. The correlation between dissolved and particulate δ66Zn shows that adsorption processes are not the dominant process making Zn enrichment in SPM. We report here for the first time systematic δ66Zn data in waters of a whole river basin, showing Zn isotopes a powerful probe to trace contamination sources and biogeochemical processes in hydrologic systems.

Fe, Zn, and Cd stable isotopes from the eastern tropical South Pacific from GEOTRACES cruise GP16 - Methods and data

NASA Astrophysics Data System (ADS)

Helgoe, J. M.; Townsend, E.; John, S.

2014-12-01

A new method has been developed for the rapid analysis of metal concentrations and stable isotope ratios using a prepFAST automated sample processing robot. Although concentrations and isotopes are processed separately, similar methods are used for both. Initially all seawater is acidified to pH 2. Then Nobias resin with EDTA/IDA functional groups is added to either 10mL of sample for concentrations or ~1L samples for isotopes. Fe binds to the resin at low pH, and the pH is subsequently raised to allow Zn and Cd to bind. For concentration analyses, all subsequent chemistry is automated on the prepFAST including removal of seawater, rinsing of resin, and elution of resin into acid. For isotope samples these extraction techniques are performed manually, but the subsequent purification of Fe, Zn, and Cd by anion exchange chromatography is automated using the prepFAST. With these new methods, samples from the US GEOTRACES cruise GP16, in the eastern tropical South Pacific, are being analyzed. High concentrations of dissolved Fe are observed near the continental shelf and near submarine hydrothermal vents. Interestingly, isotope data show that dissolved Fe near the continental shelf generally has a δ56Fe close to 0 ‰. This δ56 Fe signature is suggestive of a non-reductive dissolution source for Fe, as Fe(II) released by reductive dissolution is typically closer to -2 ‰. Preliminary data show nutrient-type profiles for Zn and Cd, with Zn matching Si and Cd having a similar distribution to P. An increase in dissolved Zn near hydrothermal vents suggests a possible hydrothermal zinc source to the deep ocean. Continuing analysis of isotope data will reveal more about the source and biogeochemical cycling of these three chemically and biologically important trace metals throughout the eastern tropical Pacific Ocean.

Non-traditional stable isotope behaviors in immiscible silica-melts in a mafic magma chamber

PubMed Central

Zhu, Dan; Bao, Huiming; Liu, Yun

2015-01-01

Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ57Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ57Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ57Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted. PMID:26620121

Stable isotope studies of metasomatic Ca-Fe-Al-Si skarns and associated metamorphic and igneous rocks, Osgood Mountains, Nevada

USGS Publications Warehouse

Taylor, B.E.; O'Neil, J.R.

1977-01-01

Garnet-pyroxene skarns were formed 90 m.y. B.P. in the Osgood Mountains at or near contacts of grandiorite with calcareous rocks of the Cambrian Preble Formation. The metasomatic replacement followed contact metamorphic recrystallization of the Preble. The sources, temperature, and variation in H2O/CO2 ratios of the metasomatic fluid are interpreted from 269 analyses of oxygen, carbon, hydrogen, and sulfur isotopes in whole rocks, minerals and inclusion fluids. Skarns formed in three mineralogical stages. Oxygen isotope data indicate that temperatures during the crystallization of garnet, pyroxene and wollastonite (Stage I) were least 550 ?? C, and that the metasomatic fluid had an {Mathematical expression} ??? 0.035 in the massive skarns, and ??? 0.12 in vein skarns up to 3 cm thick. Pore fluids in isotopic equilibrium with garnet in calc-silicate metamorphic rocks, on the other hand, had {Mathematical expression} ??? 0.15. The metasomatic fluids of Stage I were derived primarily from the crystallizing magma. The isotopic composition of magmatic water was ??18O =+9.0, ??D= -30 to -45. Oxygen isotope temperatures of greater than 620 ?? C were determined for the granodiorite. Isotopic and chemical equilibria between mineral surfaces and the metasomatic fluid were approached simultaneously in parts of the skarn several meters or more apart, while isotopic and chemical disequilibria (i.e. zoning) have been preserved between 20 to 40 ??m-thick zones in grandite garnet. More Fe-, or andradite-rich garnet crystallized in more H2O-rich C-O-H fluids ( {Mathematical expression} ??? 0.01) than present with grossularite-rich garnet ( {Mathematical expression}??? 0.035). Stage II was marked by the replacement of garnet and pyroxene by quartz, amphibole, plagioclase, epidote, magnetite, and calcite. Many of the replacement reactions took place over a relatively narrow range in temperature (480-550 ?? C), as indicated by 18O fractionations between quartz and amphibole. Meteoric water comprised 20 to 50% of the metasomatic fluid during Stage II. Calcite was formed along with pyrite, minor pyrrhotite, and chalcopyrite during Stage III, although the crystallization of pyrite and calcite had begun earlier, during Stages I and II, respectively. Carbon and sulfur isotope compositions of calcite and pyrite indicate a magmatic source for most of the C and S in the metasomatic fluids of Stage III. By the end of Stage III, meteoric water constituted as much as 100% of the metasomatic fluid. Minerals from grandiorite and skarn do not show large depletions in 18O because the oxygen isotope composition of the metasomatic fluid was buffered by the calcareous wall rocks and the grandiorite. Meteoric water in the vicinity of the Osgood Mountains during the Late Crectaceous (??18Ocale. ??? -14.0, ??D = - 107) was slightly enriched in 18O and D relative to present-day meteoric water (??18O = 15.9, ??D = - 117) ?? 1977 Springer-Verlag.

Textural and isotopic development of marble assemblages during the Barrovian-style M2 metamorphic event, Naxos, Greece

NASA Astrophysics Data System (ADS)

Baker, Judy; Matthews, Alan

1994-03-01

A detailed petrological analysis of the marble assemblages observed within the M2 metamorphic complex on Naxos is presented. Two distinct periods of mineral growth are documented; the first is associated with prograde M2 metamorphism and the second with retrograde M2 metamorphism occurring during ductile extensional thinning of the complex. The textural and miner-alogical characteristics and the carbon and oxygen isotope compositions of each generation are described, and the P-T-X CO 2 conditions at which these two mineral generations were stable, and the compositions of the fluids present during metamorphism are characterised. Whereas the low variance and stable isotope compositions of prograde siliceous dolomite assemblages are consistent with internally buffered fluid evolution, the retrograde mineral generation is shown to have grown as a result of the infiltration of a water-rich fluid phase that transported silica, Al2O3, Na2O and FeO into the host rocks. This observation, together with the stable isotope compositions of the retrograde calcite, and the fact that occurrences of veins of this type are limited to marbles in the highest grade areas ( T>600° C) of the metamorphic complex, suggests that the fluids responsible for vein formation were generated during the crystallisation of melts as the metamorphic complex cooled from peak temperatures. The existence of this second generation of minerals has significant implications for previous studies of heat transport by fluid flow on Naxos, because many of the unusually low δ18O compositions of pelites at high grades may be ascribable to the effects of interaction with retrograde M2 fluids, rather than with prograde fluids.

Status Report on Irradiation Capsules Containing Welded FeCrAl Specimens for Radiation Tolerance Evaluation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Field, Kevin G.; Howard, Richard H.

2016-02-26

This status report provides the background and current status of a series of irradiation capsules, or “rabbits”, that were designed and built to test the contributions of microstructure, composition, damage dose, and irradiation temperature on the radiation tolerance of candidate FeCrAl alloys being developed to have enhanced weldability and radiation tolerance. These rabbits will also test the validity of using an ultra-miniature tensile specimen to assess the mechanical properties of irradiated FeCrAl base metal and weldments. All rabbits are to be irradiated in the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory (ORNL) to damage doses up tomore » ≥15 dpa at temperatures between 200-550°C.« less

The formation and alteration of the Renazzo-like carbonaceous chondrites I: Implications of bulk-oxygen isotopic composition

NASA Astrophysics Data System (ADS)

Schrader, Devin L.; Franchi, Ian A.; Connolly, Harold C., Jr.; Greenwood, Richard C.; Lauretta, Dante S.; Gibson, Jenny M.

2011-01-01

To better understand the role of aqueous alteration on the CR chondrite parent asteroid, a whole-rock oxygen isotopic study of 20 meteorites classified as Renazzo-like carbonaceous chondrites (CR) was conducted. The CR chondrites analyzed for their oxygen isotopes were Dhofar 1432, Elephant Moraine (EET) 87770, EET 92042, EET 96259, Gao-Guenie (b), Graves Nunataks (GRA) 95229, GRA 06100, Grosvenor Mountains (GRO) 95577, GRO 03116, LaPaz Ice Field (LAP) 02342, LAP 04720, Meteorite Hills (MET) 00426, North West Africa (NWA) 801, Pecora Escarpment (PCA) 91082, Queen Alexandra Range (QUE) 94603, QUE 99177, and Yamato-793495 (Y-793495). Three of the meteorites, Asuka-881595 (A-881595), GRA 98025, and MET 01017, were found not to be CR chondrites. The remaining samples concur petrographically and with the well-established oxygen-isotope mixing line for the CR chondrites. Their position along this mixing line is controlled both by the primary oxygen-isotopic composition of their individual components and their relative degree of aqueous alteration. Combined with literature data and that of this study, we recommend the slope for the CR-mixing line to be 0.70 ± 0.04 (2σ), with a δ 17O-intercept of -2.23 ± 0.14 (2σ). Thin sections of Al Rais, Shişr 033, Renazzo, and all but 3 samples analyzed for oxygen isotopes were studied petrographically. The abundance of individual components is heterogeneous among the CR chondrites, but FeO-poor chondrules and matrix are the most abundant constituents and therefore, dominate the whole-rock isotopic composition. The potential accreted ice abundance, physico-chemical conditions of aqueous alteration (e.g. temperature and composition of the fluid) and its duration control the degree of alteration of individual CR chondrites. Combined with literature data, we suggest that LAP 02342 was exposed to lower temperature fluid during alteration than GRA 95229. With only two falls, terrestrial alteration of the CR chondrites complicates the interpretation of their whole rock isotopic composition, particularly in the most aqueously altered samples, and those with relatively higher matrix abundances. We report that QUE 99177 is the isotopically lightest whole rock CR chondrite known (δ 18O = -2.29‰, δ 17O = -4.08‰), possibly due to isotopically light unaltered matrix; which shows that the anhydrous component of the CR chondrites is isotopically lighter than previously thought. Although it experienced aqueous alteration, QUE 99177 provides the best approximation of the pristine CR-chondrite parent body's oxygen-isotopic composition, before aqueous alteration took place. Using this value as a new upper limit on the anhydrous component of the CR chondrites, water/rock ratios were recalculated and found to be higher than previously thought; ratios now range from 0.281 to 1.157. We also find that, according to their oxygen isotopes, a large number of CR chondrites appear to be minimally aqueously altered; although sample heterogeneity complicates this interpretation.

Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

PubMed

Frick, Daniel A; Schuessler, Jan A; von Blanckenburg, Friedhelm

2016-09-28

Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous stable isotope measurement and chemical composition analysis LASS-ICP-MS in combination with MC-ICP-MS is the method of choice. Copyright © 2016 Elsevier B.V. All rights reserved.

The End of Monterey Submarine Canyon Incision and Potential River Source Areas-Os, Nd, and Pb Isotope Constraints from Hydrogenetic Fe-Mn Crusts

NASA Astrophysics Data System (ADS)

Conrad, T. A.; Nielsen, S.; Ehrenbrink, B. P. E.; Blusztajn, J.; Hein, J. R.; Paytan, A.

2015-12-01

The Monterey Canyon off central California is the largest submarine canyon off North America and is comparable in scale to the Grand Canyon. The age and history of the Monterey Canyon are poorly constrained due to thick sediment cover and sediment disruption from turbidity currents. To address this deficit we analyzed isotopic proxies (Os, Pb, Nd) from hydrogenetic ferromanganese (Fe-Mn) crusts, which grow over millions of years on elevated rock surfaces by precipitation of metals from seawater. Fe-Mn crusts were studied from Davidson Seamount near the base of the Monterey submarine fan, the Taney Seamount Chain, and from Hoss Seamount, which serves as a regional control (Fig.). Fe-Mn crusts were dated using Os isotope ratios compared to those that define the Cenozoic Os isotope seawater curve. Four Fe-Mn crust samples from Davidson and Taney Seamounts deviate from the Os isotopic seawater curve towards radiogenic values after 4.5±1 Ma. Osmium is well mixed in the global ocean and is not subject to significant diffusive reequilibration in Fe-Mn crusts. We therefore attribute deviations from the Os isotope seawater curve to large-scale terrestrial input that ended about 4.5±1 Ma. The two Davidson samples also show more radiogenic Nd isotope values from about 4.5±1 Ma. Lead isotopes in one Davidson Seamount crust, measured by LA-ICPMS, deviate from regional values after 4.5±1 Ma for about 500 ka towards terrestrial sources. The Taney Seamount Fe-Mn crust does not deviate from regional Nd nor Pb isotope values due to its greater distance from Monterey Canyon and the shorter marine residence times of Nd and Pb. Isotope plots of our crust data and compiled data for potential source rocks indicate that the river that carved Monterey Canyon carried sediment with values closer to the Sierra Nevada than to a Colorado Plateau source, with cessation of major riverine input occurring approximately 4.5±1 Ma, an age that we interpret as the end of the Monterey Canyon incision.

East Asian origin of central Greenland last glacial dust: just one possible scenario?

NASA Astrophysics Data System (ADS)

Újvári, Gábor; Stevens, Thomas; Svensson, Anders; Klötzli, Urs Stephan; Manning, Christina; Németh, Tibor; Kovács, János

2016-04-01

Dust in Greenland ice cores is used to reconstruct the activity of dust emitting regions and atmospheric circulation for the last glacial period. However, the source dust material to Greenland over this period is the subject of considerable uncertainty. Here we use new clay mineral and Sr-Nd isotopic data from eleven loess samples collected around the Northern Hemisphere and compare the 87Sr/86Sr and 143Nd/144Nd isotopic signatures of fine (<10 μm) separates to existing Greenland ice core dust data (GISP2, GRIP; [1]; [2]). Smectite contents and kaolinite/chlorite (K/C) ratios allow exclusion of continental US dust emitting regions as potential sources, because of the very high (>3.6) K/C ratios and extremely high (>~70%) smectite contents. At the same time, Sr-Nd isotopic compositions demonstrate that ice core dust isotopic compositions can be explained by East Asian (Chinese loess) and/or Central/East Central European dust contributions. Central/East Central European loess Sr-Nd isotopic compositions overlap most with ice core dust, while the Sr isotopic signature of Chinese loess is slightly more radiogenic. Nevertheless, an admixture of 90‒10 % from Chinese loess and circum-Pacific volcanic material would also account for the Sr‒Nd isotopic ratios of central Greenland LGM dust. At the same time, sourcing of ice core dust from Alaska, continental US and NE Siberia seems less likely based on Sr and Nd isotopic signatures. The data demonstrate that currently no unique source discrimination for Greenland dust is possible using both published and our new data [3]. Thus, there is a need to identify more diagnostic tracers. Based on initial Hf isotope analyses of fine separates of three loess samples (continental US, Central Europe, China), an apparent dependence of Hf isotopic signatures on the relative proportions of radiogenic clay minerals (primarily illite) was found, as these fine dust fractions are apparently zircon-free. The observed difference between major potential source regions in 176Hf/177Hf that reach several ɛHf units and the first order clay mineralogy dependence of Hf isotopic signatures means there is strong potential for distinguishing between the two hypothesized Greenland dust sources using Hf isotopes [3]. [1] Biscaye P.E., Grousset F.E., Revel M., Van der Gaast S., Zielinski G.A., Vaars A., Kukla G. (1997). Asian provenance of glacial dust (stage 2) in the Greenland Ice Sheet Project 2 Ice Core, Summit, Greenland. Journal of Geophysical Research 102, 26765-26781. [2] Svensson A., Biscaye P.E., Grousset F.E. (2000) Characterization of late glacial continental dust in the Greenland Ice Core Project ice core. Journal of Geophysical Research 105, 4637-4656. [3] Újvári G., Stevens T., Svensson A., Klötzli U.S., Manning, C., Németh T., Kovács J., Sweeney M.R., Gocke M., Wiesenberg G.L.B., Markovic S.B., Zech M. (in press). Two possible source regions for Central Greenland last glacial dust. Geophysical Research Letters, doi: 10.1002/2015GL066153.

Tracing anthropogenic aerosol Fe sources in the North Atlantic Ocean using dissolved Fe isotope ratios

NASA Astrophysics Data System (ADS)

Conway, T. M.; Shelley, R.; Aguilar-Islas, A. M.; Landing, W. M.; Mahowald, N. M.; John, S.

2016-02-01

Supply of iron (Fe) to the surface ocean from atmospheric deposition plays a vital role in marine biogeochemical cycles, especially in Fe-limited areas or regions close to dust sources. However, large uncertainties remain over the fluxes, solubility and bioavailability of Fe supplied by aerosol dust. Additionally, aerosol Fe is likely to consist of a mixture of natural and anthropogenic (urban, biomass burning and combustion) components, which may have very different solubilities in seawater [e.g. 1]. To constrain soluble Fe supply to the oceans, it is thus vitally important to understand the relative contributions of different types of aerosol Fe, their solubilities and spatial distributions. Stable Fe isotopes (δ56Fe) may offer a way to discriminate between different dust sources [2], because of differential fractionation during a range of chemical processes. In this study, we measured δ56Fe in North Atlantic marine aerosols collected during two US GEOTRACES GA03 cruises (Lisbon to Woods Hole via Cape Verde, 2010-11) and we present δ56Fe measurements (relative to IRMM-014) from both the bulk aerosol (HF-HNO3 digested) and the water-soluble (10s ultrapure water leach) fractions. Aerosols collected from different air-masses (Saharan, European and N. American) allowed us to investigate the variability in δ56Fe due to different regional dust sources. The bulk phase was characterized by near-crustal δ56Fe values of +0.1±0.2‰, indicating the dominance of mineral dust. In contrast, the water-soluble fraction showed great variability; aerosols from European and North American air-masses were very isotopically light (-1.2±0.2‰ and -1.1±0.7‰) while those from Saharan air-masses were crustal (+0.1‰). Comparison of this data with isotope-informed model predictions of soluble Fe from mineral and anthropogenic sources (combustion, biofuels and biomass burning) [1], suggests that the data is consistent with mixing of either 1) Fe from mineral dust (+0.1‰) and a distinctly light anthropogenic Fe (-1.6‰), or 2) Fe from crustal mineral dust, isotopically heavy combustion Fe (+0.1 to +0.3‰), and biomass Fe that is both isotopically light (-1.6‰) and very soluble (>50%). [1] Luo, C. et al. (2008), Glob. Biogeochem. Cyc., 22, GB1012. [2] Mead, C. et al. (2013), Geophys. Res. Lett., 40, 5722-5727.

Silicon in Mars' Core: A Prediction Based on Mars Model Using Nitrogen and Oxygen Isotopes in SNC Meteorites

NASA Technical Reports Server (NTRS)

Mohapatra, R. K.; Murty, S. V. S.

2002-01-01

Chemical and (oxygen) isotopic compositions of SNC meteorites have been used by a number of workers to infer the nature of precursor materials for the accretion of Mars. The idea that chondritic materials played a key role in the formation of Mars has been the central assumption in these works. Wanke and Dreibus have proposed a mixture of two types of chondritic materials, differing in oxygen fugacity but having CI type bulk chemical composition for the nonvolatile elements, for Mars' precursor. But a number of studies based on high pressure and temperature melting experiments do not favor a CI type bulk planet composition for Mars, as it predicts a bulk planet Fe/Si ratio much higher than that reported from the recent Pathfinder data. Oxygen forms the bulk of Mars (approximately 40% by wt.) and might provide clues to the type of materials that formed Mars. But models based on the oxygen isotopic compositions of SNC meteorites predict three different mixtures of precursor materials for Mars: 90% H + 10% CM, 85% H + 11% CV + 4% CI and 45% EH + 55% H. As each of these models has been shown to be consistent with the bulk geophysical properties (such as mean density, and moment of inertia factor) of Mars, the nature of the material that accreted to form Mars remains ambiguous.

Iron silicide formation at different layers of (Fe/Si)3 multilayered structures determined by conversion electron Mössbauer spectroscopy

NASA Astrophysics Data System (ADS)

Badía-Romano, L.; Rubín, J.; Magén, C.; Bürgler, D. E.; Bartolomé, J.

2014-07-01

The morphology and the quantitative composition of the Fe-Si interface layer forming at each Fe layer of a (Fe/Si)3 multilayer have been determined by means of conversion electron Mössbauer spectroscopy (CEMS) and high-resolution transmission electron microscopy (HRTEM). For the CEMS measurements, each layer was selected by depositing the Mössbauer active 57Fe isotope with 95% enrichment. Samples with Fe layers of nominal thickness dFe = 2.6 nm and Si spacers of dSi = 1.5 nm were prepared by thermal evaporation onto a GaAs(001) substrate with an intermediate Ag(001) buffer layer. HRTEM images showed that Si layers grow amorphous and the epitaxial growth of the Fe is good only for the first deposited layer. The CEMS spectra show that at all Fe/Si and Si/Fe interfaces a paramagnetic c-Fe1-xSi phase is formed, which contains 16% of the nominal Fe deposited in the Fe layer. The bottom Fe layer, which is in contact with the Ag buffer, also contains α-Fe and an Fe1-xSix alloy that cannot be attributed to a single phase. In contrast, the other two layers only comprise an Fe1-xSix alloy with a Si concentration of ≃0.15, but no α-Fe.

Database on Performance of Neutron Irradiated FeCrAl Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Field, Kevin G.; Briggs, Samuel A.; Littrell, Ken

The present report summarizes and discusses the database on radiation tolerance for Generation I, Generation II, and commercial FeCrAl alloys. This database has been built upon mechanical testing and microstructural characterization on selected alloys irradiated within the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory (ORNL) up to doses of 13.8 dpa at temperatures ranging from 200°C to 550°C. The structure and performance of these irradiated alloys were characterized using advanced microstructural characterization techniques and mechanical testing. The primary objective of developing this database is to enhance the rapid development of a mechanistic understanding on the radiation tolerancemore » of FeCrAl alloys, thereby enabling informed decisions on the optimization of composition and microstructure of FeCrAl alloys for application as an accident tolerant fuel (ATF) cladding. This report is structured to provide a brief summary of critical results related to the database on radiation tolerance of FeCrAl alloys.« less

Actualistic models of mantle metasomatism documented in a composite xenolith from Dish Hill, California

USGS Publications Warehouse

Nielson, J.E.; Budahn, J.R.; Unruh, D.M.; Wilshire, H.G.

1993-01-01

Major and trace-element whole rock and mineral variations in composite hornblendite-peridotite xenolith Ba-2-1, from Dish Hill, CA, are due to a single event of metasomatism in the mantle. The hornblendite is the crystallized selvage of a dike conduit charged with incompatible-element-enriched hydrous mafic magma. The magma infiltrated the refractory peridotite wallrock, reacted with its constituent minerals, and simultaneously deposited amphibole. The systematic data from this study show considerable variation in isotopic values and trace elements. These data provide insight into a mantle process that was defined previously from samples without context, lacking evidence about the number or source of metasomatic events. In the contact zone of Ba-2-1, peridotite is enriched in Fe, Ti, CO2) and H2O; clinopyroxene and amphibole also are enriched in Fe and Ti, but clinopyroxene appears slightly depleted in CaO. Compared to chondrites, peridotite, clinopyroxene, and probably amphibole are enriched in light rare earth (LREEcn) and other incompatible trace elements. Values of 87Sr 86Sr and 143Nd 144Nd in the contact zone are close to isotopic equilibrium with the dike. Whole rock and constituent clinopyroxene compositions change to those of refractory peridotite with distance from the contact. These compositional variations were modelled using Gresens' equation for whole-rock major and minor elements, and calculations for isotopic ratios and REEs, which emulate the effects of Chromatographic fractionation. The choice of endmembers was restricted to compositions actually present in mantle samples from Dish Hill. Model results indicate that: 1. (1) the variations can be explained as the result of a single metasomatic event, probably a single pulse of previously fractionated liquid; 2. (2) the ratio of total interacting liquid to peridotite was at least 1:3 by weight in the contact zone; and 3. (3) the composition of the metasomatic liquid changed progressively as it infiltrated beyond that zone. The small distance over which variations occur is due to the small amount of liquid that infiltrated. Only in the contact zone was peridotite wallrock saturated by a liquid composition similar to the dike. Comparison of the Ba-2-1 data with those of another xenolith from Dish Hill suggests that the compositional variations of mantle metasomatism result from both the compositional contrast between the metasomatizing liquid and wallrock and the relative abundances of each. Compositional and volumetric variations of mantle partial melts and their fractionates, and repeated events of melting and reaction in contiguous mantle, can create broad ranges of metasomatic "signatures" from the same process. ?? 1993.

Controls on the Transition Metal Isotopic Composition of Seawater: Diatom Culture Experiments

NASA Astrophysics Data System (ADS)

Vance, D.; Archer, C.; Kennaway, G.; Cox, E.; Statham, P. J.

2004-12-01

Many transition metals are essential micronutrients for marine phytoplankton. As a result the expectation is that biological processes play an important, perhaps a dominant, role in their marine isotope geochemistry. These observations raise the prospect of using isotope records to trace transition metal micronutrient usage in the past oceans, an issue that is of importance to the efficiency of the biological pump and atmospheric carbon dioxide. As such, the characterisation of trace metal isotopic fractionations associated with marine primary productivity are an important scientific goal. Here we report fractionations associated with Fe, Cu and Zn sequestration by diatoms, one of the main primary producers in the oceans. Axenic unialgal cultures of Thalassiosira weissflogii and Thalassiosira pseudonana were established in artificial seawater + F/2 medium at 18° C on a 16:8 light:dark cycle. The cultures were filtered to separate diatom material from residual media and analysed for Zn, Cu and Fe concentrations and isotope composition using techniques described elsewhere1,2. Aliquots of the starting medium were also measured for each batch of cultures. The diatom organic material shows small, but consistent and resolvable, positive fractionations (0.1-0.3 per mil) for Fe, Cu and Zn relative to the starting medium. In the case of all three metals, but particularly for Zn (70-95% depending on experiment size), the diatoms had sequestered a large proportion of the available metal, suggesting that the fractionation factor for metal usage by the diatoms is much greater than 1.0001 to 1.0003. Time-series experiments are under way to determine the exact magnitude of the fractionation factor. The mass-balance is supported by the fact that the residual medium is around -0.4 per mil for Zn. The fact that diatoms incorporate trace metals that are isotopically heavier than the nutrient pool is a surprising result, the expectation having been that, as with carbon, the biological usage of trace metals would result in kinetic fractionations3. The positive fractionations necessitate an equilibrium process and, perhaps, active extra-cellular sequestration of trace metals. The second broader implication is that given the proposed role of diatoms in controlling the extreme depletion of Zn in open ocean surface waters, particularly in the Pacific where surface waters are have up to a factor of 250 less Zn than deep waters4, the depletion of the light isotope in surface waters and its enrichment in deep waters are predicted to be extreme. Zn, and other trace metal, isotopes may have an important role in recording this process in the past oceans. 1 C. Archer and D. Vance, 2004, J. Anal. Atom. Spectr. 19, 656-665. 2 J. Bermin, et al., 2004, this volume. 3 Pichat, S et al., 2003, Earth Planet. Sci. Lett. 210, 167-178. 4 Lohan, M.C. et al., 2002, Deep-Sea Res. II 49, 5793-5808.

Carbon isotopic variation in ureilites: Evidence for an early, volatile-rich Inner Solar System

NASA Astrophysics Data System (ADS)

Barrat, Jean-Alix; Sansjofre, Pierre; Yamaguchi, Akira; Greenwood, Richard C.; Gillet, Philippe

2017-11-01

We analyzed the C isotopic compositions of 32 unbrecciated ureilites, which represent mantle debris from a now disrupted, C-rich, differentiated body. The δ13C values of their C fractions range from -8.48 to +0.11‰. The correlations obtained between δ13C, δ18O and Δ17O values and the compositions of the olivine cores, indicate that the ureilite parent body (UPB) accreted from two reservoirs displaying distinct O and C isotopic compositions. The range of Fe/Mg ratios shown by its mantle was not the result of melting processes involving reduction with C ("smelting"), but was chiefly inherited from the mixing of these two components. Because smelting reactions are pressure-dependent, this result has strong implications for the size of the UPB, and points to a large parent body, at least 690 km in diameter. It demonstrates that C-rich primitive matter distinct from that represented by carbonaceous chondrites was present in some areas of the early inner Solar System, and could have contributed to the growth of the terrestrial planets. We speculate that differentiated, C-rich bodies, or debris produced by their disruption, were an additional source of volatiles during the later accretion stages of the rocky planets, including Earth.

Carbon and Oxygen Isotope Measurements of Ordinary Chondrite (OC) Meteorites from Antarctica Indicate Distinct Terrestrial Carbonate Species using a Stepped Acid Extraction Procedure Impacting Mars Carbonate Research

NASA Astrophysics Data System (ADS)

Evans, M. E.; Niles, P. B.; Locke, D.

2015-12-01

The purpose of this study is to characterize the stable isotope values of terrestrial, secondary carbonate minerals from five OC meteorites collected in Antarctica. These samples were selected for analysis based upon their size and collection proximity to known Martian meteorites. They were also selected based on petrologic type (3+) such that they were likely to be carbonate-free before falling to Earth. This study has two main tasks: 1) characterize the isotopic composition of terrestrial, secondary carbonate minerals formed on meteorites in Antarctica, and 2) study the mechanisms of carbonate formation in cold and arid environments with Antarctica as an analog for Mars. Two samples from each meteorite, each ~0.5g, was crushed and dissolved in pure phosphoric acid for 3 sequential reactions: a) Rx0 for 1 hour at 30°C, b) Rx1 for 18 hours at 30°C, and c) Rx2 for 3 hours at 150°C. CO2 was distilled by freezing with liquid nitrogen from each sample tube, then separated from organics and sulfides with a TRACE GC using a Restek HayeSep Q 80/100 6' 2mm stainless column, and then analyzed on a Thermo MAT 253 IRMS in Dual Inlet mode. This system was built at NASA/JSC over the past 3 years and proof tested with known carbonate standards to develop procedures, assess yield, and quantify expected uncertainties. Two distinct species of carbonates are found based on the stepped extraction technique: 1) Ca-rich carbonate released at low temperatures, and 2) Mg, or Fe-rich carbonate released at high temperatures. Preliminary results indicate that most of the carbonates present in the ordinary chondrites analyzed have δ13C=+5‰, which is consistent with formation from atmospheric CO2 δ13C=-7‰ at -20°C. The oxygen isotopic compositions of the carbonates vary between +4‰ and +34‰ with the Mg-rich and/or Fe-rich carbonates possessing the lowest δ18O values. This suggests that the carbonates formed under a wide range of temperatures. However, the carbonate oxygen isotope compositions are consistently heavier than what would be expected if the carbonates formed in equilibrium with melted ice in Antarctica.

Isotopic chemical weathering behaviour of Pb derived from a high-Alpine Holocene lake-sediment record

NASA Astrophysics Data System (ADS)

Gutjahr, Marcus; Süfke, Finn; Gilli, Adrian; Anselmetti, Flavio; Glur, Lukas; Eisenhauer, Anton

2017-04-01

Several studies assessing the chemical weathering systematics of Pb isotopes provided evidence for the incongruent release of Pb from source rocks during early stages of chemical weathering, resulting in runoff compositions more radiogenic (higher) than the bulk source-rock composition [e.g. 1]. Deep NW Atlantic seawater Pb isotope records covering the last glacial-interglacial transition further support these findings. Clear excursions towards highly radiogenic Pb isotopic input in the deep NW Atlantic seen during the early Holocene, hence after the large-scale retreat of the Laurentide Ice Sheet in North America, are interpreted to be controlled by preferential release of radiogenic Pb from U- and Th-rich mineral phases during early stages of chemical weathering that are less resistant to chemical dissolution than other rock-forming mineral phases [2-4]. To date, however, no terrestrial Pb isotope record exists that could corroborate the evidence from deep marine sites for efficient late deglacial weathering and washout of radiogenic Pb. We present a high-resolution adsorbed Pb isotope record from a sediment core retrieved from Alpine Lake Grimsel (1908 m.a.s.l.) in Switzerland, consisting of 117 Pb compositions over the past 10 kyr. This high-Alpine study area is ideally located for incipient and prolonged chemical weathering studies. The method used to extract the adsorbed lake Pb isotope signal is identical to previous marine approaches targeting the authigenic Fe-Mn oxyhydroxides fraction within the lake sediments [5, 6]. The Pb isotope compositions are further accompanied by various elemental ratios derived from the same samples that equally trace climatic boundary conditions in the Grimsel Lake area. The Pb isotopic composition recorded in Lake Grimsel is remarkably constant throughout the majority of the Holocene until ˜2.5 ka BP, despite variable sediment composition and -age, and isotopically relatively close to the signature of the granitic source rock. In contrast, adsorbed Th and U concentrations (given in concentrations of ng/g of sediment) are indeed significantly elevated during the earliest part of the record, while other adsorbed metals such as Al and Ti display highest adsorbed concentrations during the mid-Holocene. Elements such as Nd display fairly constant normalised concentrations throughout the record. Hence, while our Pb isotopic record appears remarkably insensitive towards climatic perturbations seen during the Holocene, the various elemental records display a striking sensititivity towards the overall climate evolution of the Holocene. Finally, the rise and fall of the Roman Empire as well as the onset of the industrial revolution are clearly resolvable in our Pb isotopic records. References [1] Harlavan, Y. Y. et al. (1998), GCA 62, 33-46; [2] Gutjahr, M. et al. (2009), EPSL 286, 546-555; [3] Kurweil, F. et al. (2010), EPSL 299, 458-465; [4] Crocket, K.C. et al. (2012) QSR 38, 89-99; [5] Gutjahr et al. (2007) Chem. Geol. 242, 351-370; [6] Blaser, P. et al. (2016) Chem. Geol. 439, 189-204.

Chemical leaching methods and measurements of marine labile particulate Fe

NASA Astrophysics Data System (ADS)

Revels, B. N.; John, S.

2012-12-01

Iron (Fe) is an essential nutrient for life. Yet its low solubility and concentration in the ocean limits marine phytoplankton productivity in many regions of the world. Dissolved phase Fe (<0.4μm) has traditionally been considered the most biologically accessible form, however, the particulate phase (>0.4μm) may contain an important, labile reservoir of Fe that may also be available to phytoplankton. However, concentration data alone cannot elucidate the sources of particulate Fe to the ocean and to what extent particulate iron may support phytoplankton growth. Isotopic analysis of natural particles may help to elucidate the biogeochemical cycling of Fe, though it is important to find a leaching method which accesses bioavailable Fe. Thirty-three different chemical leaches were performed on a marine sediment reference material, MESS-3. The combinations included four different acids (25% acetic acid, 0.01M HCl, 0.5M HCl, 0.1M H2SO4 at pH2), various redox conditions (0.02M hydroxylamine hydrochloride or 0.02M H2O2), three temperatures (25°C, 60°C, 90°C), and three time points (10 minutes, 2 hours, 24 hours). Leached Fe concentrations varied from 1mg/g to 35mg/g, with longer treatment times, stronger acids, and hotter temperatures generally associated with an increase in leached Fe. δ56Fe in these leaches varied from -1.0‰ to +0.2‰. Interestingly, regardless of leaching method used, there was a very similar relationship between the amount of Fe leached from the particles and the δ56Fe of this iron. Isotopically lighter δ56Fe values were associated with smaller amounts of leached Fe whereas isotopically heavier δ56Fe values were associated with larger amounts of leached Fe. Two alternate hypotheses could explain these data. Either, the particles may contain pools of isotopically light Fe that are easily accessed early in dissolution, or isotopically light Fe may be preferentially leached from the particle due to a kinetic isotope effect during dissolution. To explore the first hypothesis, we modeled dissolution of Fe from particles assuming two separate pools, labile and refractory. The model produces a good fit to the data assuming 3mg/g of a labile Fe pool with δ56Fe = -0.9‰ and a refractory Fe pool with δ56Fe = +0.1‰. If the second hypothesis is true, and there is a kinetic isotope effect during dissolution, the similar relationship between amount of Fe leached and δ56Fe for both organic and mineral acids suggests that Fe is leached from particles via proton-promoted dissolution. Several of these leaching techniques will be employed on sediment trap material from the Cariaco Basin to further investigate the relationship between δ56Fe and the labile, bioavailable fraction of iron particles. A leach or series of leaches will be chosen to provide the most useful information about the bioavailability of iron from particles, and they will be applied to filtered particle samples from portions of the US GEOTRACES A10 (North Atlantic) transect. δ56Fe values from particulate material in these regions will provide a better understanding of the sources of particulate iron to the ocean, and may help to trace how particulate iron is involved in global biogeochemical cycles.

Paleogene Seawater Osmium Isotope Records

NASA Astrophysics Data System (ADS)

Rolewicz, Z.; Thomas, D. J.; Marcantonio, F.

2012-12-01

Paleoceanographic reconstructions of the Late Cretaceous and early Cenozoic require enhanced geographic coverage, particularly in the Pacific, in order to better constrain meridional variations in environmental conditions. The challenge with the existing inventory of Pacific deep-sea cores is that they consist almost exclusively of pelagic clay with little existing age control. Pelagic clay sequences are useful for reconstructions of dust accumulation and water mass composition, but accurate correlation of these records to other sites requires improved age control. Recent work indicates that seawater Os isotope analyses provide useful age control for red clay sequences. The residence time of Os in seawater is relatively long compared to oceanic mixing, therefore the global seawater 187Os/188Os composition is practically homogeneous. A growing body of Late Cretaceous and Cenozoic data has constrained the evolution of the seawater Os isotopic composition and this curve is now a viable stratigraphic tool, employed in dating layers of Fe-Mn crusts (e.g., Klemm et al., 2005). Ravizza (2007) also demonstrated that the seawater Os isotopic composition can be extracted reliably from pelagic red clay sediments by analyzing the leached oxide minerals. The drawback to using seawater Os isotope stratigraphy to date Paleogene age sediments is that the compilation of existing data has some significant temporal gaps, notably between ~38 and 55 Ma. To improve the temporal resolution of the seawater Os isotope curve, we present new data from Ocean Drilling Program (ODP) Site 865 in the equatorial Pacific. Site 865 has excellent biostratigraphic age control over the interval ~38-55Ma. Preliminary data indicate an increase in the seawater composition from 0.427 at 53.4 Ma to 0.499 by 43 Ma, consistent with the apparent trend in the few existing data points. We also analyzed the Os isotopic composition recorded by oxide minerals at Integrated Ocean Drilling Program (IODP) Site U1370 to construct an age model for this predominantly pelagic clay section. The 187Os/188Os values generally increase from 0.312 at 64.46 mbsf to 0.531 at 28.26 mbsf. The low value recorded at 64.46 likely reflects the Os isotope minimum recorded across the K/Pg boundary, while the uppermost value likely correlates to the E/O interval. Comparison of the Os-derived ages with a crude linearly interpolated sedimentation rate age model reveals variations in sediment accumulation rate between 0.86 and 1.5 m/Myr.

Tracing Pleistocene to Holocene meltwater events and provenance of sediments in Baffin Bay using radiogenic isotope signals

NASA Astrophysics Data System (ADS)

Kirillova, Valeriia; Kasemann, Simone A.; Lucassen, Friedrich

2016-04-01

Large meltwater discharge is the principal carrier of detritus from the continent into the ocean and the dispersion of this detritus by ocean currents is a measure for the spatially focused addition of freshwater in the ocean in the high latitude areas. To trace Greenland ice sheet dynamics and freshwater routing during late Pleistocene to Holocene climate transition, we generate strontium (Sr), neodymium (Nd) and lead (Pb) isotope records on sediment cores in the Baffin Bay: GeoTÜ SL 170, covering the last 18.000 years of climate history and GeoTÜ SL 174, covering 40.000 years. Sr, Nd and Pb isotopes are used as proxies for the provenance of continental detritus and seawater sources. Isotope analyses were performed on two separated fractions from the sedimentary core material: the chemically leached fraction and the remaining detritus. Leachates are supposed to represent Fe-Mn coatings formed on the surface of the sediment grains and to reflect the bottom water signal. The detrital fraction acts as a tracer for the meltwater event and weathering regime of the nearby continental masses. For the detrital fraction of the core SL 170, a pronounced shift can be observed in all three isotope systems at ˜ 12 ka, what coincides with the Younger Dryas cold event. For the detrital fraction the 87Sr/86Sr is around ˜0,72 before the event and reaches up to ˜0,74 after. Nd isotope composition (ɛNd) changed from ˜-26 to ˜-32. The shift suggests a change in the continental sources from West and West-South Greenland to the Baffin Island and Canadian Archipelago. It can be explained by the ice sheet melting processes. The 206Pb/204Pb values for the detrital fraction range from ˜17 before the shift to ˜18 after. On the contrary, the leachates show pronounced radiogenic signatures with values changing from ˜21 to ˜23. The reason for such an unusual high values is most likely in the composition of the leached material, which doesn't seem to show the presence of Fe-Mn coatings as was suggested before. The work on the second core SL 174 is in progress. Up to now the results show similar patterns for isotope ratios as in the case of SL 170.

δ2H isotopic flux partitioning of evapotranspiration over a grass field following a water pulse and subsequent dry down

NASA Astrophysics Data System (ADS)

Good, Stephen P.; Soderberg, Keir; Guan, Kaiyu; King, Elizabeth G.; Scanlon, Todd M.; Caylor, Kelly K.

2014-02-01

The partitioning of surface vapor flux (FET) into evaporation (FE) and transpiration (FT) is theoretically possible because of distinct differences in end-member stable isotope composition. In this study, we combine high-frequency laser spectroscopy with eddy covariance techniques to critically evaluate isotope flux partitioning of FET over a grass field during a 15 day experiment. Following the application of a 30 mm water pulse, green grass coverage at the study site increased from 0 to 10% of ground surface area after 6 days and then began to senesce. Using isotope flux partitioning, transpiration increased as a fraction of total vapor flux from 0% to 40% during the green-up phase, after which this ratio decreased while exhibiting hysteresis with respect to green grass coverage. Daily daytime leaf-level gas exchange measurements compare well with daily isotope flux partitioning averages (RMSE = 0.0018 g m-2 s-1). Overall the average ratio of FT to FET was 29%, where uncertainties in Keeling plot intercepts and transpiration composition resulted in an average of uncertainty of ˜5% in our isotopic partitioning of FET. Flux-variance similarity partitioning was partially consistent with the isotope-based approach, with divergence occurring after rainfall and when the grass was stressed. Over the average diurnal cycle, local meteorological conditions, particularly net radiation and relative humidity, are shown to control partitioning. At longer time scales, green leaf area and available soil water control FT/FET. Finally, we demonstrate the feasibility of combining isotope flux partitioning and flux-variance similarity theory to estimate water use efficiency at the landscape scale.

The biogeochemical iron cycle and astrobiology

NASA Astrophysics Data System (ADS)

Schröder, Christian; Köhler, Inga; Muller, Francois L. L.; Chumakov, Aleksandr I.; Kupenko, Ilya; Rüffer, Rudolf; Kappler, Andreas

2016-12-01

Biogeochemistry investigates chemical cycles which influence or are influenced by biological activity. Astrobiology studies the origin, evolution and distribution of life in the universe. The biogeochemical Fe cycle has controlled major nutrient cycles such as the C cycle throughout geological time. Iron sulfide minerals may have provided energy and surfaces for the first pioneer organisms on Earth. Banded iron formations document the evolution of oxygenic photosynthesis. To assess the potential habitability of planets other than Earth one looks for water, an energy source and a C source. On Mars, for example, Fe minerals have provided evidence for the past presence of liquid water on its surface and would provide a viable energy source. Here we present Mössbauer spectroscopy investigations of Fe and C cycle interactions in both ancient and modern environments. Experiments to simulate the diagenesis of banded iron formations indicate that the formation of ferrous minerals depends on the amount of biomass buried with ferric precursors rather than on the atmospheric composition at the time of deposition. Mössbauer spectra further reveal the mutual stabilisation of Fe-organic matter complexes against mineral transformation and decay of organic matter into CO2. This corresponds to observations of a `rusty carbon sink' in modern sediments. The stabilisation of Fe-organic matter complexes may also aid transport of particulate Fe in the water column while having an adverse effect on the bioavailability of Fe. In the modern oxic ocean, Fe is insoluble and particulate Fe represents an important source. Collecting that particulate Fe yields small sample sizes that would pose a challenge for conventional Mössbauer experiments. We demonstrate that the unique properties of the beam used in synchrotron-based Mössbauer applications can be utilized for studying such samples effectively. Reactive Fe species often occur in amorphous or nanoparticulate form in the environment and are therefore difficult to study with standard mineralogical tools. Sequential extraction techniques are commonly used as proxies. We provide an example where Mössbauer spectroscopy can replace sequential extraction techniques where mineralogical information is sought. Where mineral separation is needed, for example in the investigation of Fe or S isotope fractionation, Mössbauer spectroscopy can help to optimize sequential extraction procedures. This can be employed in a large number of investigations of soils and sediments, potentially even for mineral separation to study Fe and S isotope fractionation in samples returned from Mars, which might reveal signatures of biological activity. When looking for the possibility of life outside Earth, Jupiter's icy moon Europa is one of the most exciting places. It may be just in reach for a Mössbauer spectrometer deployed by a future lander to study the red streak mineral deposits on its surface to look for clues about the composition of the ocean hidden under the moon's icy surface.

The chemical composition of red giants in 47 Tucanae. II. Magnesium isotopes and pollution scenarios

NASA Astrophysics Data System (ADS)

Thygesen, A. O.; Sbordone, L.; Ludwig, H.-G.; Ventura, P.; Yong, D.; Collet, R.; Christlieb, N.; Melendez, J.; Zaggia, S.

2016-04-01

Context. The phenomenon of multiple populations in globular clusters is still far from understood, with several proposed mechanisms to explain the observed behaviour. The study of elemental and isotopic abundance patterns are crucial for investigating the differences among candidate pollution mechanisms. Aims: We derive magnesium isotopic ratios for 13 stars in the globular cluster 47 Tucanae (NGC 104) to provide new, detailed information about the nucleosynthesis that has occurred within the cluster. For the first time, the impact of 3D model stellar atmospheres on the derived Mg isotopic ratios is investigated. Methods: Using both tailored 1D atmospheric models and 3D hydrodynamical models, we derive magnesium isotopic ratios from four features of MgH near 5135 Å in 13 giants near the tip of the red giant branch, using high signal-to-noise, high-resolution spectra. Results: We derive the magnesium isotopic ratios for all stars and find no significant offset of the isotopic distribution between the pristine and the polluted populations. Furthermore, we do not detect any statistically significant differences in the spread in the Mg isotopes in either population. No trends were found between the Mg isotopes and [Al/Fe]. The inclusion of 3D atmospheres has a significant impact on the derived 25Mg/24Mg ratio, increasing it by a factor of up to 2.5, compared to 1D. The 26Mg/24Mg ratio, on the other hand, essentially remains unchanged. Conclusions: We confirm the results seen from other globular clusters, where no strong variation in the isotopic ratios is observed between stellar populations, for observed ranges in [Al/Fe]. We see no evidence for any significant activation of the Mg-Al burning chain. The use of 3D atmospheres causes an increase of a factor of up to 2.5 in the fraction of 25Mg, resolving part of the discrepancy between the observed isotopic fraction and the predictions from pollution models. Based on observations made with the ESO Very Large Telescope at Paranal Observatory, Chile (Programmes 084.B-0810 and 086.B-0237).

Stable Nickel Isotopes in Fusion Crusts from Iron Meteorites and from Metallic Particles in a Black Wabar Impact Glass

NASA Astrophysics Data System (ADS)

Xue, S.; Herzog, G. F.; Hall, G. S.

1993-07-01

Iron and nickel isotopes may undergo mass fractionation in systems subjected to high-temperature vaporization [1-3]. We report here a search for nickel fractionation in fusion crusts from iron meteorites and in metal-rich material separated from Wabar impact glasses. Fusion-crust bearing samples of Bogou (IA), N'Goureyma (I-an), and Pitts (IB) were potted in epoxy and were "shaved" with a milling machine. Microscopic examination of the shavings showed the presence of some material from the interior of the meteorites as well as from the fusion crust. A fourth meteorite, Cape of Good Hope (IVB), was prepared for use as a reference standard. About 1.4 mg of magnetic material was collected from a 2-g sample of black Wabar impact glass ground in a Spex mill; microscopic examination indicated that adhering silicates comprised ~5% of the sample. These (terrestrial) silicates contain relatively little Ni [4] so their presence does not interfere with the nickel analysis. Nickel was separated from all samples and its isotopic composition determined as in [2]. Results and Discussion: Nickel isotopic abundances are given in Table 1 both as delta values and as an average fractionation, PHI, where PHI is the slope of a plot of delta vs. mass for each sample. Within the precision of our measurements (from 0.3 to 1.5%, depending on the isotope) all the samples had normal (i.e., terrestrial) isotopic abundances of Ni. Clayton et al. [5] reported that delta-18O in fusion crust is lower than in the atmosphere, probably as a result of a kinetic isotope effect, while in metallic deep-sea spheres, heavy oxygen isotopes are enriched. They inferred that the metallic spheres are not the ablation products of larger meteorites. Similarly, the Ni isotopic abundances in fusion crust are normal, while those in deep-sea metallic spheres are enriched in the heavier isotopes [1]. We note, however, that material ablated from the surface of an iron could have undergone fractionation after separation from the incoming meteorite (see [4]). Horz et al. [6] found variable Fe/Ni ratios (from 0.1 to 222) in black melt glasses associated with the Wabar impact. The Fe/Ni ratio in our metal sample is 2, which is considerably lower than that in the bulk meteorite (~12.4). Several lines of evidence suggest that vapor fractionation is to be expected in samples that have Fe/Ni ratios greater than those in the bulk impactor [2-6]. Thus it is not surprising that our first results for Wabar impactites show no Ni isotopic fractionation. Isotopic analyses of Wabar impactites with high Fe/Ni ratios should be made to test the importance of vapor fractionation. References: [1] Herzog G. F. et al. (1992) LPSC XXIII, 527-528. [2] Xue S. et al. (1993) LPSC XXIV, 1547-1548. [3] Davis A. et al. (1993) LPSC XXIV, 373- 374. [4] Mittlefehldt D. W. et al. (1992) Meteoritics, 27, 361-370. [5] Clayton R. N. et al. (1986) EPSL, 79, 235-240. [6] Horz F. et al. (1989) Proc. LPSC 19th, 697-710. Table 1, which appears in the hard copy, shows delta (permil) and average isotope fractionation PHI (%/amu) for Ni isotopes in iron meteorites and black Wabar impact glass.

Detection of Remarkably Low Isotopic Ratio of Iron in Anthropogenic Aerosols and Evaluation of its Contribution to the Surface Ocean

NASA Astrophysics Data System (ADS)

Kurisu, M.; Iizuka, T.; Sakata, K.; Uematsu, M.; Takahashi, Y.

2015-12-01

It has been reported that phytoplankton growth in the High Nutrient-Low Chlorophyll (HNLC) regions is limited by dissolved iron (DFe) concentration (e.g., Martin and Fitzwater, 1988). Aerosol is known as one of the dominant sources of DFe to the ocean and classified into two origins such as anthropogenic and natural. A series of recent studies showed that Fe in anthropogenic aerosols is more soluble than that in natural aerosols (Takahashi et al., 2013) and has lower isotopic ratio (Mead et al., 2013). However, the difference between Fe isotopic ratio　(δ56Fe: [(56Fe/54Fe)sample/(56Fe/54Fe)IRMM-14]-1) of two origins reported in Mead et al. (2013) is not so large compared with the standard deviation. Therefore, the aim of this study is to determine Fe species and δ56Fe in anthropogenic aerosols more accurately and to evaluate its contribution to the ocean surface. Iron species were determined by X-ray absorption fine structure (XAFS) analysis, while δ56Fe in size-fractionated aerosols were measured by MC-ICP-MS (NEPTUNE Plus) after chemical separation using anion exchange resin. Dominant Fe species in the samples were, ferrihydrite, hematite, and biotite. It was also revealed that coarse particles contained a larger amount of biotite and that fine particles contained a larger amount of hematite, which suggested that anthropogenic aerosols were emitted during combustion processes. In addition, results of Fe isotopic ratio analysis suggested that δ56Fe of coarse particles were around +0.25‰, whereas that of fine particles were -0.5 ˜ -2‰, which was lower than the δ56Fe in anthropogenic aerosol by Mead et al. (2013). The size-fractionated sampling made it possible to determine the δ56Fe in anthropogenic aerosol. Soluble component in fine particles extracted by simulated rain water also showed much lower δ56Fe (δ56Fe = -3.9±0.12‰), suggesting that anthropogenic Fe has much lower isotopic ratio. The remarkably low δ56Fe may be caused by the anthropogenic combustion process. The δ56Fe in anthropogenic aerosols measured here is important to model the budget of iron in the surface ocean.

The role of bacterial consortium and organic amendment in Cu and Fe isotope fractionation in plants on a polluted mine site.

PubMed

Pérez Rodríguez, Nathalie; Langella, Francesca; Rodushkin, Ilia; Engström, Emma; Kothe, Erika; Alakangas, Lena; Öhlander, Björn

2014-01-01

Copper and iron isotope fractionation by plant uptake and translocation is a matter of current research. As a way to apply the use of Cu and Fe stable isotopes in the phytoremediation of contaminated sites, the effects of organic amendment and microbial addition in a mine-spoiled soil seeded with Helianthus annuus in pot experiments and field trials were studied. Results show that the addition of a microbial consortium of ten bacterial strains has an influence on Cu and Fe isotope fractionation by the uptake and translocation in pot experiments, with an increase in average of 0.99 ‰ for the δ(65)Cu values from soil to roots. In the field trial, the amendment with the addition of bacteria and mycorrhiza as single and double inoculation enriches the leaves in (65)Cu compared to the soil. As a result of the same trial, the δ(56)Fe values in the leaves are lower than those from the bulk soil, although some differences are seen according to the amendment used. Siderophores, possibly released by the bacterial consortium, can be responsible for this change in the Cu and Fe fractionation. The overall isotopic fractionation trend for Cu and Fe does not vary for pot and field experiments with or without bacteria. However, variations in specific metabolic pathways related to metal-organic complexation and weathering can modify particular isotopic signatures.

Properties of the suprathermal heavy ion population near 1 AU during solar cycles 23 and 24

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dayeh, Maher A., E-mail: maldayeh@swri.edu; Ebert, Robert W.; Desai, Mihir I.

2016-03-25

Using measurements from the Advanced Composition Explorer/Ultra-Low Energy Isotope Spectrometer (ACE/ULEIS) near 1 AU, we surveyed the composition and spectra of heavy ions (He-through-Fe) during interplanetary quiet times from 1998 January 1 to 2014 December 31 at suprathermal energies between ∼0.11 and ∼1.28 MeV nucleon{sup −1}. The selected time period covers the maxima of solar cycles 23 and 24 and the extended solar minimum in between. We find the following: (1) The number of quiet-hours in each year correlates well with the sunspot number, year 2009 was the quietest for about 90% of the time; (2) The composition of the quiet-timemore » suprathermal heavy ion population ({sup 3}He, C-through-O, and Fe) correlates well with the level of solar activity, exhibiting SEP-like composition signatures during solar maximum, and CIR- or solar wind-like composition during solar minimum; (3) The heavy ion spectra at ∼0.11-0.32 MeV nucleon{sup −1} exhibit suprathermal tails with power-law spectral indices ranging from 1.4 to 2.7. (4) Fe spectral indices get softer (steeper) from solar minimum of cycle 23 to solar cycle 24 maximum. These results imply that during IP quiet times and at energies above ∼0.1 MeV nucleon{sup −1}, the IP medium is dominated by material from prior solar and interplanetary events.« less

Nitrogen isotope fractionation by alternative nitrogenases and past ocean anoxia

PubMed Central

Zhang, Xinning; Sigman, Daniel M.; Morel, François M. M.; Kraepiel, Anne M. L.

2014-01-01

Biological nitrogen fixation constitutes the main input of fixed nitrogen to Earth’s ecosystems, and its isotope effect is a key parameter in isotope-based interpretations of the N cycle. The nitrogen isotopic composition (δ15N) of newly fixed N is currently believed to be ∼–1‰, based on measurements of organic matter from diazotrophs using molybdenum (Mo)-nitrogenases. We show that the vanadium (V)- and iron (Fe)-only “alternative” nitrogenases produce fixed N with significantly lower δ15N (–6 to –7‰). An important contribution of alternative nitrogenases to N2 fixation provides a simple explanation for the anomalously low δ15N (<–2‰) in sediments from the Cretaceous Oceanic Anoxic Events and the Archean Eon. A significant role for the alternative nitrogenases over Mo-nitrogenase is also consistent with evidence of Mo scarcity during these geologic periods, suggesting an additional dimension to the coupling between the global cycles of trace elements and nitrogen. PMID:24639508

Lunar and Planetary Science XXXV: Terrestrial Planets: Building Blocks and Differentiation

NASA Technical Reports Server (NTRS)

2004-01-01

The session "Terrestrial Planets: Building Blocks and Differentiation: included the following topics:Magnesium Isotopes in the Earth, Moon, Mars, and Pallasite Parent Body: High-Precision Analysis of Olivine by Laser-Ablation Multi-Collector ICPMS; Meteoritic Constraints on Collision Rates in the Primordial Asteroid Belt and Its Origin; New Constraints on the Origin of the Highly Siderophile Elements in the Earth's Upper Mantle; Further Lu-Hf and Sm-Nd Isotopic Data on Planetary Materials and Consequences for Planetary Differentiation; A Deep Lunar Magma Ocean Based on Neodymium, Strontium and Hafnium Isotope Mass Balance Partial Resetting on Hf-W System by Giant Impacts; On the Problem of Metal-Silicate Equilibration During Planet Formation: Significance for Hf-W Chronometry ; Solid Metal-Liquid Metal Partitioning of Pt, Re, and Os: The Effect of Carbon; Siderophile Element Abundances in Fe-S-Ni-O Melts Segregated from Partially Molten Ordinary Chondrite Under Dynamic Conditions; Activity Coefficients of Silicon in Iron-Nickel Alloys: Experimental Determination and Relevance for Planetary Differentiation; Reinvestigation of the Ni and Co Metal-Silicate Partitioning; Metal/Silicate Paritioning of P, Ga, and W at High Pressures and Temperatures: Dependence on Silicate Melt Composition; and Closure of the Fe-S-Si Liquid Miscibility Gap at High Pressure and Its Implications for Planetary Core Formation.

Evidence of subduction and crust-mantle mixing from a single diamond

NASA Astrophysics Data System (ADS)

Schulze, Daniel J.; Harte, Ben; Valley, John W.; Channer, Dominic M. DeR.

2004-09-01

Cathodoluminescence (CL) imaging of polished sections of a diamond from the Guaniamo region of Venezuela suggests a history of the diamond involving two periods of growth separated by a period of resorption and possibly brittle deformation. In situ electron probe analysis of multiple eclogitic garnet inclusions reveals a correlation between garnet composition and location in the stone. An early-formed garnet in the diamond core has higher Ca/(Ca+Mg) and lower Mg/(Mg+Fe) values than later garnets associated with the second period of diamond growth. This variation conforms to an extensive trend of variation in the suite of eclogitic garnets extracted from Venezuelan diamonds. The diamond is zoned in carbon isotope composition (in situ secondary ion mass spectrometry, SIMS, data). The core compositions ( δ13C PDB), corresponding to the first stage of growth, average -17.7‰. The second period of growth is apparently in two sub-sets of CL zones with mean values of -13.0‰ and -7.9‰. Nitrogen contents of diamond are low (30-300 atomic ppm) and do not correlate with carbon isotope composition. Oxygen isotope ratios of the garnet inclusions are elevated substantially above those expected for "common mantle"; δ18O VSMOW of early garnet is approximately +10.5‰ and two late garnets average +8.8‰. The evolutionary trend of magnesium enrichment in garnet is unlikely to represent igneous fractionation. The stable isotope data are consistent with diamond formation in subducted meta-basic rocks that had interacted with sea water at low temperatures at or near the sea floor and contained a substantial biogenic carbon component. During or following subduction, diamonds continued to form in an evolving system that was progressively modified by interaction with mantle material.

Barnacles - recorders of environmental conditions with unique geochemical signatures

NASA Astrophysics Data System (ADS)

Vinzenz Ullmann, Clemens; Gale, Andy; Korte, Christoph; Frei, Robert; Huggett, Jenny; Wray, Dave

2017-04-01

Barnacles are calcite-forming arthropods that occur in a wide range of habitats in modern times and are found in sedimentary successions reaching back to the Paleozoic. Despite potential use of their mostly low-Mg calcite hard parts for palaeoenvironmental reconstructions, their geochemical composition has been little studied. Here, we present the first comprehensive overview of barnacle geochemistry, with C and O isotope, as well as Mg/Ca, Sr/Ca, Mn/Ca and Fe/Ca data for multiple samples of 42 species covering the orders Sessilia, Scalpelliformes, and Lepadiformes. XRD analyses confirm calcite as the only significant carbonate mineral of the studied barnacle shell material. Apart from one species, median Mg/Ca ratios fall below 50 mmol/mol, the approximate limit for low-Mg-calcite. In the order Sessilia, the scuta and terga are on average enriched in Mg by 36 % over the unmoveable plates. Amongst the calcite-forming marine animals, barnacles have very high Sr/Ca ratios of 2.6 to 5.9 mmol/mol, amongst the highest known for calcite secreting animals. Mn/Ca and Fe/Ca ratios are commonly low and compatible with other modern shell calcite, but can be strongly enriched to > 1 mmol/mol in proximal habitats, particularly close to areas strongly affected by human activity. Carbon and oxygen isotope data indicate formation of the calcite in or near isotopic equilibrium with ambient water conditions. Apart from species showing δ18O values below 0 ‰ V-PDB, a negative correlation of oxygen isotope ratios with Sr/Ca ratios is observed, which may be related to metabolic activity. Compositional patterns in barnacle shell material, particularly high Sr concentrations and Mg distribution in shell plates of the Sessilia, point to a great potential of barnacles for high fidelity reconstruction of past seawater chemistry and environmental conditions complementary to other archives.

The isotropic condition of energetic particles emitted from a large solar flare. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Spalding, J.

1983-01-01

Isotope abundance ratios for 5 to 50 MeV/nuc nuclei from a large solar flare were measured. The measurements were made by the heavy isotope spectrometer telescope (HIST) on the ISEE-3 satellite orbiting the Sun near an Earth-Sun liberation point approximately one million miles sunward of the Earth. Finite values for the isotope abundance ratios C-13/C-12, N-15/N-14, O-18/O-16, Ne-22/Ne-20, Mg-25/Mg-24, and Mg-26/Mg-24, and upper limits for the isotope abundance ratios He-3/He-4, C-14/C-12, O-17/O-16 and Ne-21/Ne-20 were reported. Element abundances and spectra were measured to compare the flare with other reported flares. The flare is a typical large flare with low Fe/O abundance or = to 0.1). For C-13/C-12, N-15/N-14, O-18/O-16, Mg-25/Mg-24 and Mg-26/Mg-24 isotope abundance ratios agree with the solar system abundance ratios. Measurement for Ne-22/Ne-20 agree with the isotopic composition of the meteoritic component neon-A.

The role of microbial iron reduction in the formation of Proterozoic molar tooth structures

NASA Astrophysics Data System (ADS)

Hodgskiss, Malcolm S. W.; Kunzmann, Marcus; Poirier, André; Halverson, Galen P.

2018-01-01

Molar tooth structures are poorly understood early diagenetic, microspar-filled voids in clay-rich carbonate sediments. They are a common structure in sedimentary successions dating from 2600-720 Ma, but do not occur in rocks older or younger, with the exception of two isolated Ediacaran occurrences. Despite being locally volumetrically significant in carbonate rocks of this age, their formation and disappearance in the geological record remain enigmatic. Here we present iron isotope data, supported by carbon and oxygen isotopes, major and minor element concentrations, and total organic carbon and sulphur contents for 87 samples from units in ten different basins spanning ca. 1900-635 Ma. The iron isotope composition of molar tooth structures is almost always lighter (modal depletion of 2‰) than the carbonate or residue components in the host sediment. We interpret the isotopically light iron in molar tooth structures to have been produced by dissimilatory iron reduction utilising Fe-rich smectites and Fe-oxyhydroxides in the upper sediment column. The microbial conversion of smectite to illite results in a volume reduction of clay minerals (∼30%) while simultaneously increasing pore water alkalinity. When coupled with wave loading, this biogeochemical process is a viable mechanism to produce voids and subsequently precipitate carbonate minerals. The disappearance of molar tooth structures in the mid-Neoproterozoic is likely linked to a combination of a decrease in smectite abundance, a decline in the marine DIC reservoir, and an increase in the concentration of O2 in shallow seawater.

Relationships Among Intrinsic Properties of Ordinary Chondrites: Oxidation State, Bulk Chemistry, Oxygen-isotopic Composition, Petrologic Type, and Chondrule Size

NASA Technical Reports Server (NTRS)

Rubin, Alan E.

2006-01-01

The properties of ordinary chondrites (OC) reflect both nebular and asteroidal processes. OC are modeled here as having acquired nebular water, probably contained within phyllosilicates, during agglomeration. This component had high Ai70 and acted like an oxidizing agent during thermal metamorphism. The nebular origin of this component is consistent with negative correlations in H, L, and LL chondrites between oxidation state (represented by olivine Fa) and bulk concentration ratios of elements involved in the metal-silicate fractionation (e.g., NdSi, Ir/Si, Ir/Mn, Ir/Cr, Ir/Mg, Ni/Mg, As/Mg, Ga/Mg). LL chondrites acquired the greatest abundance of phyllosilicates with high (delta)O-17 among OC (and thus became the most oxidized group and the one with the heaviest O isotopes); H chondrites acquired the lowest abundance, becoming the most reduced OC group with the lightest O isotopes. Chondrule precursors may have grown larger and more ferroan with time in each OC agglomeration zone. Nebular turbulence may have controlled the sizes of chondrule precursors. H-chondrite chondrules (which are the smallest among OC) formed from the smallest precursors. In each OC region, low-FeO chondrules formed before high-FeO chondrules during repeated episodes of chondrule formation. During thermal metamorphism, phyllosilicates were dehydrated; the liberated water oxidized metallic Fe-Ni. This caused correlated changes with petrologic type including decreases in the modal abundance of metal, increases in olivine Fa and low-Ca pyroxene Fs, increases in the olivine/pyroxene ratio, and increases in the kamacite Co and Ni contents. As water (with its heavy 0 isotopes) was lost during metamorphism, inverse correlations between bulk (delta)O-18 and bulk (delta)O-17 with petrologic type were produced. The H5 chondrites that were ejected from their parent body approx.7.5 Ma ago during a major impact event probably had been within a few kilometers of each other since they accreted approx.4.5 Ga ago. There are significant differences in the olivine compositional distributions among these rocks; these reflect stochastic nebular sampling of the oxidant (Le., phyllosilicates with high (delta)O-17) on a 0.1-1 km scale during agglomeration.

Trace Element Compositions of Pallasite Olivine Grains and Pallasite Origin

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Herrin, J. S.

2010-01-01

Pallasites are mixtures of metal with magnesian olivine. Most have similar metal compositions and olivine oxygen isotopic compositions; these are the main-group pallasites (PMG). The Eagle Station grouplet of pallasites (PES) have distinctive metal and olivine compositions and oxygen isotopic compositions. Pallasites are thought to have formed at the core-mantle boundary of their parent asteroids by mixing molten metal with solid olivine of either cumulatic or restitic origin. We have continued our investigation of pallasite olivines by doing in situ trace element analyses in order to further constrain their origin. We determined Al, P, Ca, Ga and first row transition element contents of olivine grains from suite of PMG and PES by LA-ICP-MS at JSC. Included in the PMG suite are some that have anomalous metal compositions (PMG-am) and atypically ferroan olivines (PMG-as). Our EMPA work has shown that there are unanticipated variations in olivine Fe/Mn, even within those PMG that have uni-form Fe/Mg. Manganese is homologous with Fe2+, and thus can be used the same way to investigate magmatic fractionation processes. It has an advantage for pallasite studies in that it is unaffected by redox exchange with the metal. PMG can be divided into three clusters on the basis of Mn/Mg; low, medium and high that can be thought of as less, typically and more fractionated in an igneous sense. The majority of PMG have medium Mn/Mg ratios. PMG-am occur in all three clusters; there does not seem to be any relationship between putative olivine igneous fractionation and metal composition. The PMG-as and one PMG-am make up the high Mn/Mg cluster; no PMG are in this cluster. The high Mn/Mg cluster ought to be the most fractionated (equivalent to the most Fe-rich in igneous suites), yet they have among the lowest contents of incompatible lithophile elements Al and Ti and the two PMG-as in this cluster also have low Ca and Sc contents. This is inconsistent with simple igneous fractionation on a single, initially homogeneous parent asteroid. For Al and Ti, the low and high Mn/Mg clusters have generally uniform contents, while the medium cluster has wide ranges. This is also true of analyses of duplicate grains from the medium cluster pallasites which can have very different Al and Ti contents. Those from the low and high clusters do not. These observations suggest that pallasite olivines are not cumulates, but rather are restites from high degrees of melting. The moderately siderophile elements P and Ga show wide ranges in the high Mn/Mg cluster, but very uniform compositions in the medium cluster, opposite the case for Al and Ti. There is no correlation of P or Ga and Fe/Mn as might be expected if redox processes controlled the contents of moderately siderophile elements in the olivines. The lack of correlation of P could reflect equilibration with phosphates, although there is no correlation of Ca with P as might be expected

Diamond brecciation and annealing accompanying major metasomatism in eclogite xenoliths from the Sask Craton, Canada

NASA Astrophysics Data System (ADS)

Czas, Janina; Stachel, Thomas; Pearson, D. Graham; Stern, Richard A.; Read, George H.

2018-05-01

We studied eclogite xenoliths (diamond-free n = 28; diamondiferous n = 22) from the Cretaceous Fort à la Corne Kimberlite Field in Western Canada for their major element, trace element and oxygen isotope compositions to assess their origin and metasomatic history, and possible relationships between metasomatism and diamond formation. All eclogites have major element and oxygen isotope compositions consistent with a derivation from different levels of subducted, seawater altered oceanic crust. While barren xenoliths are more likely to be of gabbroic origin, diamond-bearing samples commonly have signatures consistent with shallow basaltic protoliths. The mineral chemistry in bimineralic diamond-free eclogites spans a wide compositional range, yet it is typically homogenous within individual xenoliths. Temperatures calculated from Mg-Fe exchange between garnet and clinopyroxene range widely for these eclogites, from 740 to 1300 °C, indicating the presence of eclogite through most of the lithospheric mantle. Diamondiferous samples are restricted to high temperatures (1180-1390 °C), consistent with derivation from the zone of diamond stability. Compositionally, diamond-bearing eclogites span a broad range similar to their barren counterparts, but there is also heterogeneity in mineral chemistry on the intra-sample level and in particular garnets are characterised by strong internal chemical gradients. This intra-sample heterogeneity is interpreted as the result of intense melt metasomatism, which occurred in temporal proximity to host kimberlite magmatism, strongly affected major, trace and even oxygen isotope values and resulted in diamond brecciation and annealing.

Source of boron in the Palokas gold deposit, northern Finland: evidence from boron isotopes and major element composition of tourmaline

NASA Astrophysics Data System (ADS)

Ranta, Jukka-Pekka; Hanski, Eero; Cook, Nick; Lahaye, Yann

2017-06-01

The recently discovered Palokas gold deposit is part of the larger Rompas-Rajapalot gold-mineralized system located in the Paleoproterozoic Peräpohja Belt, northern Finland. Tourmaline is an important gangue mineral in the Palokas gold mineralization. It occurs as tourmalinite veins and as tourmaline crystals in sulfide-rich metasomatized gold-bearing rocks. In order to understand the origin of tourmaline in the gold-mineralized rocks, we have investigated the major element chemistry and boron isotope composition of tourmaline from three areas: (1) the Palokas gold mineralization, (2) a pegmatitic tourmaline granite, and (3) the evaporitic Petäjäskoski Formation. Based on textural evidence, tourmaline in gold mineralization is divided into two different types. Type 1 is located within the host rock and is cut by rock-forming anthophyllite crystals. Type 2 occurs in late veins and/or breccia zones consisting of approximately 80% tourmaline and 20% sulfides, commonly adjacent to quartz veins. All the studied tourmaline samples belong to the alkali-group tourmaline and can be classified as dravite and schorl. The δ11B values of the three localities lie in the same range, from 0 to -4‰. Tourmaline from the Au mineralization and from the Petäjäskoski Formation has similar compositional trends. Mg is the major substituent for Al; inferred low Fe3+/Fe2+ ratios and Na values (<0.8 atoms per formula unit (apfu)) of all tourmaline samples suggest that they precipitated from reduced, low-salinity fluids. Based on the similar chemical and boron isotope composition and the Re-Os age of molybdenite related to the tourmaline-sulfide-quartz veins, we propose that the tourmaline-forming process is a result of a single magmatic-hydrothermal event related to the extensive granite magmatism at around 1.79-1.77 Ga. Tourmaline was crystallized throughout the hydrothermal process, which resulted in the paragenetic variation between type 1 and type 2. The close association of tourmaline and gold suggests that the gold precipitated from the same boron-rich source as tourmaline.

New perspectives on the Li isotopic composition of the upper continental crust and its weathering signature

NASA Astrophysics Data System (ADS)

Sauzéat, Lucie; Rudnick, Roberta L.; Chauvel, Catherine; Garçon, Marion; Tang, Ming

2015-10-01

Lithium isotopes are increasingly used to trace both present-day and past weathering processes at the surface of the Earth, and could potentially be used to evaluate the average degree of past weathering recorded by the upper continental crust (UCC). Yet the previous estimate of average δ7Li of the UCC has a rather large uncertainty, hindering the use of Li isotopes for this purpose. New δ7Li for desert and periglacial loess deposits (windblown dust) from several parts of the world (Europe, Argentina, China and Tajikistan) demonstrate that the former are more homogeneous than the latter, and may therefore serve as excellent proxies of the average composition of large tracts of the UCC. The Li isotopic compositions and concentrations of desert loess samples are controlled by eolian sorting that can be quantified by a binary mixing between a weathered, fine-grained end-member, dominated by phyllosilicates and having low δ7Li, and an unweathered, coarse-grained end-member, that is a mixture of quartz and plagioclase having higher δ7Li. We use correlations between insoluble elements (REE, Nd/Hf and Fe2O3/SiO2), Li concentrations (henceforth referred as [Li]), and δ7Li to estimate a new, more precise, average Li isotopic composition and concentration for the UCC: [ Li ] = 30.5 ± 3.6 (2 σ) ppm, and δ7Li = + 0.6 ± 0.6 (2 σ). The δ7Li for desert loess deposits is anti-correlated with the chemical index of alteration (CIA). Using this relationship, along with our average δ7Li, we infer that (1) the present-day CIA of the average UCC is 61-2+4 (2 σ), higher than the common reference value of 53, and (2) the average proportion of chemically weathered components is as high as 37-10+17 (2 σ)% at the surface of the Earth.

Coal fly ash interaction with environmental fluids: Geochemical and strontium isotope results from combined column and batch leaching experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brubaker, Tonya M; Stewart, Brian W; Capo, Rosemary C

2013-05-01

The major element and Sr isotope systematics and geochemistry of coal fly ash and its interactions with environmental waters were investigated using laboratory flow-through column leaching experiments (sodium carbonate, acetic acid, nitric acid) and sequential batch leaching experiments (water, acetic acid, hydrochloric acid). Column leaching of Class F fly ash samples shows rapid release of most major elements early in the leaching procedure, suggesting an association of these elements with soluble and surface bound phases. Delayed release of certain elements (e.g., Al, Fe, Si) signals gradual dissolution of more resistant silicate or glass phases as leaching continues. Strontium isotope resultsmore » from both column and batch leaching experiments show a marked increase in {sup 87}Sr/{sup 86}Sr ratio with continued leaching, yielding a total range of values from 0.7107 to 0.7138. For comparison, the isotopic composition of fluid output from a fly ash impoundment in West Virginia falls in a narrow range around 0.7124. The experimental data suggest the presence of a more resistant, highly radiogenic silicate phase that survives the combustion process and is leached after the more soluble minerals are removed. Strontium isotopic homogenization of minerals in coal does not always occur during the combustion process, despite the high temperatures encountered in the boiler. Early-released Sr tends to be isotopically uniform; thus the Sr isotopic composition of fly ash could be distinguishable from other sources and is a useful tool for quantifying the possible contribution of fly ash leaching to the total dissolved load in natural surface and ground waters.« less

Effect of Wood Aging on Wine Mineral Composition and 87Sr/86Sr Isotopic Ratio.

PubMed

Kaya, Ayse D; Bruno de Sousa, Raúl; Curvelo-Garcia, António S; Ricardo-da-Silva, Jorge M; Catarino, Sofia

2017-06-14

The evolution of mineral composition and wine strontium isotopic ratio 87 Sr/ 86 Sr (Sr IR) during wood aging were investigated. A red wine was aged in stainless steel tanks with French oak staves (Quercus sessiliflora Salisb.), with three industrial scale replicates. Sampling was carried out after 30, 60, and 90 days of aging, and the wines were evaluated in terms of general analysis, phenolic composition, total polysaccharides, multielement composition, and Sr IR. Li, Be, Mg, Al, Sc, Ti, V, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Mo, Sb, Cs, Ba, Pr, Nd, Sm, Eu, Dy, Ho, Er, Yb, Lu, Tl, and Pb elements and 87 Sr/ 86 Sr were determined by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) and Na, K, Ca, and Fe by flame atomic absorption spectrometry (FAAS). Two-way ANOVA was applied to assess wood aging and time effect on Sr IR and mineral composition. Wood aging resulted in significantly higher concentrations of Mg, V, Co, Ni, and Sr. At the end of the aging period, wine exhibited statistically identical Sr IR compared to control. Study suggests that wood aging does not affect 87 Sr/ 86 Sr, not precluding the use of this parameter for wine traceability purposes.

Tennantite-tetrahedrite series from the Madan Pb-Zn deposits, Central Rhodopes, Bulgaria

NASA Astrophysics Data System (ADS)

Vassileva, Rossitsa D.; Atanassova, Radostina; Kouzmanov, Kalin

2014-08-01

Minerals from the tennantite-tetrahedrite series (fahlores) are found as single euhedral crystals and crustiform aggregates in hydrothermal veins of the Gradishte and Petrovitsa Pb-Zn deposits of the Madan ore field, southern Bulgaria. Unusually large compositional variations and fine oscillatory crystal zoning were investigated with electron microprobe analysis. The Gradishte samples correspond dominantly to tennantite, while Petrovitsa crystals have exclusively tetrahedrite composition. Fahlore compositions at Madan correspond to zincian varieties (1.6-1.95 apfu), with low Fe-content (<0.45 apfu). Minor silver is characteristic only for the Petrovitsa samples, reaching a maximum of 0.30 apfu. The (Cu+Ag) content of the Petrovitsa tennantites and the Cu content of the Gradishte tetrahedrites systematically exceed 10 apfu resulting in compensation of the excess Cu in the structure by Fe3+. Textural characteristics, mineral relationships and available fluid inclusion and stable isotope data suggest that fahlores precipitated in the late stages of mineralization at Madan, at temperature interval of 300-200 °C from oxidizing fluids with mixed (magmatic-meteoric) signatures.

Geochemical constraints on the spatial distribution of recycled oceanic crust in the mantle source of late Cenozoic basalts, Vietnam

NASA Astrophysics Data System (ADS)

Hoang, Thi Hong Anh; Choi, Sung Hi; Yu, Yongjae; Pham, Trung Hieu; Nguyen, Kim Hoang; Ryu, Jong-Sik

2018-01-01

This study presents a comprehensive analysis of the major and trace element, mineral, and Sr, Nd, Pb and Mg isotopic compositions of late Cenozoic intraplate basaltic rocks from central and southern Vietnam. The Sr, Nd, and Pb isotopic compositions of these basalts define a tight linear array between Indian mid-ocean-ridge basalt (MORB)-like mantle and enriched mantle type 2 (EM2) components. These basaltic rocks contain low concentrations of CaO (6.4-9.7 wt%) and have high Fe/Mn ratios (> 60) and FeO/CaO-3MgO/SiO2 values (> 0.54), similar to partial melts derived from pyroxenite/eclogite sources. This similarity is also supported by the composition of olivine within these samples, which contains low concentration of Ca and high concentrations of Ni, and shows high Fe/Mn ratios. The basaltic rocks have elevated Dy/Yb ratios that fall within the range of melts derived from garnet lherzolite material, although their Yb contents are much higher than those of modeled melts derived from only garnet lherzolite material and instead plot near the modeled composition of eclogite-derived melts. The Vietnamese basaltic rocks have lighter δ26Mg values (- 0.38 ± 0.06‰) than is expected for the normal mantle (- 0.25 ± 0.07‰), and these values decrease with decreasing Hf/Hf* and Ti/Ti* ratios, indicating that these basalts were derived from a source containing carbonate material. On primitive mantle-normalized multi-element variation diagrams, the central Vietnamese basalts are characterized by positive Sr, Eu, and Ba anomalies. These basalts also plot within the pelagic sediment field in Pbsbnd Pb isotopic space. This suggests that the mantle source of the basalts contained both garnet peridotite and recycled oceanic crust. A systematic analysis of variations in geochemical composition in basalts from southern to central Vietnam indicates that the recycled oceanic crust (possibly the paleo-Pacific slab) source material contains varying proportions of gabbro, basalt, and sediment. The basalts from south-central Vietnam (12°N-14°N) may be dominated by the lowest portion of the residual slab that contains rutile-bearing plagioclase-rich gabbroic eclogite, whereas the uppermost portion of the recycled slab, including sediment and basaltic material with small amounts of gabbro, may be a major constituent of the source for the basalts within the central region of Vietnam (14°N-16°N). Finally, the southern region (10°N-12°N) contains basalts sourced mainly from recycled upper oceanic crust that is basalt-rich and contains little or no sediment.

Evidence for the extraterrestrial origin of a natural quasicrystal.

PubMed

Bindi, Luca; Eiler, John M; Guan, Yunbin; Hollister, Lincoln S; MacPherson, Glenn; Steinhardt, Paul J; Yao, Nan

2012-01-31

We present evidence that a rock sample found in the Koryak Mountains in Russia and containing icosahedrite, an icosahedral quasicrystalline phase with composition Al(63)Cu(24)Fe(13), is part of a meteorite, likely formed in the early solar system about 4.5 Gya. The quasicrystal grains are intergrown with diopside, forsterite, stishovite, and additional metallic phases [khatyrkite (CuAl(2)), cupalite (CuAl), and β-phase (AlCuFe)]. This assemblage, in turn, is enclosed in a white rind consisting of diopside, hedenbergite, spinel (MgAl(2)O(4)), nepheline, and forsterite. Particularly notable is a grain of stishovite (from the interior), a tetragonal polymorph of silica that only occurs at ultrahigh pressures (≥ 10 Gpa), that contains an inclusion of quasicrystal. An extraterrestrial origin is inferred from secondary ion mass spectrometry (18)O/(16)O and (17)O/(16)O measurements of the pyroxene and olivine intergrown with the metal that show them to have isotopic compositions unlike any terrestrial minerals and instead overlap those of anhydrous phases in carbonaceous chondrite meteorites. The spinel from the white rind has an isotopic composition suggesting that it was part of a calcium-aluminum-rich inclusion similar to those found in CV3 chondrites. The mechanism that produced this exotic assemblage is not yet understood. The assemblage (metallic copper-aluminum alloy) is extremely reduced, and the close association of aluminum (high temperature refractory lithophile) with copper (low temperature chalcophile) is unexpected. Nevertheless, our evidence indicates that quasicrystals can form naturally under astrophysical conditions and remain stable over cosmic timescales, giving unique insights on their existence in nature and stability.

Isotopic fractionation associated with [NiFe]- and [FeFe]-hydrogenases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Hui; Gandhi, Hasand; Cornish, Adam J.

2016-01-30

Hydrogenases catalyze the reversible formation of H2 from electrons and protons with high efficiency. Understanding the relationships between H2 production, H2 uptake, and H2-H2O exchange can provide insight into the metabolism of microbial communities in which H2 is an essential component in energy cycling. In this manuscript, we used stable H isotopes (1H and 2H) to probe the isotope effects associated with three [FeFe]-hydrogenases and three [NiFe]-hydrogenases. All six hydrogenases displayed fractionation factors for H2 formation that were significantly less than 1, producing H2 that was severely depleted in 2H relative to the substrate, water. Consistent with differences in theirmore » active site structure, the fractionation factors for each class appear to cluster, with the three [NiFe]-hydrogenases (α = 0.27-0.40) generally having smaller values than the three [FeFe]-hydrogenases (α = 0.41-0.55). We also obtained isotopic fractionation factors associated with H2 uptake and H2-H2O exchange under conditions similar to those utilized for H2 production, providing us with a more complete picture of the three reactions catalyzed by hydrogenases. The fractionation factors determined in our studies can be used as signatures for different hydrogenases to probe their activity under different growth conditions and to ascertain which hydrogenases are most responsible for H2 production and/or uptake in complex microbial communities.« less

METHOD FOR PURIFYING URANIUM

DOEpatents

Kennedy, J.W.; Segre, E.G.

1958-08-26

A method is presented for obtaining a compound of uranium in an extremely pure state and in such a condition that it can be used in determinations of the isotopic composition of uranium. Uranium deposited in calutron receivers is removed therefrom by washing with cold nitric acid and the resulting solution, coataining uranium and trace amounts of various impurities, such as Fe, Ag, Zn, Pb, and Ni, is then subjected to various analytical manipulations to obtain an impurity-free uranium containing solution. This solution is then evaporated on a platinum disk and the residue is ignited converting it to U2/sub 3//sub 8/. The platinum disk having such a thin film of pure U/sub 2/O/sub 8/ is suitable for use with isotopic determination techaiques.

Re-Os and S isotope evidence for the origin of Platreef mineralization (Bushveld Complex)

NASA Astrophysics Data System (ADS)

Yudovskaya, M.; Belousova, E.; Kinnaird, J.; Dubinina, E.; Grobler, D. F.; Pearson, N.

2017-10-01

The Bushveld Complex contains the largest platinum-group element (PGE) deposits of the world that are represented by persistent stratiform reefs highly enriched with PGE with respect to underlying and overlying rocks. New Re-Os isotope and elemental LA MC-ICPMS data on platinum-group minerals (PGM) from the mineralized reefs are presented with implications to correlation between the different segments of the Bushveld Complex and a role of superimposed processes at the reef formation. We analyzed laurite (RuS2), hollingworthite (RhAsS), sperrylite (PtAs2) and Pt-Fe alloys from the Merensky Reef, Pseudoreef and the PGE reef of the Platreef. The measured 187Os/188Os value for Platreef laurite is 0.1751 ± 0.0004 whereas the ratios for sperrylite and hollingworthite range to slightly higher values (0.1713-0.1818 and 0.1744-0.1835 respectively). The observed textures of the analyzed PGM, such as Pt-Fe symplectites in base metal sulfides (BMS), laurite inclusions in chromite and sperrylite rims around sulfide-silicate aggregates, are interpreted as features of primary magmatic crystallization whereas hollingworthite overgrowths and exsolutions in sperrylite are likely to have originated from later solid state transformation or metasomatic processes. The Platreef is a composite sill-like body in the northern limb correlative to the Critical Zone in terms of stratigraphic position, whole-rock geochemistry and isotope characteristics. The pristine magmatic character of sulfides and PGM in the stratiform reefs at the top of the Platreef strongly resembles the style of Merensky Reef mineralization. However, the basal part of the Platreef pyroxenitic sequence is variably contaminated and mineralized with a significant hydrothermal overprint. Sulfides from underlying Lower Zone peridotite yield δ34S values varying from +9‰ to +14.2‰ that are much higher than the values for the overlying Platreef and are a consequence of sulfur assimilation from sedimentary sulfates. The same homogeneous mantle-like S isotope compositions in the high-grade PGE reef of the Platreef and the Merensky Reef can be explained by enhanced S isotope exchange through the orthomagmatic process of sulfide upgrading. The similar values and the limited variations of the initial Os isotopic ratios of all PGMs in both reefs also support their magmatic crystallization and origin from a common source.

Cu isotopes in marine black shales record the Great Oxidation Event

PubMed Central

Rodríguez, Nathalie P.; Partin, Camille A.; Andersson, Per; Weiss, Dominik J.; El Albani, Abderrazak; Rodushkin, Ilia; Konhauser, Kurt O.

2016-01-01

The oxygenation of the atmosphere ∼2.45–2.32 billion years ago (Ga) is one of the most significant geological events to have affected Earth’s redox history. Our understanding of the timing and processes surrounding this key transition is largely dependent on the development of redox-sensitive proxies, many of which remain unexplored. Here we report a shift from negative to positive copper isotopic compositions (δ65CuERM-AE633) in organic carbon-rich shales spanning the period 2.66–2.08 Ga. We suggest that, before 2.3 Ga, a muted oxidative supply of weathering-derived copper enriched in 65Cu, along with the preferential removal of 65Cu by iron oxides, left seawater and marine biomass depleted in 65Cu but enriched in 63Cu. As banded iron formation deposition waned and continentally sourced Cu became more important, biomass sampled a dissolved Cu reservoir that was progressively less fractionated relative to the continental pool. This evolution toward heavy δ65Cu values coincides with a shift to negative sedimentary δ56Fe values and increased marine sulfate after the Great Oxidation Event (GOE), and is traceable through Phanerozoic shales to modern marine settings, where marine dissolved and sedimentary δ65Cu values are universally positive. Our finding of an important shift in sedimentary Cu isotope compositions across the GOE provides new insights into the Precambrian marine cycling of this critical micronutrient, and demonstrates the proxy potential for sedimentary Cu isotope compositions in the study of biogeochemical cycles and oceanic redox balance in the past. PMID:27091980

Modeling the global distribution of the oxygen isotopic composition of sulfate aerosols: Importance of transition metal catalyzed S(IV) oxidation chemistry

NASA Astrophysics Data System (ADS)

Alexander, B.; Park, R. J.

2006-12-01

The oxygen isotopic composition of sulfate aerosols (Δ17O ~ δ&&17O 0.5*δ18O) reflects the relative importance of different photochemical oxidation pathways in the atmosphere. Simulated isotopic variability in a global chemical transport model (GEOS-Chem) shows good agreement with observations in oceanic [Alexander et al., 2005] and some continental sites. However, a large discrepancy exists between modeled and measured isotopic composition in the high northern latitudes, reflecting an incomplete understanding of the sulfur budget in this region. Recent oxygen isotope measurements of sulfate aerosols collected at Alert, Canada suggest that transition metal catalyzed oxidation of SO2 by O2 in the aqueous-phase is significant during winter [Mc Cabe et al.,2006]. Global chemistry models ignore this oxidation pathway because it is believed to be important only regionally, and because of the large uncertainties in atmospheric metal concentrations and oxidation states. We have incorporated Fe(III) and Mn(II) catalyzed oxidation of S(IV) (S(IV) = SO2·H2O + HSO3- + SO32-) by O2 into the GEOS-Chem model using the McCabe et al. [2006] isotope measurements as a constraint. We will examine the importance of this oxidation pathway for the sulfur budget in the Arctic, and on the global scale. Preliminary results suggest that, during winter, up to 75% of aerosol sulfate at Alert forms via the metal catalysis pathway. The addition of this chemical pathway decreases the SO2 burden in the Arctic (north of 60°N) by 40% due to an increase in the oxidation rate. The comparison of large-scale sulfate aerosol models study (COSAM) showed that on average, models over-predict SO2 mixing ratios by factors of 2 or more [Barrie et al., 2001]. This "missing" S(IV) oxidation pathway can partially explain this discrepancy.

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ(57/54)Fe Observations.

PubMed

Toner, Brandy M; Rouxel, Olivier J; Santelli, Cara M; Bach, Wolfgang; Edwards, Katrina J

2016-01-01

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ(57)Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.

Multiple oxygen and sulfur isotope compositions of secondary atmospheric sulfate in the city of Wuhan, central China

NASA Astrophysics Data System (ADS)

Li, X.; Bao, H.; Zhou, A.; Wang, D.

2012-12-01

Secondary atmospheric sulfate (SAS) is the oxidation product and sink for sulfur gases of biological, volcanic, and anthropogenic origins on Earth. SAS can be produced from gas-phase OH-radical oxidation and five aqueous-phase chemical reactions including aqueous-phase S (IV) oxidation reactions by H2O2, O3, oxygen catalyzed by Fe3+ and Mn2+, and methyle hydrogen peroxide and peroxyacetic acid. The tropospheric sulfur oxidation pathway is therefore determined by cloud-water pH, dissolved [Fe2+] or [Mn2+] content, S emission rate, meteorological condition, and other factors. The S isotope composition is a good tracer for the source while the O isotopes, especially the triple O isotope compositions are a good tracer for S oxidation pathway. Jerkins and Bao (2006) provided the first set of multiple stable isotope compositions (δ34S, δ18O and Δ17O) for SAS collected from bulk atmosphere in Baton Rouge in the relatively rural southern USA. Their study revealed a long-tern average Δ17O value of ~+0.7‰ for SAS, and speculated that much of the Earth mid-latitudes may have a similar average SAS Δ17O value. Additional sampling campaign at different sites is necessarily for constructing and testing models on sulfur oxidation and transport in the troposphere. A total of 33 sulfate samples were collected from bulk atmospheric deposition over a 950-day period from May 2009 to December 2011 in the city of Wuhan, Hubei Province, China. Differing from Baton Rouge, Wuhan is an industrial metropolis with a population of 9.8 million and a high particulate matter content (115 μg/m3). It also has a subtropical monsoon climate, with rainwater pH at ~5.3 year-around. The rainwater ion concentrations have seasonal variations, typically low in summer and high in winter. The anions are dominated by SO42-, at an average concentration of 8.5 mg/L. There is little sulfate contribution from sea-salt (SS) sulfate or dusts in Wuhan. The isotopic compositions for bulk atmospheric sulfate range from 0.00‰ to 1.02‰ for the Δ17O, 8.0‰ to 17.8‰ for the δ18O, and 2.1‰ to 24.1‰ for the δ34S. No apparent correlation is found among Δ17O, δ18O, or δ34S values. No significant temporal pattern exists for the Δ17O over the collection period. The positive Δ17O values for SAS have a time-weighted average of 0.52 ± 0.23‰, lower than the average in Baton Rouge, raising the possibility that the high particulate matter content in Wuhan may have played a role in promoting S oxidation via surface and/or Fe(III)-catalyzed pathways that do not generate positive 17O anomaly in product sulfate. The average Δ17O value also supports the assertion that the long-term average Δ17O value for SAS in the mid-latitude sites fall within a range (0.6~0.8‰) that is much lower than that in polar areas. The SAS δ18O values in Wuhan lie within the range reported for other sites (+5.0‰ to +19.6‰), with a time-weighted average value of 12.0 ± 2.3‰. Not counting three outlier (>13‰), the δ34S values are at a narrow range with a time-weighted average of +4.5 ±1.3‰ (n=30), which is higher than those from Baton Rouge but is typical for the heavily populated regions in China.

Nature and origin of the nonsulfide zinc deposits in the Sierra Mojada District, Coahuila, Mexico: constraints from regional geology, petrography, and isotope analyses

NASA Astrophysics Data System (ADS)

Kyle, J. Richard; Ahn, Hyein; Gilg, H. Albert

2018-02-01

The Sierra Mojada District comprises multiple types of near-surface mineral concentrations ranging from polymetallic sulfide zones, "nonsulfide Zn" (NSZ) deposits, and a silver-rich Pb carbonate deposit hosted by lower Cretaceous carbonate strata. Hypogene concentrations of Fe-Zn-Pb-Cu-Ag sulfides and sulfosalts are locally preserved and are associated with hydrothermal dolomite and silica. Alteration mineralogy and sulfur isotope data suggest primary Zn-Pb-Ag mineralization from circa 200 °C hydrothermal fluids. The NSZ deposits dominantly consist of smithsonite and hemimorphite associated with local Mn-Fe oxides. The Red Zinc Zone consists of strata-bound zones dominantly of hemimorphite that fills pores in residual and resedimented Fe oxides. The White Zinc Zone shows local dissolution features, including internal sediments interbanded with and cemented by smithsonite. Similar Pb isotopic compositions of smithsonite, hemimorphite, and cerussite to Sierra Mojada galena document that the NSZ deposits originated from polymetallic carbonate-replacement sulfide deposits, with flow of metal-bearing groundwater being controlled by local topography and structural features in this extensional terrane. Oxygen isotope values for Sierra Mojada smithsonite are relatively constant (δ18OVSMOW = 20.9 to 23.3‰) but are unusually low compared to other supergene smithsonites. Using δ18OVSMOW (- 8‰) of modern groundwater at nearby Cuatrociénegas, smithsonite formational temperatures are calculated to have been between 26 to 35 °C. Smithsonite precipitation was favored by near-neutral conditions typical of carbonate terranes, whereas hemimorphite precipitated by reaction with wallrock silica and locally, or episodically, more acidic conditions resulting from sulfide oxidation. Transition to, and stabilization of, the modern desert climate over the past 9000 years from the Late Pleistocene wetter, cooler climate of northern Mexico resulted in episodic drawdown of the water table and termination of local supergene metal mobilization.

Magnesium Isotope Ratios in ω Centauri Red Giants

NASA Astrophysics Data System (ADS)

Da Costa, G. S.; Norris, John E.; Yong, David

2013-05-01

We have used the high-resolution observations obtained at the Anglo-Australian Telescope with Ultra-High Resolution Facility (R ~ 100,000) and at Gemini-S with b-HROS (R ~ 150,000) to determine magnesium isotope ratios for seven ω Cen red giants that cover a range in iron abundance from [Fe/H] = -1.78 to -0.78 dex, and for two red giants in M4 (NGC 6121). The ω Cen stars sample both the "primordial" (i.e., O-rich, Na- and Al-poor) and the "extreme" (O-depleted, Na- and Al-rich) populations in the cluster. The primordial population stars in both ω Cen and M4 show (25Mg, 26Mg)/24Mg isotopic ratios that are consistent with those found for the primordial population in other globular clusters with similar [Fe/H] values. The isotopic ratios for the ω Cen extreme stars are also consistent with those for extreme population stars in other clusters. The results for the extreme population stars studied indicate that the 26Mg/24Mg ratio is highest at intermediate metallicities ([Fe/H] < -1.4 dex), and for the highest [Al/Fe] values. Further, the relative abundance of 26Mg in the extreme population stars is notably higher than that of 25Mg, in contrast to model predictions. The 25Mg/24Mg isotopic ratio in fact does not show any obvious dependence on either [Fe/H] or [Al/Fe] nor, intriguingly, any obvious difference between the primordial and extreme population stars.

Formation and resulfidization of a South Texas roll-type uranium deposit

USGS Publications Warehouse

Goldhaber, Martin B.; Reynolds, Richard L.; Rye, Robert O.

1979-01-01

Core samples from a roll type uranium deposit in Live Oak County, south Texas have been studied and results are reported for Se, Mo, FeS2 and organic-carbon distribution, sulfide mineral petrology, and sulfur isotopic composition of iron-disulfide phases. In addition, sulfur isotopic compositions of dissolved sulfate and sulfide from the modern ground water within the ore bearing sand have been studied. The suite of elements in the ore sand and their geometric relationships throughout the deposit are those expected for typical roll-type deposits with well-developed oxidation-reduction interfaces. However, iron-disulfide minerals are abundant in the altered tongue, demonstrating that this interval has been sulfidized after mineralization (resulfidized or rereduced). Iron disulfide minerals in the rereduced interval differ mineralogically and isotopically from those throughout the remainder of the deposit. The resulfidized sand contains dominantly pyrite that is enriched in 34S, whereas the sand beyond the altered tongue contains abundant marcasite that is enriched in the light isotope, 32S. Textural relationships between pyrite and marcasite help to establish relative timing of iron disulfide formation. In reduced rock outside the altered tongue, three distinct generations of iron disulfide are present. The oldest of these generations consists largely of pyrite with lesser amounts of marcasite. A major episode of marcasite formation contemporaneous with ore genesis postdates the oldest pyrite generation but predates a younger pyrite generation. Resulfidization probably led to the final pyrite stage recognized beyond the altered tongue. Stable isotope data establish that the source of sulfur for the resulfidization was fault-leaked H2S probably derived from the Edwards Limestone of Cretaceous age which underlies the deposit. The deposit formed in at least two stages: (1) a pre-ore process of host rock sulfidization which produced disseminated pyrite as the dominant iron disulfide phase; and (2) an ore-stage process which led to the development of the uranium roll with emplacement of the characteristic suite of minor and accessory elements and which produced abundant isotopically light marcasite. The host rock was modified by a post-ore stage of resulfidization which precipitated isotopically heavy pyrite. Sulfur isotopic compositions of sulfide and sulfate present in modern ground water within the host sand differ greatly from sulfur isotopic composition of iron disulfides formed during the resulfidization episode. Iron disulfide minerals formed from the sulfur species of modern ground water have not been unequivocally identified.

The He isotope composition of the earliest picrites erupted by the Ethiopia plume, implications for mantle plume source

NASA Astrophysics Data System (ADS)

Stuart, Finlay; Rogers, Nick; Davies, Marc

2016-04-01

The earliest basalts erupted by mantle plumes are Mg-rich, and typically derived from mantle with higher potential temperature than those derived from the convecting upper mantle at mid-ocean ridges and ocean islands. The chemistry and isotopic composition of picrites from CFB provide constraints on the composition of deep Earth and thus the origin and differentiation history. We report new He-Sr-Nd-Pb isotopic composition of the picrites from the Ethiopian flood basalt province from the Dilb (Chinese Road) section. They are characterized by high Fe and Ti contents for MgO = 10-22 wt. % implying that the parent magma was derived from a high temperature low melt fraction, most probably from the Afar plume head. The picrite 3He/4He does not exceed 21 Ra, and there is a negative correlation with MgO, the highest 3He/4He corresponding to MgO = 15.4 wt. %. Age-corrected 87Sr/86Sr (0.70392-0.70408) and 143Nd/144Nd (0.512912-0.512987) display little variation and are distinct from MORB and OIB. Age-corrected Pb isotopes display a significant range (e.g. 206Pb/204Pb = 18.70-19.04) and plot above the NHRL. These values contrast with estimates of the modern Afar mantle plume which has lower 3He/4He and Sr, Nd and Pb isotope ratios that are more comparable with typical OIB. These results imply either interaction between melts derived from the Afar mantle plume and a lithospheric component, or that the original Afar mantle plume had a rather unique radiogenic isotope composition. Regardless of the details of the origins of this unusual signal, our observations place a minimum 3He/4He value of 21 Ra for the Afar mantle plume, significantly greater than the present day value of 16 Ra, implying a significant reduction over 30 Myr. In addition the Afar source was less degassed than convecting mantle but more degassed than mantle sampled by the proto-Iceland plume (3He/4He ~50 Ra). This suggests that the largest mantle plumes are not sourced in a single deep mantle domain with a common depletion history and that they do not mix with shallower mantle reservoirs to the same extent.

Molybdenum isotope fractionation during adsorption to organic matter

NASA Astrophysics Data System (ADS)

King, E. K.; Perakis, S. S.; Pett-Ridge, J. C.

2018-02-01

Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2-170 h) and pH (2-7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (±0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffractionmore » (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ 57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. Lastly, these micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.« less

Compositions of HIMU, EM1, and EM2 from Global Trends between Radiogenic Isotopes and Major Elements in Ocean Island Basalts

NASA Astrophysics Data System (ADS)

Jackson, M. G.; Dasgupta, R.

2008-12-01

Sr and Pb isotopes exhibit global trends with the concentrations of major elements (SiO2, TiO2, FeO, Al2O3 and K2O) and major elements ratios (CaO/Al2O3 and K2O/TiO2) in the shield-stage lavas from 18 oceanic hotspots (including Hawaii, Iceland, Galapagos, Cook-Australs, St. Helena, Cape Verde, Cameroon, Canary, Madeira, Comoros, Azores, Samoa, Society, Marquesas, Mascarene, Kerguelen, Pitcairn, and Selvagen). Based on the relationships between major elements and isotopes in ocean island basalts (OIBs), we find that the lavas derived from the mantle end members, HIMU (or high 'ì' = 238U/204Pb), EM1 (enriched mantle 1), EM2 (enriched mantle 2), and DMM (depleted MORB [mid-ocean ridge basalt] mantle) exhibit distinct major element characteristics: When compared to oceanic hotspots globally, the hotspots with a HIMU (radiogenic Pb-isotopes and low 87Sr/86Sr) component, such as St. Helena and Cook-Australs, exhibit high CaO/Al2O3, FeOT, and TiO2 and low SiO2 and Al2O3. EM1 (enriched mantle 1; intermediate 87Sr/86Sr and low 206Pb/204Pb; sampled by hotspots like Pitcairn and Kerguelen) and EM2 (enriched mantle 2; high 87Sr/86Sr and intermediate 206Pb/204Pb; sampled by hotspots like Samoa and Societies) exhibit higher K2O concentrations and K2O/TiO2 weight ratios than HIMU lavas. EM1 lavas exhibit the lowest CaO/Al2O3 in the OIB dataset, and this sets EM1 apart from EM2. A plot of CaO/Al2O3 vs K2O/TiO2 perfectly resolves the four mantle end member lavas. Melting processes (pressure, temperature and degree of melting) fail to provide an explanation for the full spectrum of major element concentrations in OIBs. Such processes also fail to explain the correlations between major elements and radiogenic isotopes. Instead, a long, time integrated history of various parent- daughter elements appears to be coupled to major element and/or volatile heterogeneity in the mantle source. End member lava compositions are compared with experimental partial melt compositions to place constraints on the lithological characteristics of the mantle end members.

Compositions of HIMU, EM1, and EM2 from global trends between radiogenic isotopes and major elements in ocean island basalts

NASA Astrophysics Data System (ADS)

Jackson, Matthew G.; Dasgupta, Rajdeep

2008-11-01

Sr and Pb isotopes exhibit global trends with the concentrations of major elements (SiO 2, TiO 2, FeO, Al 2O 3 and K 2O) and major elements ratios (CaO/Al 2O 3 and K 2O/TiO 2) in the shield-stage lavas from 18 oceanic hotspots (including Hawaii, Iceland, Galapagos, Cook-Australs, St. Helena, Cape Verde, Cameroon, Canary, Madeira, Comoros, Azores, Samoa, Society, Marquesas, Mascarene, Kerguelen, Pitcairn, and Selvagen). Based on the relationships between major elements and isotopes in ocean island basalts (OIBs), we find that the lavas derived from the mantle end members, HIMU (or high 'μ' = 238U/ 204Pb), EM1 (enriched mantle 1), EM2 (enriched mantle 2), and DMM (depleted MORB [mid-ocean ridge basalt] mantle) exhibit distinct major element characteristics: When compared to oceanic hotspots globally, the hotspots with a HIMU (radiogenic Pb-isotopes and low 87Sr/ 86Sr) component, such as St. Helena and Cook-Australs, exhibit high CaO/Al 2O 3, FeO T, and TiO 2 and low SiO 2 and Al 2O 3. EM1 (enriched mantle 1; intermediate 87Sr/ 86Sr and low 206Pb/ 204Pb; sampled by hotspots like Pitcairn and Kerguelen) and EM2 (enriched mantle 2; high 87Sr/ 86Sr and intermediate 206Pb/ 204Pb; sampled by hotspots like Samoa and Societies) exhibit higher K 2O concentrations and K 2O/TiO 2 weight ratios than HIMU lavas. EM1 lavas exhibit the lowest CaO/Al 2O 3 in the OIB dataset, and this sets EM1 apart from EM2. A plot of CaO/Al 2O 3 vs K 2O/TiO 2 perfectly resolves the four mantle end member lavas. Melting processes (pressure, temperature and degree of melting) fail to provide an explanation for the full spectrum of major element concentrations in OIBs. Such processes also fail to explain the correlations between major elements and radiogenic isotopes. Instead, a long, time integrated history of various parent-daughter elements appears to be coupled to major element and/or volatile heterogeneity in the mantle source. End member lava compositions are compared with experimental partial melt compositions to place constraints on the lithological characteristics of the mantle end members.

Sulfate and sulfide sulfur isotopes (δ34S and δ33S) measured by solution and laser ablation MC-ICP-MS: An enhanced approach using external correction

USGS Publications Warehouse

Pribil, Michael; Ridley, William I.; Emsbo, Poul

2015-01-01

Isotope ratio measurements using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) commonly use standard-sample bracketing with a single isotope standard for mass bias correction for elements with narrow-range isotope systems measured by MC-ICP-MS, e.g. Cu, Fe, Zn, and Hg. However, sulfur (S) isotopic composition (δ34S) in nature can range from at least − 40 to + 40‰, potentially exceeding the ability of standard-sample bracketing using a single sulfur isotope standard to accurately correct for mass bias. Isotopic fractionation via solution and laser ablation introduction was determined during sulfate sulfur (Ssulfate) isotope measurements. An external isotope calibration curve was constructed using in-house and National Institute of Standards and Technology (NIST) Ssulfate isotope reference materials (RM) in an attempt to correct for the difference. The ability of external isotope correction for Ssulfate isotope measurements was evaluated by analyzing NIST and United States Geological Survey (USGS) Ssulfate isotope reference materials as unknowns. Differences in δ34Ssulfate between standard-sample bracketing and standard-sample bracketing with external isotope correction for sulfate samples ranged from 0.72‰ to 2.35‰ over a δ34S range of 1.40‰ to 21.17‰. No isotopic differences were observed when analyzing Ssulfide reference materials over a δ34Ssulfide range of − 32.1‰ to 17.3‰ and a δ33S range of − 16.5‰ to 8.9‰ via laser ablation (LA)-MC-ICP-MS. Here, we identify a possible plasma induced fractionation for Ssulfate and describe a new method using external isotope calibration corrections using solution and LA-MC-ICP-MS.

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

USGS Publications Warehouse

Coplen, T.B.; Hopple, J.A.; Böhlke, J.K.; Peiser, H.S.; Rieder, S.E.; Krouse, H.R.; Rosman, K.J.R.; Ding, T.; Vocke, R.D.; Revesz, K.M.; Lamberty, A.; Taylor, P.; De Bievre, P.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Preparation and biodistribution of 59Fe-radiolabelled iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Pospisilova, Martina; Zapotocky, Vojtech; Nesporova, Kristina; Laznicek, Milan; Laznickova, Alice; Zidek, Ondrej; Cepa, Martin; Vagnerova, Hana; Velebny, Vladimir

2017-02-01

We report on the 59Fe radiolabelling of iron oxide nanoparticle cores through post-synthetic isotope exchange (59Fe-IONPex) and precursor labelling (59Fe-IONPpre). Scanning electron microscopy and dynamic light scattering measurements showed no impact of radiolabelling on nanoparticle size or morphology. While incorporation efficiencies of these methods are comparable—83 and 90% for precursor labelling and post-synthetic isotope exchange, respectively—59Fe-IONPpre exhibited much higher radiochemical stability in citrated human plasma. Quantitative ex vivo biodistribution study of 59Fe-IONPpre coated with triethylene glycol was performed in Wistar rats. Following the intravenous administration, high 59Fe concentration was observed in the lung and the organs of the reticuloendothelial system such as the liver, the spleen and the femur.

Elemental and isotopic behaviour of Zn in Deccan basalt weathering profiles: Chemical weathering from bedrock to laterite and links to Zn deficiency in tropical soils.

PubMed

Suhr, Nils; Schoenberg, Ronny; Chew, David; Rosca, Carolina; Widdowson, Mike; Kamber, Balz S

2018-04-01

Zinc (Zn) is a micronutrient for organisms and essential for plant growth, therefore knowledge of its elemental cycling in the surface environment is important regarding wider aspects of human nutrition and health. To explore the nature of Zn cycling, we compared its weathering behaviour in a sub-recent regolith versus an ancient laterite profile of the Deccan Traps, India - an area of known soil Zn deficiency. We demonstrate that progressive breakdown of primary minerals and the associated formation of phyllosilicates and iron oxides leads to a depletion in Zn, ultimately resulting in a loss of 80% in lateritic residues. This residue is mainly composed of resistant iron oxides and hydroxides ultimately delivering insufficient amounts of bio-available Zn. Moreover, (sub)-tropical weathering in regions experiencing extended tectonic quiescence (e.g., cratons) further enhance the development of old and deep soil profiles that become deficient in Zn. This situation is clearly revealed by the spatial correlation of the global distribution of laterites, cratons (Africa, India, South America and Australia) and known regions of Zn deficient soils that result in health problems for humans whose diet is derived from such land. We also investigate whether this elemental depletion of Zn is accompanied by isotope fractionation. In the saprolitic horizons of both weathering profiles, compositions of δ 66 Zn JMC-Lyon lie within the "crustal average" of +0.27±0.07‰ δ 66 Zn JMC-Lyon . By contrast, soil horizons enriched in secondary oxides show lighter isotope compositions. The isotopic signature of Zn (Δ 66 Zn sample-protolith up to ~ -0.65‰) during the formation of the ferruginous-lateritic weathering profile likely resulted from a combination of biotically- and kinetically-controlled sorption reactions on Fe-oxyhydroxides. Our findings suggest that oxide rich soil types/horizons in (sub)-tropical regions likely exert a control on riverine Zn isotope compositions such that these become heavier than the crustal average. This isotopic behaviour invites a broader study of global soils to test whether light isotope composition alone could serve as an indicator for reduced bioavailability of Zn. Copyright © 2017 Elsevier B.V. All rights reserved.

Mechanism of Nitrogenase H 2 Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khadka, Nimesh; Milton, Ross D.; Shaw, Sudipta

Nitrogenase catalyzes the reduction of dinitrogen (N2) to ammonia (NH3) with obligatory reduction of protons (H+) to dihydrogen (H2) through a mechanism involving reductive elimination of two [Fe-H-Fe] bridging hydrides at its active site FeMo-cofactor. The overall rate-limiting step is associated with ATP-driven electron delivery from Fe protein, precluding isotope effect measurements on substrate reduction steps. Here, we use mediated bioelectrocatalysis to drive electron delivery to MoFe protein without Fe protein and ATP hydrolysis, thereby eliminating the normal rate-limiting step. The ratio of catalytic current in mixtures of H2O and D2O, the proton inventory, changes linearly with the D2O/H2O ratio,more » revealing that a single H/D is involved in the rate limiting step. Kinetic models, along with measurements that vary the electron/proton delivery rate and use different substrates, reveal that the rate-limiting step under these conditions is the H2 formation reaction. Altering the chemical environment around the active site FeMo-cofactor in the MoFe protein either by substituting nearby amino acids or transferring the isolated FeMo-cofactor into a different peptide matrix, changes the net isotope effect, but the proton inventory plot remains linear, consistent with an unchanging rate-limiting step. Density functional theory predicts a transition state for H2 formation where the proton from S-H+ moves to the hydride in Fe-H-, predicting the number and magnitude of the observed H/D isotope effect. This study not only reveals the mechanism of H2 formation, but also illustrates a strategy for mechanistic study that can be applied to other enzymes and to biomimetic complexes.« less

Laboratory studies of refractory metal oxide smokes

NASA Technical Reports Server (NTRS)

Nuth, Joseph A.; Nelson, R. N.; Donn, Bertram

1989-01-01

Studies of the properties of refractory metal oxide smokes condensed from a gas containing various combinations of SiH4, Fe(CO)5, Al(CH3)3, TiCl4, O2 and N2O in a hydrogen carrier stream at 500 K greater than T greater than 1500 K were performed. Ultraviolet, visible and infrared spectra of pure, amorphous SiO(x), FeO(x), AlO(x) and TiO(x) smokes are discussed, as well as the spectra of various co-condensed amorphous oxides, such as FE(x)SiO(y) or Fe(x)AlO(y). Preliminary studies of the changes induced in the infrared spectra of iron-containing oxide smokes by vacuum thermal annealing suggest that such materials become increasingly opaque in the near infrared with increased processing: hydration may have the opposite effect. More work on the processing of these materials is required to confirm such a trend: this work is currently in progress. Preliminary studies of the ultraviolet spectra of amorphous Si2O3 and MgSiO(x) smokes revealed no interesting features in the region from 200 to 300 nm. Studies of the ultraviolet spectra of both amorphous, hydrated and annealed SiO(x), TiO(x), AlO(x) and FeO(x) smokes are currently in progress. Finally, data on the oxygen isotopic composition of the smokes produced in the experiments are presented, which indicate that the oxygen becomes isotopically fractionated during grain condensation. Oxygen in the grains is as much as 3 percent per amu lighter than the oxygen in the original gas stream. The authors are currently conducting experiments to understand the mechanism by which fractionation occurs.

Authigenic oxide Neodymium Isotopic composition as a proxy of seawater: applying multivariate statistical analyses.

NASA Astrophysics Data System (ADS)

McKinley, C. C.; Scudder, R.; Thomas, D. J.

2016-12-01

The Neodymium Isotopic composition (Nd IC) of oxide coatings has been applied as a tracer of water mass composition and used to address fundamental questions about past ocean conditions. The leached authigenic oxide coating from marine sediment is widely assumed to reflect the dissolved trace metal composition of the bottom water interacting with sediment at the seafloor. However, recent studies have shown that readily reducible sediment components, in addition to trace metal fluxes from the pore water, are incorporated into the bottom water, influencing the trace metal composition of leached oxide coatings. This challenges the prevailing application of the authigenic oxide Nd IC as a proxy of seawater composition. Therefore, it is important to identify the component end-members that create sediments of different lithology and determine if, or how they might contribute to the Nd IC of oxide coatings. To investigate lithologic influence on the results of sequential leaching, we selected two sites with complete bulk sediment statistical characterization. Site U1370 in the South Pacific Gyre, is predominantly composed of Rhyolite ( 60%) and has a distinguishable ( 10%) Fe-Mn Oxyhydroxide component (Dunlea et al., 2015). Site 1149 near the Izu-Bonin-Arc is predominantly composed of dispersed ash ( 20-50%) and eolian dust from Asia ( 50-80%) (Scudder et al., 2014). We perform a two-step leaching procedure: a 14 mL of 0.02 M hydroxylamine hydrochloride (HH) in 20% acetic acid buffered to a pH 4 for one hour, targeting metals bound to Fe- and Mn- oxides fractions, and a second HH leach for 12 hours, designed to remove any remaining oxides from the residual component. We analyze all three resulting fractions for a large suite of major, trace and rare earth elements, a sub-set of the samples are also analyzed for Nd IC. We use multivariate statistical analyses of the resulting geochemical data to identify how each component of the sediment partitions across the sequential extractions. Here we present results comparing the two sites, and examine how the composition of the sediment impacts the resulting Nd IC.

Strontium isotope quantification of siderite, brine and acid mine drainage contributions to abandoned gas well discharges in the Appalachian Plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chapman, Elizabeth C.; Capo, Rosemary C.; Stewart, Brian W.

2013-04-01

Unplugged abandoned oil and gas wells in the Appalachian region can serve as conduits for the movement of waters impacted by fossil fuel extraction. Strontium isotope and geochemical analysis indicate that artesian discharges of water with high total dissolved solids (TDS) from a series of gas wells in western Pennsylvania result from the infiltration of acidic, low Fe (Fe < 10 mg/L) coal mine drainage (AMD) into shallow, siderite (iron carbonate)-cemented sandstone aquifers. The acidity from the AMD promotes dissolution of the carbonate, and metal- and sulfate-contaminated waters rise to the surface through compromised abandoned gas well casings. Strontium isotopemore » mixing models suggest that neither upward migration of oil and gas brines from Devonian reservoirs associated with the wells nor dissolution of abundant nodular siderite present in the mine spoil through which recharge water percolates contribute significantly to the artesian gas well discharges. Natural Sr isotope composition can be a sensitive tool in the characterization of complex groundwater interactions and can be used to distinguish between inputs from deep and shallow contamination sources, as well as between groundwater and mineralogically similar but stratigraphically distinct rock units. This is of particular relevance to regions such as the Appalachian Basin, where a legacy of coal, oil and gas exploration is coupled with ongoing and future natural gas drilling into deep reservoirs.« less

Iron Cycling in Marine Sediments - New Insights from Isotope Analysis on Sequentially Extracted Fe Fractions

NASA Astrophysics Data System (ADS)

Henkel, S.; Kasten, S.; Poulton, S.; Hartmann, J.; Staubwasser, M.

2014-12-01

Reactive Fe (oxyhydr)oxides preferentially undergo early diagenetic cycling and may cause a diffusive flux of dissolved Fe2+ from sediments towards the sediment-water interface. The partitioning of Fe in sediments has traditionally been studied by applying sequential extractions based on reductive dissolution of Fe minerals. We complemented the sequential leaching method by Poulton and Canfield [1] in order to be able to gain δ56Fe data for specific Fe fractions, as such data are potentially useful to study Fe cycling in marine environments. The specific mineral fractions are Fe-carbonates, ferrihydrite + lepidocrocite, goethite + hematite, and magnetite. Leaching was performed with acetic acid, hydroxylamine-HCl, Na-dithionite and oxalic acid. The processing of leachates for δ56Fe analysis involved boiling the samples in HCl/HNO3/H2O2, Fe precipitation and anion exchange column chromatography. The new method was applied to short sediment cores from the North Sea and a bay of King George Island (South Shetland Islands, Antarctica). Downcore mineral-specific variations in δ56Fe revealed differing contributions of Fe (oxyhydr)oxides to redox cycling. A slight decrease in easily reducible Fe oxides correlating with a slight increase in δ56Fe for this fraction with depth, which is in line with progessive dissimilatory iron reduction [2,3], is visible in the top 10 cm of the North Sea core, but not in the antarctic sediments. Less reactive (dithionite and oxalate leachable) fractions did not reveal isotopic trends. The acetic acid-soluble fraction displayed pronounced δ56Fe trends at both sites that cannot be explained by acid volatile sulfides that are also extracted by acetic acid [1]. We suggest that low δ56Fe values in this fraction relative to the pool of easily reducible Fe oxides result from adsorbed Fe(II) that was open to isotopic exchange with oxide surfaces, affirming the experimental results of Crosby el al. [2]. Hence, δ56Fe analyses on marine sediments appear to be particularly useful when targeting specific Fe pools, rather than the total highly reactive Fe fraction, since isotopic trends may be masked within the latter pool. [1] Poulton and Canfield (2005), Chemical Geology 214, 209-221. [2] Crosby et al., Geobiology 5 (2007), 169-189. [3] Staubwasser et al., Geology 34 (2006), 629-632.

Evaluating Volatility-controlled Isotope Fractionation During Planet Formation: Kinetics versus Equilibrium

NASA Astrophysics Data System (ADS)

Young, E. D.

2017-12-01

Recent advances in our ability to measure stable isotope ratios of light, rock-forming elements, including those for Zn, K, Fe, Si, and Mg, among others, has resulted in an emerging hypothesis that collisions among rocky planetesimals, planetary embryos, and/or proto-planets caused losses of moderately volatile elements (e.g., K) and "common" or moderately refractory elements (e.g., Mg and Si). The primary evidence is in the form of heavy isotope enrichments in rock-forming elements relative to the chondrite groups that are thought to be representative of planetary precursors. Equilibrium volatility-controlled isotope fractionation for planetesimal magma oceans might have occurred for bodies larger than 0.1% of an Earth mass (½ the mass of Pluto) as these bodies had sufficient gravity to overpower the escape velocities of hot gas at 2000K. Both Jean's escape and viscous drag hydrodynamic escape can obviate the escape velocity limit but will fractionate by mass, not by volatility. Equilibrium vapor/melt fractionation is qualitatively consistent with the greater disparity in 29Si/28Si between Earth and chondrites than in 25Mg/24Mg. However, losses of large masses of vapor are required to record the fractionation in the melts. We consider that if Earth was derived from E chondrite-like materials, the bulk composition of the Earth, assuming refractory Ca was retained, requires > 60% loss of Mg. This is a lot of vapor loss for a process relying on at least intermittent equilibrium, although it comports with the isotopic lever-rule requirements. Paradoxically, the alternative of evaporative loss of rock-forming elements requires less total mass loss. For example, the calculated Mg and Si isotopic compositions of residues resulting from evaporation of chondritic melts can fit the Mg and Si isotopic compositions of Earth, Mars, and angrites with varying background pressures and with total mass losses of near 5% or less. These mass losses are closer to, and even lower than, those suggested by Ca concentrations relative to CI chondrite. Equilibrium models achieve greater Si than Mg isotope fractionation by large mass losses while evaporation models produce this effect for small mass losses. Additional constraints involving other isotope systems as well as models for vapor loss can distinguish between the two scenarios.

Isotope studies to the sorption behavior of atmospheric sulfate in humus layers of scots pine ecosystems.

PubMed

Schulz, H; Neue, H-U

2005-03-01

The sorption potential for SO4(2-) in humus layer samples from field sites along a deposition gradient was determined experimentally in batch experiments. The Freundlich equation was used to quantify the sorption of added SO4(2-) in humus layer samples and to determine site-dependent sorption parameters. SO4(2-) sorption in humus layers is a concentration-dependent process. The linearity of isotherms reveals that SO4(2-) is reversibly bound in the organic surface layer, as long as soil solution concentrations remain above 26 to 44 mg SO4(2-) L(-1). Natural isotope variations of sulfur in SO4(2-) were analysed to investigate the degree of sorption of dissolved atmospheric and added SO4(2-). Both sulfate species differed significantly in their isotope composition. The pattern of delta34S values for SO4(2-) in all equilibrium solutions confirm the findings from sorption isotherms, showing a close relationship between the sulfur isotope ratios of SO4(2-) in soil solutions and the amount of SO4(2-) sorbed at the humus layer matrix. Stored atmospheric SO4(2-) in humus layers is released at sites where sulfate concentration in throughfall drops below 26 mg SO4(2-) L(-1). Concentration of soluble Fe decreased with increasing sulfate sorption, thus supporting the assumption that active Fe for example is important. Iron probably stabilizes the reactive surface of humus complexes and therefore has a positive influence on the SO4(2-) sorption in humus layers.

Investigation of micrometre-sized fossil by laser mass spectrometer (LMS) designed for in situ space research

NASA Astrophysics Data System (ADS)

Tulej, Marek; Neubeck, Anna; Ivarsson, Magnus; Brigitte Neuland, Maike; Riedo, Andreas; Wurz, Peter

2015-04-01

Search for signatures of life on other planets is one of the most important goals of current planetary missions. Among various possible biomarkers, which can be investigated in situ on planetary surfaces, the detection of bio-relevant elements in planetary materials is of considerable interest and the abundance of isotopes can be important signatures of past and present bioactivities [1, 2]. We investigate the chemical composition of fossilised biological inclusions embedded in a carbonate host phase by a miniature laser ablation mass spectrometer (LMS) [3]. The LMS instrument combines a laser ablation ion source for ablation, atomisation and ionisation of surface material with a reflectron time-of-flight (TOF) mass spectrometer. LMS delivers mass spectra of almost all elements and their isotopes. In the current setup a fs-laser ablation ion source is applied with high lateral (15 um) and vertical (sub-um) resolution [4, 7] and the mass analyser supports mass resolution of 400-500 (at 56Fe mass peak) and dynamic range of eight orders of magnitude [5, 6]. From the 200 mass spectra recorded at 200 different locations on the carbonate sample surface, five mass spectra were identified which recorded the chemical composition of inclusions; from the other mass spectra the composition of the carbonate host matrix could be determined. The microscopic inspection of the sample surface and correlation with the coordinates of the laser ablation measurements made the confirmation to the location of the inclusion [8]. For the carbonate host matrix, the mass spectrometric analysis yielded the major elements H, C, O, Na, Mg, K and Ca and the trace elements Li, B and Cl. The measurements at the inclusion locations yielded in addition, the detection of F, Si, P, S, Mn, Fe, Ni, Co and Se. For most of the major elements the isotope ratios were found to be conform to the terrestrial values within a few per mills, while for minor and trace elements the determination of isotope ratios were less accurate due to low signal to noise ratios (SNR). The isotope abundances for the lightest isotope of B, S were observed to be larger than terrestrial, which is consistent with isotope fractionation by bio-relevant processes and a salty ocean. The studies demonstrates the current performance of the miniature LMS for in situ investigation of highly heterogeneous samples and its capabilities for the identification of fossilised biological matter. References: [1] Summons et al., Astrobiology, 11, 157, 2011. [2] Wurz et al., Sol. Sys. Res. 46 408, 2012. [3] Rohner et al.,Meas. Sci. Technol., 14, 2159, 2003. [4] Riedo et al., J. Anal. Atom. Spectrom. 28, 1256, 2013. [5] Riedo et al., J. Mass Spectrom.48, 1, 2013. [6] Neuland et al., Planet. Space. Sci. 101, 196, 2014. [7] Grimaudo et al., Anal. Chem. 2014, submitted. [8] Tulej et al. Geostand. Geoanal. Res., 2014; DOI: 10.1111/j.1751-908X.2014.00302.x

A novel procedure for Rubidium separation and its isotope measurements on geological samples by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Ma, J.; Zhang, Z.; Wei, G.; Zhang, L.

2017-12-01

A method including a novel column Rb separation procedure and high-precision Rb isotope measurement in geological materials by using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in standard-sample-bracketing (SSB) mode has been developed. Sr-Spec resin was employed, in which the distribution coefficients for Rb, K, Ba and Sr are different in nitric acid, to sequentially separate them from the matrix. The dissolved samples were loaded on the column in 3 M HNO3, the main matrix such as Al, Ca, Fe, Mg, Mn and Na were removed by rinsing with 4.5 mL HNO3, Rb and K were then sequentially eluted by 3 M HNO3 in different volumes. After that, Ba was eluted by 8 M HNO3, and Sr was finally eluted by Milli-Q water. This enable us to collect the pure Rb, K, Ba and Sr one by one with recovery close to 100% for their isotopic compositions measurement on MC-ICP-MS. We here focus on Rb isotope measurement. The measurement using MC-ICP-MS yielded an internal precision for δ87Rb of < ± 0.03‰ (2SE), and the external precision was generally better than ± 0.06‰ (2SD) based on the long-term results of the Rb standard solutions NIST SRM 984. A series of geological rock standards, were analyzed using this method, and the results indicate significant Rb isotope differences in different geologic materials. This will provide a powerful tool to investigate Rb isotope fractionation during geological processes.Based on this method, Rb isotope compositions from a basaltic weathering profile were carried out. The data show the lighter Rb (85Rb) isotope is preferentially leached from the weathering profile and remains heavy Rb isotope (87Rb) in the weathered residues during the incipient weathering stage. From the moderate to advanced weathering stage, the significant variations of Rb isotope were observed and multiple factors, such as leaching, adsorption, desorption, and precipitation, should play important role in fractionating Rb isotope.

Evaporation and Accompanying Isotopic Fractionation of Sulfur from FE-S Melt During Shock Wave Heating

NASA Technical Reports Server (NTRS)

Tachibana, S.; Huss, G. R.; Miura, H.; Nakamoto, T.

2004-01-01

Chondrules probably formed by melting and subsequent cooling of solid precursors. Evaporation during chondrule melting may have resulted in depletion of volatile elements in chondrules. It is known that kinetic evaporation, especially evaporation from a melt, often leads to enrichment of heavy isotopes in an evaporation residue. However, no evidence for a large degree of heavy-isotope enrichment has been reported in chondrules for K, Mg, Si, and Fe (as FeO). The lack of isotopic fractionation has also been found for sulfur in troilites (FeS) within Bishunpur (LL3.1) and Semarkona (LL3.0) chondrules by an ion microprobe study. The largest fractionation, found in only one grain, was 2.7 +/- 1.4 %/amu, while all other troilite grains showed isotopic fractionations of <1 %/amu. The suppressed isotopic fractionation has been interpreted as results of (i) rapid heating of precursors at temperatures below the silicate solidus and (ii) diffusion-controlled evaporation through a surrounding silicate melt at temperatures above the silicate solidus. The kinetic evaporation model suggests that a rapid heating rate of >10(exp 4)-10(exp 6) K/h for a temperature range of 1000-1300 C is required to explain observed isotopic fractionations. Such a rapid heating rate seems to be difficult to be achieved in the X-wind model, but can be achieved in shock wave heating models. In this study, we have applied the sulfur evaporation model to the shock wave heating conditions of to evaluate evaporation of sulfur and accompanying isotopic fractionation during shock wave heating at temperatures below the silicate solidus.

MAGNESIUM ISOTOPE RATIOS IN {omega} CENTAURI RED GIANTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Da Costa, G. S.; Norris, John E.; Yong, David

2013-05-20

We have used the high-resolution observations obtained at the Anglo-Australian Telescope with Ultra-High Resolution Facility (R {approx} 100,000) and at Gemini-S with b-HROS (R {approx} 150,000) to determine magnesium isotope ratios for seven {omega} Cen red giants that cover a range in iron abundance from [Fe/H] = -1.78 to -0.78 dex, and for two red giants in M4 (NGC 6121). The {omega} Cen stars sample both the ''primordial'' (i.e., O-rich, Na- and Al-poor) and the ''extreme'' (O-depleted, Na- and Al-rich) populations in the cluster. The primordial population stars in both {omega} Cen and M4 show ({sup 25}Mg, {sup 26}Mg)/{sup 24}Mgmore » isotopic ratios that are consistent with those found for the primordial population in other globular clusters with similar [Fe/H] values. The isotopic ratios for the {omega} Cen extreme stars are also consistent with those for extreme population stars in other clusters. The results for the extreme population stars studied indicate that the {sup 26}Mg/{sup 24}Mg ratio is highest at intermediate metallicities ([Fe/H] < -1.4 dex), and for the highest [Al/Fe] values. Further, the relative abundance of {sup 26}Mg in the extreme population stars is notably higher than that of {sup 25}Mg, in contrast to model predictions. The {sup 25}Mg/{sup 24}Mg isotopic ratio in fact does not show any obvious dependence on either [Fe/H] or [Al/Fe] nor, intriguingly, any obvious difference between the primordial and extreme population stars.« less

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ57/54Fe Observations

PubMed Central

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; Bach, Wolfgang; Edwards, Katrina J.

2016-01-01

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50′N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits. PMID:27242685

Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ 57/54Fe observations

DOE PAGES

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; ...

2016-05-10

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffractionmore » (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ 57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. Lastly, these micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.« less

Isotopic variation in the Tuolumne Intrusive Suite, central Sierra Nevada, California

USGS Publications Warehouse

Kistler, R.W.; Chappell, B.W.; Peck, D.L.; Bateman, P.C.

1986-01-01

Granitoid rocks of the compositionally zoned Late Cretaceous Toulumne Intrusive Suite in the central Sierra Nevada, California, have initial87Sr/86Sr values (Sri) and143Nd/144Nd values (Ndi) that vary from 0.7057 to 0.7067 and from 0.51239 to 0.51211 respectively. The observed variation of both Sri and Ndi and of chemical composition in rocks of the suite cannot be due to crystal fractionation of magma solely under closed system conditons. The largest variation in chemistry, Ndi, and Sri is present in the outer-most equigranular units of the Tuolumne Intrusive Suite. Sri varies positively with SiO2, Na2O, K2O, and Rb concentrations, and negatively with Ndi, Al2O3, Fe2O3, MgO, FeO, CaO, MnO, P2O5, TiO2, and Sr concentrations. This covariation of Sri, Ndi and chemistry can be modeled by a process of simple mixing of basaltic and granitic magmas having weight percent SiO2 of 48.0 and 73.3 respectively. Isotopic characteristic of the mafic magma are Sri=0.7047, Ndi=0.51269 and ??18O=6.0, and of the felsic magma are Sri=0.7068, Ndi=0.51212 and ??18O=8.9. The rocks sampled contain from 50 to 80% of the felsic component. An aplite in the outer equigranular unit of the Tuolumne Intrusive Suite apparently was derived by fractional crystallization of plagioclase and hornblende from magma with granudiorite composition that was a product of mixing of the magmas described above. Siliceous magmas derived from the lower crust, having a maximum of 15 percent mantle-derived mafic component, are represented by the inner prophyritic units of the Tuolumne Intrusive Suite. ?? 1986 Springer-Verlag.

Evidence for the extraterrestrial origin of a natural quasicrystal

PubMed Central

Bindi, Luca; Eiler, John M.; Guan, Yunbin; Hollister, Lincoln S.; MacPherson, Glenn; Steinhardt, Paul J.; Yao, Nan

2012-01-01

We present evidence that a rock sample found in the Koryak Mountains in Russia and containing icosahedrite, an icosahedral quasicrystalline phase with composition Al63Cu24Fe13, is part of a meteorite, likely formed in the early solar system about 4.5 Gya. The quasicrystal grains are intergrown with diopside, forsterite, stishovite, and additional metallic phases [khatyrkite (CuAl2), cupalite (CuAl), and β-phase (AlCuFe)]. This assemblage, in turn, is enclosed in a white rind consisting of diopside, hedenbergite, spinel (MgAl2O4), nepheline, and forsterite. Particularly notable is a grain of stishovite (from the interior), a tetragonal polymorph of silica that only occurs at ultrahigh pressures (≥10 Gpa), that contains an inclusion of quasicrystal. An extraterrestrial origin is inferred from secondary ion mass spectrometry 18O/16O and 17O/16O measurements of the pyroxene and olivine intergrown with the metal that show them to have isotopic compositions unlike any terrestrial minerals and instead overlap those of anhydrous phases in carbonaceous chondrite meteorites. The spinel from the white rind has an isotopic composition suggesting that it was part of a calcium-aluminum-rich inclusion similar to those found in CV3 chondrites. The mechanism that produced this exotic assemblage is not yet understood. The assemblage (metallic copper-aluminum alloy) is extremely reduced, and the close association of aluminum (high temperature refractory lithophile) with copper (low temperature chalcophile) is unexpected. Nevertheless, our evidence indicates that quasicrystals can form naturally under astrophysical conditions and remain stable over cosmic timescales, giving unique insights on their existence in nature and stability. PMID:22215583

Multi-stage evolution of the lithospheric mantle beneath the westernmost Mediterranean: Geochemical constraints from peridotite xenoliths in the eastern Betic Cordillera (SE Spain)

NASA Astrophysics Data System (ADS)

Marchesi, Claudio; Konc, Zoltán; Garrido, Carlos J.; Bosch, Delphine; Hidas, Károly; Varas-Reus, María Isabel; Acosta-Vigil, Antonio

2017-04-01

Spinel (± plagioclase) peridotite xenoliths from the Tallante and Los Perez volcanic centres in the eastern Betics (SE Spain) range from depleted (clinopyroxene-poor) harzburgites to fertile (clinopyroxene-rich) lherzolites and orthopyroxene-free wehrlites. Significantly, only one harzburgite, which is depleted in heavy rare earth elements (HREE), retains the imprint of ca. 20% ancient melting of an original garnet lherzolite source. In contrast, REE abundances of other harzburgites and lherzolites from the eastern Betics have been increased by melt-rock reaction. The whole-rock and mineral compositions of these mantle rocks are largely controlled by three types of modal metasomatism: 1) common clinopyroxene-orthopyroxene addition and olivine consumption which increased FeOt, SiO2 and Al2O3, and decreased MgO compared to the refractory melting products; 2) subordinate orthopyroxene dissolution and precipitation of clinopyroxene and olivine, which led to higher FeOt and MgO and lower SiO2 than in common (orthopyroxene-rich) lherzolites; and 3) rare orthopyroxene consumption and olivine addition that caused higher FeOt and lower SiO2 compared to the original melting residues. These mineral modal and major element variations have been produced mostly by interactions with relatively FeOt-rich/SiO2-poor melts, likely derived from a peridotite-pyroxenite lithospheric mantle with a highly heterogeneous isotopic composition. Melting of the lithospheric mantle in the western Mediterranean was triggered by upwelling of the asthenosphere induced by back-arc extension in the Late Oligocene-Early Miocene. Trapping of small fractions of exotic melts in whole-rocks - likely the parental magmas of Miocene back-arc dykes that intruded the Betic crust - caused local disequilibrium between the trace element signatures and Pb isotopic compositions of clinopyroxene and whole-rock. Subsequent interaction with SiO2-undersaturated magmas, similar to the parental melts of the Pliocene alkali basalts that host the xenoliths, promoted orthopyroxene consumption and clinopyroxene-olivine enrichment at locations close to magma conduits, and finally generated orthopyroxene-free wehrlites. This event constitutes the last episode of the Cenozoic magmatic evolution of the westernmost Mediterranean which is recorded in the mantle xenoliths from the eastern Betics.

Grosnaja ABCs: Magnesium isotope compositions

NASA Technical Reports Server (NTRS)

Goswami, J. N.; Srinivasan, G.; Ulyanov, A. A.

1993-01-01

Three CAI's from the Grosnaja CV3 chondrite were analyzed for their magnesium isotopic compositions by the ion microprobe. The selected CAI's represent three distinct types: GR4(compact Type A), GR7(Type B) and GR2(Type C). Petrographic studies indicate that all three Grosnaja inclusions were subjected to secondary alterations. The Type A CAI GR4 is primarily composed of melilite with spinel and pyroxene occurring as minor phases. The rim of the inclusion does not exhibit distinct layered structure and secondary alteration products (garnet, Fe-rich olivine and Na-rich plagioclase) are present in some localized areas near the rim region. The average major element compositions of different mineral phases in GR4 are given. Preliminary REE data suggest a depletion of HREE relative to LREE by about a factor of 3 without any clear indication of interelement fractionation. The CAI GR7 has textural and minerological characteristics similar to Type B inclusions. The REE data show a pattern that is similar to Group 6 with enrichment in Eu and Yb. In addition, a depletion of HREE compared to LREE is also evident in this object. Melilite composition shows a broad range of akermanite content (Ak(sub 15-55)). Detailed petrographic study is in progress. GR2 is a anorthite-rich Type C inclusion with large plagioclase laths intergrown with Ti-rich pyroxene. The average plagioclase composition is close to pure anorthite (An99).

Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

NASA Technical Reports Server (NTRS)

Snead, C. J.; Keller, L. P.; McKeegan, K. D.; Messenger, S.

2016-01-01

Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass-independent fractionation. The composition of the 16O-rich reservoir is well constrained but material representing the 17O,18O-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in 17O and 18O by greater than 200 per mille. The high-carbon hydrated IDPs may be among the best materials available to search for preserved "cometary" H2O signatures. In order to better understand the origin and evolution of these particles, we have obtained 10 hydrated interplanetary dust particles for coordinated mineralogical, isotopic and organic analyses. We have previously reported the results of mineralogical and O isotopic measurements of two hydrated IDPs; here we present results of O isotopic measurements of three additional IDPs. Samples and Methods: Three interplanetary dust particles (L2079C35, L2083D46 and L2083E46) were embedded in S and partially ultramicrotomed into approximately 70 nanometer sections for analysis via transmission electron microscopy (TEM). The remainders of the unsliced particles were removed from S and pressed into high purity Au foil that was cleaned with HF acid and annealed at 800 degrees Centigrade. The pressed IDPs were analyzed via electron microprobe analysis (EPMA) for quantitative bulk chemical analysis. After EPMA analysis, the IDPs were subjected to precision O isotope analysis with the UCLA Cameca IMS-1270 ion probe. A 20 kiloelectronvolt, 0.5 nanoangstrom Cs+ primary beam of approximately 15 micrometers diameter was used for each measurement. Small particles of San Carlos olivine and Burma spinel were pressed into the Au foil for use as standards to correct for instrumental mass fractionation. The detection system was configured for multicollection, with 16O measured on a Faraday cup, and 17O and 18O measured on electron multipliers (EMs). Individual analyses consisted of 15 cycles of 10 seconds per cycle. Additionally, two microtome thin sections were measured for H isotopic compositions with the JSC NanoSIMS 50L ion probe. An 8 picoangstrom, 16 kiloelectronvolt Cs plus primary beam was used. Measurements consisted of H, C, 12C, 16O, and 18O collected with EMs in multicollection. Terrestrial biotite and kerogen were used for isotopic standards. A significant challenge in O isotope measurement of hydrated minerals is the interference from 16OH at mass 17O. We ensured that the 17O and 16OH peaks were fully resolved by using a mass resolution of greater than 7000 and by careful analyses of San Carlos olivine, Burma spinel and chlorite hydrated mineral standards. The hydride was further suppressed with a cold finger attached to an LN2 dewar to trap volatiles in the sample chamber. All sputtered ions were counted (i.e. presputtering was not used); after applying background, yield and deadtime corrections, we performed a change-point analysis on our data via R in order to determine when the sample reached sputtering equilibrium; data points collected prior to the change point were excluded. Change-point analysis was also used to determine whether the IDP had completely sputtered. Results: Mineralogy. IDPs C35 and E46 exhibited hydrated mineralogies, Fe-Ni sulfide grains, nanoglobules and occasional enstatite grains distributed throughout a fine-grained Mg-Fe saponite matrix. C35 also contained breunnerite (Mg,Fe)CO3; solar flare tracks were observed in enstatite, indicating minimal atmospheric entry heating. The mineralogy of D46 is dominated by a large FeS grain with a minor component of adhering silicate material. D46 was strongly heated during atmorpheric entry as evidenced by a well-developed magnetite rim. EPMA analyses show that both C35 and E46 have high carbon contents of 20 weight percentage (approximately 6X CI). D46 contains approximately 6 wt.weight percentage C. A significant amount of the carbon is present as carbon nanoglobules. Results: Hydrogen isotopes: Although the bulk delta D values of both sections of L2079C35 were within error of SMOW (minus 33 plus or minus 19 per mille, 1 plus or minus 14 per mille 1 sigma), several delta D-rich hotspots were also identified, reaching 2000 per mille. As shown in Fig. 1, these hotspots are clearly associated with discrete carbonaceous inclusions that are akin to nanoglobules found in many meteorites and other IDPs. Oxygen Isotopes. Results of the oxygen isotope measurements are shown in Figure 1. The oxygen isotope composition for L2079C35 was delta 18O equals plus11.6 plus or minus 1.9per mille, delta 17O equals plus 7.9 plus or minus 1.9per mille (2 standard errors). The oxygen isotope composition for L2083D46 was delta 18O equals minus 8.1 plus or minus 1.9 per mille, delta 17O equals minus 6.4 plus or minus 3.1 per mille (2 standard errors). The oxygen isotope composition for L2083E46 was delta 18O equals plus 12.0 plus or minus 1.9 per mille, delta 17O equals plus 9.2 plus or minus 2.0 per mille (2 standard errors). Discussion: Despite mineralogical similarities to highly aqueously altered carbonaceous chondrites, the hydrated IDPs we analyzed have oxygen isotopic compositions that are distinct from matrix materials in the CI, CM, and CR chondrites. The IDPs plot along the Young-Russell line, with delta 17O values for C35 and E46 suggestive of interaction with a 16O-poor reservoir. However, we have thus far not observed evidence of extreme 16O-poor reservoirs expected from self-shielding models and observed in Acfer 094 simplectite. The high carbon contents of the IDPs also set them apart from known meteoritic samples. The lack of atmospheric entry heating effects are consistent with low encounter velocities and suggest either an asteroidal source, or a low inclination, low eccentricity cometary origin. Conclusions: The unusual oxygen isotopic compositions, high carbon contents, and the abundance of Drich nanoglobules, together, suggest that the high-carbon, hydrated IDPs are derived from a primitive source that is not yet represent ed in meteorite collections.

Experimentally determined Si isotope fractionation between silicate and Fe metal and implications for Earth's core formation

NASA Astrophysics Data System (ADS)

Shahar, Anat; Ziegler, Karen; Young, Edward D.; Ricolleau, Angele; Schauble, Edwin A.; Fei, Yingwei

2009-10-01

Stable isotope fractionation amongst phases comprising terrestrial planets and asteroids can be used to elucidate planet-forming processes. To date, the composition of the Earth's core remains largely unknown though cosmochemical and geophysical evidence indicates that elements lighter than iron and nickel must reside there. Silicon is often cited as a light element that could explain the seismic properties of the core. The amount of silicon in the core, if any, can be deduced from the difference in 30Si/ 28Si between meteorites and terrestrial rocks if the Si isotope fractionation between silicate and Fe-rich metal is known. Recent studies (e.g., [Georg R.B., Halliday A.N., Schauble E.A., Reynolds B.C., 2007. Silicon in the Earth's core. Nature 447 (31), 1102-1106.]; [Fitoussi, C., Bourdon, B., Kleine, T., Oberli, F., Reynolds, B. C., 2009. Si isotope systematics of meteorites and terrestrial peridotites: implications for Mg/Si fractionation in the solar nebula and for Si in the Earth's core. Earth Planet. Sci. Lett. 287, 77-85.]) showing (sometimes subtle) differences between 30Si/ 28Si in meteorites and terrestrial rocks suggest that Si missing from terrestrial rocks might be in the core. However, any conclusion based on Earth-meteorite comparisons depends on the veracity of the 30Si/ 28Si fractionation factor between silicates and metals at appropriate conditions. Here we present the first direct experimental evidence that silicon isotopes are not distributed uniformly between iron metal and rock when equilibrated at high temperatures. High-precision measurements of the silicon isotope ratios in iron-silicon alloy and silicate equilibrated at 1 GPa and 1800 °C show that Si in silicate has higher 30Si/ 28Si than Si in metal, by at least 2.0‰. These findings provide an experimental foundation for using isotope ratios of silicon as indicators of terrestrial planet formation processes. They imply that if Si isotope equilibrium existed during segregation of Earth's core-forming metal and silicate mantle, there should be an isotopic signature of Si in the core. Our experiments, combined with previous measurements of Si isotope ratios in meteorites and rocks representing the bulk silicate Earth, suggest that the formation of the Earth's core imparted a high 30Si/ 28Si signature to the bulk silicate Earth due to dissolution of ~ 6 wt% Si into the early core.

Mass-dependent cadmium isotopic variations in nature with emphasis on the marine environment

NASA Astrophysics Data System (ADS)

Schmitt, Anne-Désirée; Galer, Stephen J. G.; Abouchami, Wafa

2009-01-01

We report a survey of natural mass-dependent cadmium isotope fractionation measured by thermal ionization mass spectrometry using a double-spike technique (DS-TIMS). Over sixty samples of natural terrestrial Cd from diverse environments, including MORB, OIB, continental loess, hydrogenic and hydrothermal ferromanganese deposits, and sphalerites (both oceanic and from major continental ore deposits) were analysed. Our results are expressed in terms of ɛ 112/110Cd, which are deviations in 112Cd/ 110Cd from our in-house JMC Cd standard in parts per 10 4. The total ɛ 112/110Cd variation is relatively small, with a range of only 5 ɛ-units, and is one-to-two orders of magnitude smaller than that previously found in meteorites. The MORB, OIB and loess ɛ 112/110Cd values are similar and provide a good estimate for the bulk silicate Earth (BSE) value which is - 0.95 ± 0.12 relative to our Cd standard (ɛ 112/110Cd = + 0.16 relative to Münster JMC Cd). Taken together, these data suggest little Cd isotope fractionation takes place during crust-mantle segregation. Cd isotopic compositions of continental sphalerite (ZnS) deposits worldwide and high-temperature oceanic hydrothermal sulphides show remarkably similar ɛ 112/110Cd values, consistent with our estimate for the BSE. In contrast, mid-temperature oceanic sulphides from a single extinct hydrothermal chimney display over 4 ɛ-units variation — along with the most negative values. These variations are most probably caused by precipitation/redissolution of sulphide phases en route within the hydrothermal system. The ɛ 112/110Cd variability found in worldwide marine Fe-Mn deposits reflects the seawater Cd isotope signal upon precipitation from ambient seawater. A decrease in ɛ 112/110Cd is observed in passing from shallow-water Fe-Mn deposits to those from deeper waters (> 2000 m depth). This shift is explained by biological fractionation related to the uptake of dissolved seawater Cd by phytoplankton in the upper water column. The relatively uniform ɛ 112/110Cd values close to zero at great depths are consistent with regeneration and remineralization of Cd at depth. Our data suggest that Cd isotopes - much like the Cd/Ca ratio in foraminifera - could potentially serve as a proxy for past changes in biological productivity. The temporal Cd isotope record in a Fe-Mn crust archive at 2000 m depth from the NE Atlantic suggests no gross long-term changes in Cd cycling took place over the past 8 Ma.

In search of the noble gas 3.52 Ga atmospheric signatures

NASA Astrophysics Data System (ADS)

Pujol, M.; Marty, B.; Philippot, P.

2008-12-01

The isotopic signatures of noble gases in the Present-day mantle and in the atmosphere permit exceptional insight into the evolution of these reservoirs through time ([1]). However, related exchange models are under- constrained and would require direct measurements of the atmospheric composition long ago, e.g., in the Archaean. Drilling in the the 3.52 Ga chert-barite ([2]) of the Dresser formation(Pilbara Drilling Project) , North Pole, Pilbara craton (Western Australia), led to recovery of exceptionally fresh samples preserving primary fluid inclusions unaffected by surface weathering. The whole formation is considered to be an already established basin when hydrothermal processes started. The chemical composition of primary fluid inclusions trapped in hydrothermal quartz from vacuolar komatiitic basalt from 110 m depth were determined by synchrotron X-ray microfluorescence (ESRF, Grenoble,France). Data show that fluids are relatively homogenous, consisting of a Ba-rich fluid and a Fe (+Ba)-rich fluid of hydrothermal origin as concluded by Foriel et al.([3]). The isotopic compositions of xenon and argon trapped in these fluids were measured by mass spectrometry following vacuum crushing. The three argon isotopes show a homogeneous signature quite different from present-day Earth atmosphere but we cannot exclude the possibility that secondary nuclear reactions produced these anomalies. Despite this, the Xe isotopic trends indicate a less radiogenic signature than the Present-day atmosphere, and probably represent a remnant of the Archaean atmosphere. If this xenon composition is primitive then it implies that there is no cosmogenic production through time. However, argon ratios could be explained by cosmogenic production which implies significant surface exposure times. Cosmogenic production will produce correlated argon and xenon isotope signatures. Therefore it is necessary to differentiate primary from secondary composition. To investigate the effects of these nuclear reactions on Xe isotope production, barite from 30m shallower depth in the same core were analyzed. Variable excesses can be linked to spallogenic and cosmogenic reactions ([4] [5] [6]) which allow the primitive Xe isotopic signature to be isolated from subsequent secondary production. Models of the archaean atmospheric noble gas signature can thereby be compared with different theories on primitive atmospheric composition. [1] Staudacher T. Allègre C.J. (1982) EPSL 60, p 389-406 [2] Van Kranendonk MJ., Hickman A.H., Williams I.R. and Nijman W. (2001) Rec.-Geol. Surv. West. Aust. 2001/9, 134 [3] Foriel J., Philippot P., Rey P., Somogyi A., Banks D. and Ménez B. (2004) EPSL, 228, 451-463 [4]Srinivasan B. (1976) EPSL, 31, 129-141 [5]Charalambus S. (1971) Nuclear Physics, A166, 145 [6]Meshik A. P., Hohenberg C. M., Pravdivtseva O. V. and Kapusta Y. (2001) Phys. Rev., C 64, 035205-1 035205-6

Observation of the 60Fe Nucleosynthesis-Clock Isotope in Galactic Cosmic Rays

NASA Technical Reports Server (NTRS)

Binns, W. R.; Israel, M. H.; Christian, E. R.; Cummings, A. C.; de Nolfo, G. A.; Lave, K. A.; Leske, R. A.; Mewaldt, R. A.; Stone, E. C.; von Rosenvinge, T. T.

2016-01-01

Iron-60 (60Fe) is a radioactive isotope in cosmic rays that serves as a clock to infer an upper limit on the time between nucleosynthesis and acceleration. We have used the ACE-CRIS instrument to collect 3.55 105 iron nuclei, with energies 195 to 500 megaelectron volts per nucleon, of which we identify 15 60Fe nuclei. The 60Fe56Fe source ratio is (7.5 2.9) 105. The detection of supernova-produced 60Fe in cosmic rays implies that the time required for acceleration and transport to Earth does not greatly exceed the 60Fe half-life of 2.6 million years and that the 60Fe source distance does not greatly exceed the distance cosmic rays can diffuse over this time, 1 kiloparsec. A natural place for 60Fe origin is in nearby clusters of massive stars.

Mineralogy and petrography of HAL, an isotopically-unusual Allende inclusion

NASA Technical Reports Server (NTRS)

Allen, J. M.; Grossman, L.; Lee, T.; Wasserburg, G. J.

1980-01-01

Results of a detailed mineralogical and textural study of the HAL (Hibonite ALlende) inclusion of the Allende meteorite, which has been found to exhibit no Mg-26 excesses despite very high Al-27/Mg-24 ratios and large fractionation effects with small nuclear effects in its Ca, are reported. The inclusion is found to consist of three up to 1-mm diameter hibonite crystals partially surrounded by a black rim resembling a devitrified glass and containing an anisotropic Al-Fe oxide, which is in turn surrounded by a 2-mm thick friable rim sequence consisting of five layers distinguishable by mineral composition. From the available evidence, it is concluded that each of the layers of the friable rim formed by the accretion of an assemblage of condensate grains rather than by the complete reaction of a HAL precursor with a nebular gas, thus explaining its unusual isotopic characteristics and supporting the conclusion that the solar nebular contained isotopically-distinct reservoirs.

Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

PubMed

Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M

2015-03-03

Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

Stochastic Simulation of Isotopic Exchange Mechanisms for Fe(II)-Catalyzed Recrystallization of Goethite.

PubMed

Zarzycki, Piotr; Rosso, Kevin M

2017-07-05

Understanding Fe(II)-catalyzed transformations of Fe(III)-(oxyhydr)oxides is critical for correctly interpreting stable isotopic distributions and for predicting the fate of metal ions in the environment. Recent Fe isotopic tracer experiments have shown that goethite undergoes rapid recrystallization without phase change when exposed to aqueous Fe(II). The proposed explanation is oxidation of sorbed Fe(II) and reductive Fe(II) release coupled 1:1 by electron conduction through crystallites. Given the availability of two tracer exchange data sets that explore pH and particle size effects (e.g., Handler et al. Environ. Sci. Technol. 2014 , 48 , 11302 - 11311 ; Joshi and Gorski Environ. Sci. Technol. 2016 , 50 , 7315 - 7324 ), we developed a stochastic simulation that exactly mimics these experiments, while imposing the 1:1 constraint. We find that all data can be represented by this model, and unifying mechanistic information emerges. At pH 7.5 a rapid initial exchange is followed by slower exchange, consistent with mixed surface- and diffusion-limited kinetics arising from prominent particle aggregation. At pH 5.0 where aggregation and net Fe(II) sorption are minimal, that exchange is quantitatively proportional to available particle surface area and the density of sorbed Fe(II) is more readily evident. Our analysis reveals a fundamental atom exchange rate of ∼10 -5 Fe nm -2 s -1 , commensurate with some of the reported reductive dissolution rates of goethite, suggesting Fe(II) release is the rate-limiting step in the conduction mechanism during recrystallization.

Petrography and geochemistry of the Permian-Triassic boundary interval, Yangou section, South China: Implications for early Griesbachian seawater δ13CDIC gradient with depth

NASA Astrophysics Data System (ADS)

Li, Rong

2017-04-01

The carbon isotopic composition (δ13Ccarb) recorded in shelf carbonates has been widely used as a proxy for the isotopic composition (δ13CDIC) of surface ocean water to establish paleocean chemistry and circulation patterns. However, δ13Ccarb values do not necessarily preserve the δ13CDIC, due to post-depositional diagenetic alteration. In order to examine the early Griesbachian surface-to-deep δ13CDIC gradient with depth, the diagenetic features of the Permian-Triassic boundary interval (beds 18 to 35) from Yangou section, located in the Yangtze carbonate platform interior, South China, are delineated to compare with those of the slope GSSP Meishan section. The petrographic and geochemical observations show that the early Griesbachian carbonates in the Yangou section underwent pervasive dolomitization in its early diagenetic history. Three types of early replacement dolomites and one type of dolomite cement are present. The dolomite crystals display internal zonation, with high-Ca calcian dolomite (HCD) core being encased successively by calcite and an outermost Fe-rich HCD cortex. The initial dolomitization took place in anoxic seawater, and underwent subsequent diagenetic system involved with meteoric water. The two most negative δ13C values in claystones of Beds 21-3 and 35 are probably related to meteoric diagenesis. Above and/or below the meteorically influenced beds, the dolomite and calcite have uniformly positive δ13C values. The primary carbon isotopic compositions are probably preserved in the early Griesbachian carbonate from the platform Yangou section, which could probably be related to the poor formation of the outermost Fe-rich HCD cortex. Compared to the slope carbonate from the Meishan section, the platform carbonate from the Yangou section has lower primary δ13Ccarb values. It is estimated that the δ13CDIC gradient with depth between Yangou and Meishan is less than the previously suggested. The results highlight the need for evaluation of local δ13Ccarb as record of δ13CDIC in paleoseawater, and carry important implications for understanding the Permian-Triassic carbonate successions throughout the world.

Abundance and Charge State of Implanted Solar Wind Transition Metals in Individual Apollo 16 and 17 Lunar Soil Plagioclase Grains Determined In Situ Using Synchrotron X-ray Fluorescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kitts, K.; Sutton, S.; Newville, M.

2007-03-06

We report (1) a new method for determining the relative abundances in situ of Cr, Mn, Fe and Ni in implanted solar wind in individual Apollo 16 and 17 lunar plagioclases via synchrotron X-ray fluorescence and (2) the charge states of these metals. By virture of its mass alone, the Sun provides a representative composition of the solar system and can be used as a background against which to gauge excesses or deficiencies of specific components. One way of sampling the Sun is by measuring solar wind implanted ions in lunar soil grains. Such measurements are valuable because of theirmore » long exposure ages which compliment shorter time scale collections, such as those obtained by the Genesis spacecraft. Kitts et al. sought to determine the isotopic composition of solar Cr by analyzing the solar wind implanted into plagioclase grains from Apollo 16 lunar soils. The isotopic composition of the solar wind bearing fraction was anomalous and did not match any other known Cr isotopic signature. This could only be explained by either (1) an enrichment in the solar wind of heavy Cr due to spallation in the solar atmosphere or (2) that the Earth and the various parent bodies of the meteorites are distinct from the Sun and must have formed from slightly different mixes of presolar materials. To help resolve this issue, we have developed a wholly independent method for determining the relative abundances of transition metals in the solar wind implanted in individual lunar soil grains. This method is based on in situ abundance measurements by microbeam x-ray fluorescence in both the implantation zone and bulk grains using the synchrotron x-ray microprobe at the Advanced Photon Source (GSECARS sector 13) at Argonne National Laboratory. Here, we report results for Apollo 16 and 17 plagioclase grains. Additionally, a micro-XANES technique was used to determine charge states of the implanted Cr, Mn, Fe and Ni.« less

Molybdenum isotope fractionation during adsorption to organic matter

USGS Publications Warehouse

King, Elizabeth K.; Perakis, Steven; Pett-Ridge, Julie C.

2018-01-01

Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2–170 h) and pH (2–7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (± 0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

Lack of Correlated Isotopic and Compositional Variations in Mauna Loa Lavas: A Serious Problem for Pyroxenite/Eclogite Plume Source Models

NASA Astrophysics Data System (ADS)

Rhodes, J. M.; Weis, D.; Norman, M. D.; Garcia, M. O.

2007-12-01

The long held notion that basaltic magmas are produced by decompressional melting of peridotite is under challenge. Recent models for the Hawaiian and other plumes argue that they consist of a heterogeneous mix of peridotite and discrete eclogite blobs, the latter derived from recycled subducted crust. Eclogite melting produces relatively siliceous magmas (dacite to andesite) which either mix with picritic melts from the peridotite, or, more plausibly, react with the peridotite to produce pyroxenite. Melting of varying proportions of the peridotite/pyroxenite mix is thought to produce the correlated compositional and isotopic characteristics of Hawaiian volcanoes. Magmas from Mauna Loa and Koolau volcanoes are thought to contain more of the recycled component; those from Loihi and Kilauea volcanoes contain less. A simple test of these mixed source models examines whether isotopic changes within the long magmatic history of a single volcano are accompanied by corresponding changes in major and trace element characteristics. Mauna Loa, where we have sampled around 400 - 500 ka of the volcano's eruptive history, provides an excellent opportunity for such a test. During this time, Mauna Loa will have traversed almost half the Hawaiian plume. According to the models, it should have erupted magmas produced from a range of pyroxenite/peridotite mixes with corresponding differences in both isotopic ratios and major and trace elements. Our data show that there is only minor isotopic (Sr, Pb, Nd, Hf) diversity in young lavas (<100 ka), but older lavas are highly diverse, ranging from modern values to those that are close to, and overlap with, those of Loihi volcano. If this isotopic diversity is a consequence of different proportions of pyroxenite and peridotite in the plume source, as the new models predict, we should expect to see correlated changes in bulk composition, particularly. in normalized SiO2, CaO/Al2O3, FeO/MgO and Ni - MgO relationships, as well as changes in Ni - Sc - V relationships. We do not. These parameters remain remarkably uniform over the 400 to 500 ka magmatic history of the volcano, with no correlated variation with isotopic ratios. We conclude that the isotopic heterogeneity within the Hawaiian plume is intrinsic to the peridotite plume source and not dependent on variable contributions from entrained, lithologically-discrete units.

Chromium Isotopes in Marine Carbonates - an Indicator for Climatic Change?

NASA Astrophysics Data System (ADS)

Frei, R.; Gaucher, C.

2010-12-01

Chromium (Cr) stable isotopes experience an increased interest as a tracer of Cr (VI) reduction in groundwater and thus showed their potential as a monitor of remediation of anthropogenic and natural contamination in water (Berna et al., 2009; Izbicki et al., 2008). Chromium stable isotopes in Fe-rich chemical sediments (BIFs and Fe-cherts) have recently also been used as a tracer for Earth's atmospheric oxygenation through time (Frei et al., 2009). We have applied the Cr isotope system to organic-rich carbonates from a late Ediacaran succession in Uruguay (Polanco Formation), from which we have previously analyzed BIFs with extremely fractionated (δ53Cr up to 5.0 ‰) Cr isotope signatures that are part of an underlying deep water clastic sediment (shale-dominated) sequence (Yerbal Formation) deposited in a glacio-marine environment (Gaucher et al.,2004). δ53Cr values of organic rich carbonates correlate with positive and negative carbon isotope excursions (δ13C PDB between -3 and +3 ‰) and with systematic changes in strontium isotope compositions, commonly interpreted as to reflect fluctuations in organic (photosynthetic algae) production related to fluctuations in atmospheric oxygen and weathering intensities, respectively. Slightly positively fractioned δ53Cr values (up to +0.25‰), paralleling positive (δ13C PDB and 87Sr/86Sr ratio excursions would thereby trace elevated atmospheric oxygen levels/pulses possibly related to glacier retreat/melting stages that caused bioproductivity to increase. While the causal link between these multiple isotopic tracers and the mechanisms of Cr stripping into carbonates has to be further investigated in detail, the first indications from this study point to a potentially promising use of stable Cr isotopes in organic-rich carbonates to monitor fluctuations of atmospheric oxygen, particularly over the Neoproterozoic and Phanerozoic ice age periods. E.C. Berna et al. (2010) Cr stable isotopes as indicators of Cr(VI) reduction in groundwater: a detailed time-series study of a point-source plume. Environ. Sci. Technol., v. 44, p. 1043-1048. J.A. Izbicki et al. (2008) Chromium, chromium isotopes and selected trace elements, western Mojave Desert, USA. Applied Geochemistry, v.23, p. 1325-1352. R. Frei et al. (2009) Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes. Nature, v. 461, p. 250-253. C. Gaucher et al. (2004) Chemostratigraphy of the Lower Arroyo del Soldado Group (Vendian, Uruguay) and palaeoclimatic implications. Gondwana Research, v.7, p. 715-730

Highly Siderophile Elements and Osmium Isotope Systematics in Ureilites: Are the Carbonaceous Veins Primary Components?

NASA Technical Reports Server (NTRS)

Rankenburg, K.; Brandon, A. D.; Humayun, M.

2005-01-01

Ureilites are an enigmatic group of primitive carbon-bearing achondrites of ultramafic composition. The majority of the 143 ureilite meteorites consist primarily of olivine and pyroxene (and occasionally chromite) [1]. They are coarse-grained, slowly cooled, and depleted in incompatible lithophile elements. Minor amounts of dark interstitial material consisting of carbon, metal, sulfides, and fine-grained silicates occur primarily along silicate grain boundaries, but also intrude the silicates along fractures and cleavage planes. Variable degrees of impact shock features have also been imparted on ureilites. The prevailing two origins proposed for these rocks are either as melting residues of carbonaceous chondritic material [2], [3], or alternatively, derivation as mineral cumulates from such melts [4], [5], [6]. It has recently been proposed that ureilites are the residues of a smelting event, i.e. residues of a partial melting event under highly reducing conditions, where a solid Fe-bearing phase reacts with a melt and carbon to form Fe metal and carbon monoxide [7]. Rapid, localized extraction and loss of the basaltic component into space resulting from high eruption velocities could preserve unequilibrated oxygen isotopes and produce the observed olivine-pyroxene residues via 25-30% partial melting of chondritic-like precursor material.

Enhanced collectivity along the N = Z line: Lifetime measurements in 44Ti, 48Cr, and 52Fe

NASA Astrophysics Data System (ADS)

Arnswald, K.; Braunroth, T.; Seidlitz, M.; Coraggio, L.; Reiter, P.; Birkenbach, B.; Blazhev, A.; Dewald, A.; Fransen, C.; Fu, B.; Gargano, A.; Hess, H.; Hirsch, R.; Itaco, N.; Lenzi, S. M.; Lewandowski, L.; Litzinger, J.; Müller-Gatermann, C.; Queiser, M.; Rosiak, D.; Schneiders, D.; Siebeck, B.; Steinbach, T.; Vogt, A.; Wolf, K.; Zell, K. O.

2017-09-01

Lifetimes of the 21+ states in 44Ti, 48,50Cr, and 52Fe were determined with high accuracy exploiting the recoil distance Doppler-shift method. The reduced E2 transition strengths of 44Ti and 52Fe differ considerably from previously known values. A systematic increase in collectivity is found for the N = Z nuclei compared to neighboring isotopes. The B (E2) values along the Ti, Cr, and Fe isotopic chains are compared to shell-model calculations employing established interactions for the 0 f 1 p shell, as well as a novel effective shell-model Hamiltonian starting from a realistic nucleon-nucleon potential. The theoretical approaches underestimate the B (E2) values for the lower-mass Ti isotopes. Strong indication is found for particle-hole cross-shell configurations, recently corroborated by similar results for the neighboring isotone 42Ca.

Discrimination of the Cigarettes Geographical Origin by DRC-ICP-MS Measurements of Pb Isotope Compositions

NASA Astrophysics Data System (ADS)

Guo, W.; Hu, S.; Jin, L.

2014-12-01

Trace Pb are taken up with the same isotopic ratios as is present in the source soil, and the isotopic composition of Pb could used to reflect these sources and provide powerful indicators of the geographic origin of agriculture products derived from vegetative matter. We developed a simple and high throughput method, which based on DRC-ICP-MS for determination of Pb isotope ratios for discriminating the geographic origin of cigarettes. After acid digestion procedure, the cigarette digested solutions were directly analyzed by ICP-QMS with a DRC pressurized by the non-reactive gas Ne. In the DRC, Ne molecules collision with Pb ions and improves Pb isotope ratios precision 3-fold, which may be due to the collisional dampling smoothes out the ion beam fluctuations. Under the optimum DRC rejection parameter Q (RPq = 0.45), the main matrix components (K, Na, Ca, Mg, Al, Fe etc.) originating from cigarettes were filtered out. Mass discrimination of 208Pb/206Pb ratio in Ne DRC mode increased 0.3% compared to the standard mode, the mass bias due to the in-cell Ne gas collision can be accurately corrected by NIST 981 Pb isotope standard. This method was verified by a tobacco reference material CTV-OTL-2. Results of 208Pb/206Pb and 207Pb/206Pb were 2.0848 ± 0.0028 (2δ) and 0.8452 ± 0.0011 (2δ) for CTA-VTL-2, which were agreed with the literature values (208Pb/206Pb = 2.0884 ± 0.0090 and 207Pb/206Pb = 0.8442 ± 0.0032). The precision of Pb isotope ratios (208Pb/206Pb and 207Pb/206Pb) for the cigarette samples are ranged from 0.01 to 0.08% (N = 5). It has sufficient precision to discriminate 91 different brand cigarettes originated from four different geographic regions (Shown in Fig).

Enhanced Continental Weathering on Antarctica During the Mid Miocene Climatic Optima Based on Pb Isotopes

NASA Astrophysics Data System (ADS)

Martin, E. E.; Fenn, C.; Basak, C.

2012-12-01

Feedbacks between climate and continental weathering can be monitored over geologic time scales using Pb isotopes preserved in marine sediments. During chemical weathering, radiogenic Pb is preferentially released to the dissolved phase, producing weathering solutions with more radiogenic isotopic values than the parent rock. The offset between the composition of the solution and rock tend to increase with the intensity of incongruent weathering (von Blanckenburg and Nägler, 2001; Harlavan and Erel, 2002). The seawater isotopic signal extracted from Fe-Mn oxides on bulk marine sediments is interpreted to represent the composition of local dissolved weathering inputs. For example, increasing seawater Pb isotopes observed during the most recent deglaciation are believed to reflect enhanced weathering of newly exposed glacial rock flour under warm conditions (Foster and Vance, 2006; Kurzweil et al., 2010). For this study we evaluated Nd and Pb isotopes from both the seawater fraction (extracted from Fe-Mn oxides) and parent rock (the detrital fraction of marine sediment) during the Mid-Miocene Climatic Optimum (MMCO) and subsequent cooling and East Antarctic Ice Sheet (EAIS) expansion (18 to 8 Ma) from Ocean Drilling Program site 744 on Kerguelen Plateau (2300 m; Indian sector) and sites 689 and 690 on Maud Rise (2080 m and 2914 m; Atlantic sector). The absolute value of seawater 206Pb/204Pb and separation between values for seawater and detrital fractions increased during the MMCO, suggesting enhanced weathering in proglacial and deglaciated areas exposed by ice sheet meltback during the warm interval. During the ensuing cooling, seawater values and the offset between the two archives decreased. Similar trends are displayed by 207Pb/204Pb and 208Pb/204Pb, although 207Pb/204Pb detrital values tend to be higher than seawater values. Reconstructions of atmospheric pCO2 in the Miocene have suggested both 1) decoupling between pCO2 and climate with consistently low, modern concentrations throughout the Miocene (Pagani et al., 2005; Pearson and Palmer, 2000), and 2) a correlation between higher pCO2 during the MMCO and decreasing values during cooling and re-establishment of a full-scale EAIS (Royer et al., 2001; Kürschner et al., 2008; Tripati et al., 2009; Foster et al., 2012). Our data suggest enhanced weathering during the MMCO would have contributed to a drawdown of CO2 leading to cooling, thereby supporting a correlation between climate and pCO2 in the Miocene. Nd isotopes may also fractionate during weathering. Our seawater Nd isotopes are consistently more radiogenic than detrital values, but there is no relationship between the magnitude of offset and climate conditions. Instead, documented depth stratification and regional distribution of seawater Nd isotopes in the water column indicate the Nd signal is dominated by water mass advection.

The cycling of iron, zinc and cadmium in the North East Pacific Ocean - Insights from stable isotopes

NASA Astrophysics Data System (ADS)

Conway, Tim M.; John, Seth G.

2015-09-01

Dissolved stable isotope ratios of the transition metals provide useful information, both for understanding the cycling of these bioactive trace elements through the oceans, and tracing their marine sources and sinks. Here, we present seawater dissolved Fe, Zn and Cd concentration and stable isotope ratio (δ56Fe, δ66Zn, and δ114Cd) profiles from two stations in the Pacific Ocean, the SAFe Station (30°N 140°W) in the subtropical North East Pacific from the GEOTRACES IC2 cruise, and the marginal San Pedro Basin (33.8°N 118.4°W) within the South California Bight. These data represent, to our knowledge, the first full-water column profiles for δ66Zn and δ56Fe from the open-ocean North Pacific, and the first observations of dissolved δ66Zn and δ114Cd in a low-oxygen marginal basin. At the SAFe station, δ56Fe is isotopically lighter throughout the water column (-0.6 to +0.1‰, relative to IRRM-014) compared to the North Atlantic, suggesting significant differences in Fe sources or Fe cycling between these two ocean basins. A broad minimum in δ56Fe associated with the North Pacific oxygen minimum zone (OMZ; <75 μmol kg-1 dissolved oxygen; ∼550-2000 m depth) is consistent with reductive sediments along the California margin being an important source of dissolved Fe to the North Pacific. Other processes which may influence δ56Fe at SAFe include biological cycling in the upper ocean, and input of Fe from hydrothermal vents and oxic sediments below the OMZ. Zn and Cd concentration profiles at both stations broadly match the distribution of the macronutrients silicate and phosphate, respectively. At SAFe, δ114Cd increases towards the surface, reflecting the biological preference for assimilation of lighter Cd isotopes, while negative Cd∗ (-0.12) associated with low oxygen waters supports the recently proposed hypothesis of water-column CdS precipitation. In contrast to δ114Cd, δ66Zn at SAFe decreases towards the surface ocean, perhaps due to scavenging of isotopically heavy Zn, while at intermediate depths δ66Zn provides further evidence of a mid-depth dissolved δ66Zn maximum. We suggest this may be a global feature of Zn biogeochemistry related to either regeneration of heavy adsorbed Zn, or to ZnS formation and removal within the water column. Data from San Pedro shows that anoxic sediments can be a source of isotopically light Zn to the water column (δ66Zn of ∼-0.3‰ relative to JMC Lyon), though evidence of this signal is not observed being transported to SAFe. Within North Pacific Intermediate Water at SAFe (NPIW; ∼500 m) elevated Cd∗ and Zn∗ and a focused minimum in δ56Fe suggest possible transport of Fe, Zn, and Cd over thousands of km from subpolar waters, meaning that NPIW may have a strong influence on the subsurface distribution of trace metals throughout the North Pacific.

The Formation of Wassonite: A New Titanium Monosulfide Mineral in the Yamato 691 Enstatite Chondrite

NASA Technical Reports Server (NTRS)

Nakamura-Messenger, K.; Keller, L. P.; Messenger, S.; Rubin, A. E.; Choi, B.-G.; Petaev, M. I.; Clemett, S. J.; Zhang, S.; Rahman, Z.; Oikawa, K.

2011-01-01

Wassonite, ideally stoichiometric TiS, is a titanium monosulfide not previously observed in nature, that was discovered within the Yamato 691 EH3 enstatite chondrite [1]. Because of the submicrometer size of the wassonite grains, it was not possible to determine conventional macroscopic properties. However, the chemical composition and crystal structure were well constrained by extensive quantitative energy dispersive x-ray analysis and electron diffraction using transmission electron microscopy (TEM). The crystal system for wassonite is rhombohedral (a = 3.42 plus or minus 0.07, c = 26.50 plus or minus 0.53 Angstroms) with space group: R(sup 3 raised bar) m (R9 type), cell volume: 268.4 plus or minus 0.53 Angstroms(sup 3), Z=9, density (calculated): 4.452 grams per cubic centimeter, empirical formula: (Ti(sub 0.93), Fe(sub 0.06), Cr(sub 0.01))S. In this study, we discuss possible formation mechanisms of wassonite and its associated minerals based on the petrology, mineralogy, crystallography, thermodynamic calculations, Al/Mg isotopic systematics and the O-isotopic composition of the wassonite-bearing BO chondrule.

Cu, Fe, and Zn Isotope Variations Within a High-Temperature Mid-Ocean Ridge Sulfide Structure

NASA Astrophysics Data System (ADS)

Ewing, S. M.; Nelson, B. K.; Kelley, D. S.; Nielsen, D. C.

2006-12-01

Hydrothermal processes at mid-ocean ridges play an important role in controlling the transition metal budget of seawater and the crust through which it circulates. Preliminary work has shown stable metal isotope variations accompany these processes. We report Cu, Zn, and Fe isotope analyses of transects through a high temperature sulfide structure ("Fin") collected during the 1998 Edifice Rex Sulfide Recovery Project. We analyzed two horizontal transects through the sulfide edifice, from inner conduit to outer surface. Transects A and F are 9 and 6 cm in length, respectively. Each displays radially zoned mineralogy progressing from a chalcopyrite (ccp) zone through zones of zinc sulfide, pyrite-anhydrite (pyr-anh) matrix, zinc sulfide-anhydrite (zns-anh) matrix, to an outer well-cemented silica (Si) zone. Additional ccp and pyr-anh zones appear in transect A resulting from a smaller breakout conduit. In transect A, Cu displays the most isotopic variation, with little variation in Fe and Zn isotopes. From the inner ccp zone outward, the Cu isotope profile shows a 0.4‰ (±0.05‰ 2σ) increase in the first pyr-anh zone over the coarse-grained ccp zone. The δ65Cu drops by 0.6‰ in the secondary ccp zone and recovers to values of the innermost wall in the following zone where it is constant until the outermost portion of the Si rich zone, which shows a 1.3‰ increase over inner zone values. The Zn isotope profile has a total variation of 0.27‰ (±0.05‰ 2σ), with a 0.2‰ increase in the first pyr- anh zone followed by a .27‰ decrease in the adjacent zone, and recovering to its heaviest values in the second pyr-anh zone. The Zn profile lacks any significant increase of the δ^{64}Zn in the outermost zones. The Fe isotope profile shows very little variation across the chimney wall, but does have a sharp 0.7‰ (±0.1‰ 2σ) increase in the δ56Fe in the well-cemented Si rich zone. In transect F, the Cu isotope profile again shows the most variation, but displays a more pronounced jump of 1.3‰ at the zinc sulfide boundary and no obvious increase of the δ65Cu in the Si rich zone. Similarly with Zn, there is a 0.35‰ increase of the δ^{64}Zn, but no outer wall increase. Fe, on the other hand, has variation of the same order as transect A, and shows a 0.6‰ increase of the δ56Fe in both the zns-anh and Si rich zones. These profiles are likely the result of a combination of diffusion and advection processes, fluid mineral equilibria, and mineral-mineral equilibria. High δ values of the outer zones likely reflect oxidation reactions with seawater. Processes responsible for isotopic variations within interior zones of the structure are ambiguous. Kinetic effects and biological activity may play a role, as Zn, which is not redox sensitive and only minimally coordination sensitive, has profiles that are qualitatively similar to Cu and Fe, but less analytically pronounced. Our findings are within the range of other published results, and further illustrate such measurable metal isotope variation exists not only on the vent field scale among chimneys, but systematically within chimney walls.

Mineralogical and geochemical evidence for hydrothermal activity at the west wall of 12°50′N core complex (Mid-Atlantic ridge): a new ultramafic-hosted seafloor hydrothermal deposit?

USGS Publications Warehouse

Dekov, Vesselin; Boycheva, Tanya; Halenius, Ulf; Billstrom, Kjell; Kamenov, George D.; Shanks, Wayne C.; Stummeyer, Jens

2011-01-01

Dredging along the west wall of the core complex at 12°50′N Mid-Atlantic Ridge sampled a number of black oxyhydroxide crusts and breccias cemented by black and dark brown oxyhydroxide matrix. Black crusts found on top of basalt clasts (rubble) are mainly composed of Mn-oxides (birnessite, 10-Å manganates) with thin films of nontronite and X-ray amorphous FeOOH on their surfaces. Their chemical composition (low trace- and rare earth-element contents, high Li and Ag concentrations, rare earth element distribution patterns with negative both Ce and Eu anomalies), Sr–Nd–Pb-isotope systematic and O-isotope data suggest low-temperature (~ 20 °C) hydrothermal deposition from a diffuse vent area on the seafloor. Mineralogical, petrographic and geochemical investigations of the breccias showed the rock clasts were hydrothermally altered fragments of MORBs. Despite the substantial mineralogical changes caused by the alteration the Sr–Nd–Pb-isotope ratios have not been significantly affected by this process. The basalt clasts are cemented by dark brown and black matrix. Dark brown cement exhibits geochemical features (very low trace- and rare earth- element contents, high U concentration, rare earth element distribution pattern with high positive Eu anomaly) and Nd–Pb-isotope systematics (similar to that of MORB) suggesting that the precursor was a primary, high-temperature Fe-sulfide, which was eventually altered to goethite at ambient seawater conditions. The data presented in this work points towards the possible existence of high- and low-temperature hydrothermal activity at the west wall of the core complex at 12°50′N Mid-Atlantic Ridge. Tectonic setting at the site implies that the proposed hydrothermal field is possibly ultramafic-hosted.

Protonation/reduction dynamics at the [4Fe-4S] cluster of the hydrogen-forming cofactor in [FeFe]-hydrogenases.

PubMed

Senger, Moritz; Mebs, Stefan; Duan, Jifu; Shulenina, Olga; Laun, Konstantin; Kertess, Leonie; Wittkamp, Florian; Apfel, Ulf-Peter; Happe, Thomas; Winkler, Martin; Haumann, Michael; Stripp, Sven T

2018-01-31

The [FeFe]-hydrogenases of bacteria and algae are the most efficient hydrogen conversion catalysts in nature. Their active-site cofactor (H-cluster) comprises a [4Fe-4S] cluster linked to a unique diiron site that binds three carbon monoxide (CO) and two cyanide (CN - ) ligands. Understanding microbial hydrogen conversion requires elucidation of the interplay of proton and electron transfer events at the H-cluster. We performed real-time spectroscopy on [FeFe]-hydrogenase protein films under controlled variation of atmospheric gas composition, sample pH, and reductant concentration. Attenuated total reflection Fourier-transform infrared spectroscopy was used to monitor shifts of the CO/CN - vibrational bands in response to redox and protonation changes. Three different [FeFe]-hydrogenases and several protein and cofactor variants were compared, including element and isotopic exchange studies. A protonated equivalent (HoxH) of the oxidized state (Hox) was found, which preferentially accumulated at acidic pH and under reducing conditions. We show that the one-electron reduced state Hred' represents an intrinsically protonated species. Interestingly, the formation of HoxH and Hred' was independent of the established proton pathway to the diiron site. Quantum chemical calculations of the respective CO/CN - infrared band patterns favored a cysteine ligand of the [4Fe-4S] cluster as the protonation site in HoxH and Hred'. We propose that proton-coupled electron transfer facilitates reduction of the [4Fe-4S] cluster and prevents premature formation of a hydride at the catalytic diiron site. Our findings imply that protonation events both at the [4Fe-4S] cluster and at the diiron site of the H-cluster are important in the hydrogen conversion reaction of [FeFe]-hydrogenases.

pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

PubMed

Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

2008-09-21

The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds.

CHILI – the Chicago Instrument for Laser Ionization – a new tool for isotope measurements in cosmochemistry

DOE PAGES

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.; ...

2016-06-17

Here, we describe CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis at high spatial resolution and high sensitivity of small samples like contemporary interstellar dust grains returned by the Stardust spacecraft. We explain how CHILI addresses the technical challenges associated with such analyses by pushing most technical specifications towards their physical limits. As an initial demonstration, after many years of designing and developing CHILI, we have analyzed presolar silicon carbide grains for their isotopic compositions of strontium, zirconium, and barium. Subsequently, after further technical improvements, we have used CHILI to analyze,more » for the first time without interference, all stable isotopes of iron and nickel simultaneously in presolar silicon carbide grains. With a special timing scheme for the ionization lasers, we separated iron and nickel isotopes in the time-of-flight spectrum such that the isobaric interference between 58Fe and 58Ni was resolved. In-depth discussion of the astrophysical implications of the presolar grain results is deferred to dedicated later publications. Here we focus on the technical aspects of CHILI, its status quo, and further developments necessary to achieve CHILI’s ultimate goals, 10 nm lateral resolution and 30–40% useful yield.« less

CHILI – the Chicago Instrument for Laser Ionization – a new tool for isotope measurements in cosmochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.

2016-08-01

We describe CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis at high spatial resolution and high sensitivity of small samples like contemporary interstellar dust grains returned by the Stardust spacecraft. We explain how CHILI addresses the technical challenges associated with such analyses by pushing most technical specifications towards their physical limits. As an initial demonstration, after many years of designing and developing CHILI, we have analyzed presolar silicon carbide grains for their isotopic compositions of strontium, zirconium, and barium. Subsequently, after further technical improvements, we have used CHILI to analyze, formore » the first time without interference, all stable isotopes of iron and nickel simultaneously in presolar silicon carbide grains. With a special timing scheme for the ionization lasers, we separated iron and nickel isotopes in the time-of-flight spectrum such that the isobaric interference between Fe-58 and Ni-58 was resolved. In-depth discussion of the astrophysical implications of the presolar grain results is deferred to dedicated later publications. Here we focus on the technical aspects of CHILI, its status quo, and further developments necessary to achieve CHILI's ultimate goals, similar to 10 nm lateral resolution and 30-40% useful yield.« less

Light element geochemistry of the Apollo 16 site

NASA Technical Reports Server (NTRS)

Kerridge, J. F.; Kaplan, I. R.; Petrowski, C.; Chang, S.

1975-01-01

The abundance and isotopic composition of carbon, sulfur, and nitrogen, the abundance of helium and hydrogen, and the content of metallic iron are reported for lunar surface samples from the Apollo 16 landing site at Cayley-Descartes. The light elements show marked interstation variability at the site. The abundances in soils of C, N, He, and H are apparently controlled mainly by exposure to the solar wind, through implantation or stripping processes. Carbon abundances (but not observed isotopic distributions) are compatible with a model in which equilibrium is established after 10,000-100,000 yr between solar wind input and loss by proton stripping. Sulfur abundances in soils are apparently controlled by abundances in local country rocks, but the lunar S cycle is quite complex. A metallic iron component may have originated by solar wind reduction of lunar Fe(2+).

Copper isotopic zonation in the Northparkes porphyry Cu-Au deposit, SE Australia

NASA Astrophysics Data System (ADS)

Li, Weiqiang; Jackson, Simon E.; Pearson, Norman J.; Graham, Stuart

2010-07-01

Significant, systematic Cu isotopic variations have been found in the Northparkes porphyry Cu-Au deposit, NSW, Australia, which is an orthomagmatic porphyry Cu deposit. Copper isotope ratios have been measured in sulfide minerals (chalcopyrite and bornite) by both solution and laser ablation multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The results from both methods show a variation in δ 65Cu of hypogene sulfide minerals of greater than 1‰ (relative to NIST976). Significantly, the results from four drill holes through two separate ore bodies show strikingly similar patterns of Cu isotope variation. The patterns are characterized by a sharp down-hole decrease from up to 0.8‰ (0.29 ± 0.56‰, 1 σ, n = 20) in the low-grade peripheral alteration zones (phyllic-propylitic alteration zone) to a low of ˜-0.4‰ (-0.25 ± 0.36‰, 1 σ, n = 30) at the margins of the most mineralized zones (Cu grade >1 wt%). In the high-grade cores of the systems, the compositions are more consistent at around 0.2‰ (0.19 ± 0.14‰, 1 σ, n = 40). The Cu isotopic zonation may be explained by isotope fractionation of Cu between vapor, solution and sulfides at high temperature, during boiling and sulfide precipitation processes. Sulfur isotopes also show an isotopically light shell at the margins of the high-grade ore zones, but these are displaced from the low δ 65Cu shells, such that there is no correlation between the Cu and S isotope signatures. Fe isotope data do not show any discernable variation along the drill core. This work demonstrates that Cu isotopes show a large response to high-temperature porphyry mineralizing processes, and that they may act as a vector to buried mineralization.

Petrology and isotopic geochemistry of the Archaean basement lithologies near Gardiner, Montana

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guy, R.E.; Sinha, A.K.

1985-01-01

In an attempt to recognize potential source rocks for some of the rhyolites of the Yellowstone Rhyolite Plateau, four major exposures of Precambrian rocks have been analyzed for major and trace elements and isotopic composition. The terrain is characterized by granitic gneisses with subordinant mica schist, quartzite, amphibolite, and two-mica granite. The gneiss units from the northern (Yankee Jim Canyon) and eastern (Lamar Canyon) outcrops are characterized by k-feldspar augen in a gneissic groundmass of two-feldspar--quartz--mica--epidote. The feldspar compositions are Or/sub 95/ and An/sub 5-15/ indicating metamorphic re-equilibration. Mafic phases are iron-rich with Fe:Mg of 1.0 in epidote, 0.7 inmore » pyroxene, and 0.5 in biotite. Sr isotopic analyses yield present day values of 0.7201-0.7519 for Lamar Canyon, 0.7157-0.7385 for Yankee Jam Canyon, and 0.7200-0.7679 for mica schist from the western and northern outcrops. Rb-Sr whole-rock data indicate a complicated isotopic history with ages ranging from 2800 to 3600 my. The 2800 my ages are consistent with ages for the Tobacco Root and Ruby Mountains to the NW (James and Hedge, 1980) and the Beartooth Range to the NE (Nunes and Tilton, 1971) while the 3600 my age may be related to the formation of the protolith. The rhyolites of the northern Yellowstone Rhyolite Plateau (Sr/sub I/=0.7100) cannot be derived from the exposed Archaean rocks based on Sr isotopic and whole-rock chemistry, and must be derived from lithologies not exposed in the area. This study shows that care must be taken when using surface lithologies to model potential sources materials for volcanic rocks in an associated terrain.« less

The retention of dust in protoplanetary disks: Evidence from agglomeratic olivine chondrules from the outer Solar System

NASA Astrophysics Data System (ADS)

Schrader, Devin L.; Nagashima, Kazuhide; Waitukaitis, Scott R.; Davidson, Jemma; McCoy, Timothy J.; Connolly, Harold C.; Lauretta, Dante S.

2018-02-01

By investigating the in situ chemical and O-isotope compositions of olivine in lightly sintered dust agglomerates from the early Solar System, we constrain their origins and the retention of dust in the protoplanetary disk. The grain sizes of silicates in these agglomeratic olivine (AO) chondrules indicate that the grain sizes of chondrule precursors in the Renazzo-like carbonaceous (CR) chondrites ranged from <1 to 80 μm. We infer this grain size range to be equivalent to the size range for dust in the early Solar System. AO chondrules may contain, but are not solely composed of, recycled fragments of earlier formed chondrules. They also contain 16O-rich olivine related to amoeboid olivine aggregates and represent the best record of chondrule-precursor materials. AO chondrules contain one or more large grains, sometimes similar to FeO-poor (type I) and/or FeO-rich (type II) chondrules, while others contain a type II chondrule core. These morphologies are consistent with particle agglomeration by electrostatic charging of grains during collision, a process that may explain solid agglomeration in the protoplanetary disk in the micrometer size regime. The petrographic, isotopic, and chemical compositions of AO chondrules are consistent with chondrule formation by large-scale shocks, bow shocks, and current sheets. The petrographic, isotopic, and chemical similarities between AO chondrules in CR chondrites and chondrule-like objects from comet 81P/Wild 2 indicate that comets contain AO chondrules. We infer that these AO chondrules likely formed in the inner Solar System and migrated to the comet forming region at least 3 Ma after the formation of the first Solar System solids. Observations made in this study imply that the protoplanetary disk retained a dusty disk at least ∼3.7 Ma after the formation of the first Solar System solids, longer than half of the dusty accretion disks observed around other stars.

Observation of the ⁶⁰Fe nucleosynthesis-clock isotope in galactic cosmic rays.

PubMed

Binns, W R; Israel, M H; Christian, E R; Cummings, A C; de Nolfo, G A; Lave, K A; Leske, R A; Mewaldt, R A; Stone, E C; von Rosenvinge, T T; Wiedenbeck, M E

2016-05-06

Iron-60 ((60)Fe) is a radioactive isotope in cosmic rays that serves as a clock to infer an upper limit on the time between nucleosynthesis and acceleration. We have used the ACE-CRIS instrument to collect 3.55 × 10(5) iron nuclei, with energies ~195 to ~500 mega-electron volts per nucleon, of which we identify 15 (60)Fe nuclei. The (60)Fe/(56)Fe source ratio is (7.5 ± 2.9) × 10(-5) The detection of supernova-produced (60)Fe in cosmic rays implies that the time required for acceleration and transport to Earth does not greatly exceed the (60)Fe half-life of 2.6 million years and that the (60)Fe source distance does not greatly exceed the distance cosmic rays can diffuse over this time, ⪍1 kiloparsec. A natural place for (60)Fe origin is in nearby clusters of massive stars. Copyright © 2016, American Association for the Advancement of Science.

Mass fractionation processes of transition metal isotopes

NASA Astrophysics Data System (ADS)

Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

2002-06-01

Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

Compositions of Normal and Anomalous Eucrite-Type Mafic Achondrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Peng, Z. X.; Mertzman, S. A.

2016-01-01

The most common asteroidal igneous meteorites are eucrite-type mafic achondrites - basalts and gabbros composed of ferroan pigeonite, ferroan augite, calcic plagioclase, silica, ilmenite, troilite, Ca-phosphate, chromite and Fe-metal. These rocks are thought to have formed on a single asteroid along with howardites and diogenites. However, high precision O-isotopic analyses have shown that some mafic achondrites have small, well-resolved, non-mass-dependent differences that have been interpreted as indicating derivation from different asteroids. Some of these O-anomalous mafic achondrites also have anomalous petrologic characteristics, strengthening the case that they hail from distinct parent asteroids. We present the results of bulk compositional studies of a suite of normal and anomalous eucrite-type basalts and cumulate gabbros.

Further Insight into the Reaction FeO+ + H2 Yields Fe+ + H2O: Temperature Dependent Kinetics, Isotope Effects, and Statistical Modeling (Postprint)

DTIC Science & Technology

2014-07-31

a laminar flow tube via a Venturi inlet, where ∼104 to 105 collisions with a He buffer gas act to thermalize the ions and carry them downstream...ISOTOPE EFFECTS , AND STATISTICAL MODELING (POSTPRINT) Shaun G. Ard, et al. 31 July 2014 Journal Article AIR FORCE RESEARCH LABORATORY Space Vehicles...Kinetics, Isotope Effects , and Statistical Modeling (Postprint) 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 61102F 6

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

USGS Publications Warehouse

Balistrieri, L.S.; Borrok, D.M.; Wanty, R.B.; Ridley, W.I.

2008-01-01

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (65Cu/63Cu) and Zn (66Zn/64Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (??soln-solid) are 0.99927 ?? 0.00008 for Cu and 0.99948 ?? 0.00004 for Zn or, alternately, the separation factors (??soln-solid) are -0.73 ?? 0.08??? for Cu and -0.52 ?? 0.04??? for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

Gas-water-rock interactions in sedimentary basins: CO2 sequestration in the Frio Formation, Texas, USA

USGS Publications Warehouse

Kharaka, Y.K.; Cole, D.R.; Thordsen, J.J.; Kakouros, E.; Nance, H.S.

2006-01-01

To investigate the potential for the geologic storage of CO2 in saline sedimentary aquifers, 1600??ton of CO2 were injected at ???1500 m depth into a 24-m sandstone section of the Frio Formation - a regional reservoir in the US Gulf Coast. Fluid samples obtained from the injection and observation wells before, during and after CO2 injection show a Na-Ca-Cl type brine with 93,000??mg/L TDS and near saturation of CH4 at reservoir conditions. As injected CO2 gas reached the observation well, results showed sharp drops in pH (6.5 to 5.7), pronounced increases in alkalinity (100 to 3000??mg/L as HCO3) and Fe (30 to 1100??mg/L), and significant shifts in the isotopic compositions of H2O and DIC. Geochemical modeling indicates that brine pH would have dropped lower, but for buffering by dissolution of calcite and Fe oxyhydroxides. Post-injection results show the brine gradually returning to its pre-injection composition. ?? 2006 Elsevier B.V. All rights reserved.

Major- and minor-metal composition of three distinct solid material fractions associated with Juan de Fuca hydrothermal fluids (northeast Pacific), and calculation of dilution fluid samples

USGS Publications Warehouse

Hinkley, T.K.; Seeley, J.L.; Tatsumoto, M.

1988-01-01

Three distinct types of solid material are associated with each sample of the hydrothermal fluid that was collected from the vents of the Southern Juan de Fuca Ridge. The solid materials appear to be representative of deposits on ocean floors near mid-ocean ridges, and interpretation of the chemistry of the hydrothermal solutions requires understanding of them. Sr isotopic evidence indicates that at least two and probably all three of these solid materials were removed from the solution with which they are associated, by precipitation or adsorption. This occurred after the "pure" hydrothermal fluid was diluted and thoroughly mixed with ambient seawater. The three types of solid materials, are, respectively, a coarse Zn- and Fe-rich material with small amounts of Na and Ca; a finer material also rich in Zn and Fe, but with alkali and alkaline-earth metals; and a scum composed of Ba or Zn, with either considerable Fe or Si, and Sr. Mineral identification is uncertain because of uncertain anion composition. Only in the cases of Ba and Zn were metal masses greater in solid materials than in the associated fluids. For all other metals measured, masses in fluids dwarf those in solids. The fluids themselves contain greater concentrations of all metals measured, except Mg, than seawater. We discuss in detail the relative merits of two methods of determining the mixing proportions of "pure" hydrothermal solution and seawater in the fluids, one based on Sr isotopes, and another previously used method based on Mg concentrations. Comparison of solute concentrations in the several samples shows that degree of dilution of "pure" hydrothermal solutions by seawater, and amounts of original solutes that were removed from it as solid materials, are not related. There is no clear evidence that appreciable amounts of solid materials were not conserved (lost) either during or prior to sample collection. ?? 1988.

Origin of the volcanic-hosted Yamansu Fe deposit, Eastern Tianshan, NW China: constraints from pyrite Re-Os isotopes, stable isotopes, and in situ magnetite trace elements

NASA Astrophysics Data System (ADS)

Huang, Xiao-Wen; Zhou, Mei-Fu; Beaudoin, Georges; Gao, Jian-Feng; Qi, Liang; Lyu, Chuan

2018-01-01

The Yamansu Fe deposit (32 Mt at 51% Fe) in the Eastern Tianshan Orogenic Belt of NW China is hosted in early Carboniferous volcano-sedimentary rocks and spatially associated with skarn. The paragenetic sequence includes garnet-diopside (I), magnetite (II), hydrous silicate-sulfide (III), and calcite-quartz (IV) stages. Pyrite associated with magnetite has a Re-Os isochron age of 322 ± 7 Ma, which represents the timing of pyrite and, by inference, magnetite mineralization. Pyrite has δ 34SVCDT values of - 2.2 to + 2.9‰, yielding δ 34SH2S values of - 3.1 to 2‰, indicating the derivation of sulfur from a magmatic source. Calcite from stages II and IV has δ 13CVPDB values from - 2.5 to - 1.2‰, and - 1.1 to 1.1‰, and δ 18OVSMOW values from 11.8 to 12.0‰ and - 7.7 to - 5.2‰, respectively. Calculated δ 13C values of fluid CO2 and water δ 18O values indicate that stage II hydrothermal fluids were derived from magmatic rocks and that meteoric water mixed with the hydrothermal fluids in stage IV. Some ores contain magnetite with obvious chemical zoning composed of dark and light domains in BSE images. Dark domains have higher Mg, Al, Ca, Mn, and Ti but lower Fe and Cr contents than light domains. The chemical zoning resulted from a fluctuating fluid composition and/or physicochemical conditions (oscillatory zoning), or dissolution-precipitation (irregular zoning) via infiltration of magmatic-hydrothermal fluids diluted by late meteoric water. Iron was mainly derived from fluids similar to that in skarn deposits.

Interstellar and Solar Nebula Materials in Cometary Dust

NASA Technical Reports Server (NTRS)

Messenger, Scott; Nakamura-Messenger, Keiko; Keller, Lindsay; Nguyen, Ann; Clemett, Simon

2017-01-01

Laboratory studies of cometary dust collected in the stratosphere and returned from comet 81P/Wild 2 by the Stardust spacecraft have revealed ancient interstellar grains and molecular cloud organic matter that record a range of astrophysical processes and the first steps of planetary formation. Presolar materials are rarer meteorites owing to high temperature processing in the solar nebula and hydrothermal alteration on their asteroidal parent bodies. The greater preservation of presolar materials in comets is attributed to their low accretion temperatures and limited planetary processing. Yet, comets also contain a large complement of high temperature materials from the inner Solar System. Owing to the limited and biased sampling of comets to date, the proportions of interstellar and Solar System materials within them remains highly uncertain. Interstellar materials are identified by coordinated isotopic, mineralogical, and chemical measurements at the scale of individual grains. Chondritic porous interplanetary dust particles (CP IDPs) that likely derive from comets are made up of 0.1 - 10 micron-sized silicates, Fe-Ni-sulfides, oxides, and other phases bound by organic material. As much as 1% of the silicates are interstellar grains that have exotic isotopic compositions imparted by nucleosynthetic processes in their parent stars. Crystalline silicates in CP IDPs dominantly have normal isotopic compositions and probably formed in the Solar System. 81P samples include isotopically normal refractory minerals that resemble Ca-Al rich inclusions and chondrules common in meteorites. The origins of sub-micron amorphous silicates in IDPs are not certain, but at least a few % of them are interstellar grains. The remainder have isotopic compositions consistent with Solar System origins and elemental compositions that are inconsistent with interstellar grain properties, thus favoring formation in the solar nebula [4]. The organic component in comets and primitive meteorites has large enrichments in D/H and N-15/N-14 relative to terrestrial materials. These isotopic signatures are probably due to low temperature chemical processes in cold molecular clouds or the outermost reaches of the protoplanetary disk. The greatest isotopic anomalies are found in sub-micron organic nanoglobules that show chemical signatures of interstellar chemistry. The observation that cometary dust is mostly composed of isotopically normal minerals within isotopically anomalous organic matter is difficult to reconcile with the formation models of each component. The mineral component likely formed in high temperature processes in the inner Solar System, while the organic fraction shows isotopic and chemical signatures of formation near 10 K. Studying more primitive remnants of the Solar System starting materials would help in resolving this paradox. Comets formed across a vast expanse of the outer disk under differing thermal and collisional regimes, and some are likely to be better preserved than others. Finding truly pristine aggregates of presolar materials may require return of a pristine sample of comet nucleus material.

Persistence of fertile and hydrous lithospheric mantle beneath the northwestern Ethiopian plateau: Evidence from modal, trace element and Sr-Nd-Hf isotopic compositions of amphibole-bearing mantle xenoliths

NASA Astrophysics Data System (ADS)

Alemayehu, Melesse; Zhang, Hong-Fu; Aulbach, Sonja

2017-07-01

We present new trace element compositions of amphiboles, Sr-Nd-Hf isotope compositions of clinopyroxenes and mineral modes for spinel peridotite xenoliths that were entrained in a Miocene alkali basalt (Gundeweyn, northwestern Ethiopian plateau), in order to understand the geochemical evolution and variation occurring within the continental lithospheric mantle (CLM) in close proximity to the East African Rift system, and its dynamic implications. With the exception of a single amphibole-bearing sample that is depleted in LREE (La/YbN = 0.45 × Cl), amphiboles in lherzolites and in one harzburgite show variable degrees of LREE enrichment (La/YbN = 2.5-12.1 × Cl) with flat HREE (Dy/YbN = 1.5-2.1 × Cl). Lherzolitic clinoyroxenes have 87Sr/86Sr (0.70227 to 0.70357), 143Nd/144Nd (0.51285 to 0.51346), and 176Hf/177Hf (0.28297 to 0.28360) ranging between depleted lithosphere and enriched mantle. LREE-enriched clinopyroxenes generally have more enriched isotope compositions than depleted ones. While lherzolites with isotope compositions similar to those of the Afar plume result from the most recent metasomatic overprint, isotope compositions more depleted than present-day MORB can be explained by an older melt extraction and/or isotopic rehomogenisation event, possibly related to the Pan-African orogeny. Several generations of amphibole are recognized in accord with this multi-stage evolution. Texturally unequilibrated amphibole occurring within the peridotite matrix and in melt pockets attest to continued hydration and refertilization of the lithospheric mantle subsequent to Oligocene flood basalt magmatism, during which an earlier-emplaced inventory of amphibole was likely largely consumed. However, a single harzburgite contains amphibole with the highest Mg# and lowest TiO2 content, which is interpreted as sampling a volumetrically subordinate mantle region beneath the Ethiopian plateau that was not tapped during flood basalt magmatism. Strikingly, both trace-element enriched and depleted lherzolites have high clinopyroxene and orthopyroxene and low olivine contents (median 15, 24 and 56 vol.%), combined with primitive olivine Mg# (median 89.5), indicating the presence of refertilized mantle beneath Gundeweyn. Despite its fertility and FeO-rich character (hence high inferred density), and impingement by the Afar plume, the CLM beneath the Ethiopian plateau, though apparently thinned through thermochemical erosion, has so far resisted whole-sale delamination or dripping. This is tentatively ascribed to insufficient stress and density contrasts at the periphery of the Afar plume, which reached its greatest thermochemical buoyancy in the Afar region, northeast of Gundeweyn.

Tourmaline's record of Alpine metamorphism and segregation formation in the Pfitsch Formation, Western Tauern Window

NASA Astrophysics Data System (ADS)

Berryman, E. J.; Kutzschbach, M.; Trumbull, R. B.; Meixner, A.; van Hinsberg, V.; Kasemann, S.; Franz, G.

2017-12-01

Tourmaline, a common accessory mineral in the metasedimentary units of the Pfitsch Formation in the Western Tauern Window, Eastern Alps, records the variation in fluid composition and B mobilization during Alpine metamorphism. These post-Variscan metasediments are part of the Subpenninic nappes, the former European distal margin, and experienced peak metamorphic conditions of 550°C, 1.0 GPa. In all investigated units, tourmaline is predominantly dravitic, with high Fe contents. Charge balance calculations combined with Fe-Mg and Fe-Al variation suggest a significant proportion of ferric iron. Tourmaline's composition reflects its host rock assemblage, with the relative predominance of Fe-Mg or Fe-Al exchange in tourmaline from different units corresponding to the presence of biotite/chlorite or muscovite, respectively. Boron content and correspondingly tourmaline abundance is highest in a 25 m thick unit of feldspathic gneiss ( 20-200 ppm B). The abundance and size of the tourmaline crystals increases near coarse-grained quartzofeldspathic segregations ( 1200 ppm B), reflecting the mobilization and concentration of B by the metamorphic fluid. Tourmaline crystals near segregations have up to three growth zones, recording pro- ( 350-500°C, 0.7-1.0 GPa) and retrograde (400°C, 0.2 GPa) growth. They show the largest amount of compositional variation, covering the range of compositional space represented by tourmaline occurring away from segregations. Tourmaline near segregations has the highest inferred ferric iron content, which decreases across growth zones, potentially reflecting the gradual reduction of the fluid during metamorphism. Whole rock δ11B values (-15 to -34‰) vary with the heaviest values found near B-rich segregations, and the lightest values in B-depleted samples. This correlation reflects the preferential mobilization of 11B towards the segregations. Isotopic zonation of individual tourmaline crystals with -11‰ in their cores and -20‰ in their rims suggests continuous volatilization and fractionation of B by a 10B-rich precursor mineral (e.g. mica) during prograde mobilization and redistribution of B within the Pfitsch Formation.

Petrogenesis and metallogenesis of the Wajilitag and Puchang Fe-Ti oxide-rich intrusive complexes, northwestern Tarim Large Igneous Province

NASA Astrophysics Data System (ADS)

Zhang, Dongyang; Zhang, Zhaochong; Huang, He; Cheng, Zhiguo; Charlier, Bernard

2018-04-01

The Wajilitag and Puchang intrusive complexes of the Tarim large igneous province (TLIP) are associated with significant resources of Fe-Ti oxide ores. These two mafic-ultramafic intrusions show differences in lithology and mineral chemistry. Clinopyroxenite and melagabbro are the dominant rock types in the Wajilitag complex, whereas the Puchang complex is generally gabbroic and anorthositic in composition with minor plagioclase-bearing clinopyroxenites in the marginal zone. Disseminated Fe-Ti oxide ores are found in the Wajilitag complex and closely associated with clinopyroxenites, whereas the Puchang complex hosts massive to disseminated Fe-Ti oxide ores mainly within its gabbroic rocks. The Wajilitag intrusive rocks are characterized by a restricted range of initial 87Sr/86Sr ratios (0.7038-0.7048) and positive εNd(t) (+0.04 - +3.01), indicating insignificant involvement of continental crustal contamination. The slightly higher initial 87Sr/86Sr ratios (0.7039-0.7059) and lower εNd(t) values (-1.05 - +2.35) of the Puchang intrusive rocks also suggest that the isotopic characteristics was controlled primarily by their mantle source, rather than by crustal contamination. Both complexes have Sr-Nd isotopic compositions close the neighboring kimberlitic rocks and their hosted mantle xenoliths in the TLIP. This indicates that the ferrobasaltic parental magmas were most probably originated from partial melting of a metasomatized subcontinental lithospheric mantle, modified recently with subduction-related materials by the impingement of the ascending mantle plume. The recycled subduction-related materials preserved in the lithospheric mantle could play a key role in the formation of the parental Fe-rich magmas in the context of an overall LIP system. The distinct variations in mineral assemblage for each complex and modeled results indicated that the Wajilitag and Puchang complexes experienced different crystallization path. Fe-Ti oxides in Wajilitag joined the liquidus earlier in the crystallization sequence, especially relative to the crystallization of plagioclase. This is attributed to the relatively high TFeO, TiO2 and initial H2O contents of the parental magma. In combination with definitive field and petrological evidence, the enrichment of highly incompatible elements (e.g., Zr, Hf, Nb and Ta) and the depletion of rare earth elements in the Fe-Ti oxide ores is consistent with the plausible interpretation that the ores could be formed by fractional crystallization and crystal accumulation of the Fe-Ti oxide crystals from the ferrobasaltic parental magmas. A considerable amount of the Fe-Ti oxides in the Puchang has transported and sunk from higher up in the chamber to the underlying unconsolidated silicate crystal pile. The highly dense Fe-Ti oxide crystal slurries further tended to effective accumulate Fe-Ti oxides to form high-grade Fe-Ti oxide ore bodies, and subsequent rapid collapse and intrusive into lower lithologies within the complex under a H2O-rich environment during the late-stage of magmatic differentiation. The development of massive Fe-Ti oxide ores in the case of the Puchang, could plausibly result from a combination of the protracted differentiation history of a Fe highly enriched parental magma and the later addition of external H2O from the country rocks (e.g., carbonates) to the slowly cooling magma chamber.

Inhibiting Substances as Tracers for the Reactivity Assessment of Fe(0)-PRBs

NASA Astrophysics Data System (ADS)

Dahmke, A.

2001-12-01

Passivation processes of Fe(0)-barriers are well known from lab-studies (Phillips et al., (2000), Schlicker et al., (2000)) and from field-sites. Normally the passivation processes are correlated with the groundwater composition but quantitative prediction and monitoring of the inhibition velocity under field conditions is a serious problem. Currently, only concentration profiles of contaminants, isotope studies or the measurement of reactivity loss with column-experiments of altered Fe(0)-material from the field sites are used for the characterization of Fe(0)-reactivity. All of theses approaches have serious disadvantages and limitations. Thus the sampling of unaltered Fe(0)-material out of the reactive barrier is difficult and the perturbed installation of the material in column experiments may lead to significant modification in the field behaviour of the Fe(0)-barrier. In addition, the concentration profile of the contaminant is not always a good tool for reactivity estimations due to uncertainties in hydrogeological boundary conditions. The same general restrictions apply also for isotope studies, in which the shift of the d13C signal is used as an indicator for degradation processes of the chlorinated aliphatics. Therefore here the use of Fe(0) inhibiting substances as reactive tracers is presented as a new approach for the characterization of the Fe(0)-reactivity. The methodology of reactive tracers to determine reactive surface areas of Fe(III) in porous was developed last year by Veehmayer et al. (2000) by interpretation of the breakthrough curves of species with known specific interactions with the solid phase. The concept is also applicable for the estimation of reactive sites in Fe(0)-columns, so that the breakthrough curves of oxidants like NO3-, CrO42- or oxidizing organic substances may be interpreted as indicative of reactive reducing sites in the Fe(0)-column. Such correlation was already shown by Schlicker et al., (2000), who explained the movement of passivation fronts by the blocking of reactive sites at the Fe(0) surface. To investigate this approach different column experiments with passivated Fe(0) are being currently carried out. Initial results from the lab indicate that different inorganic as well as organic substances can be used for characterization of the passivation state of the Fe(0) surface. Application of reactive tracer combinations also give some clues about the surface properties of the inhibiting substances, which might be helpful with respect to reactivation approaches for passivated permeable Fe(0)-barriers. Despite the first encouraging but more phenomenological lab results some theoretical problems, like the alteration of the specific surface area during the lab experiments or competition processes between organic or inorganic compounds at the altered surface of the Fe particles have to be addressed more in detail.

Tracing redox processes during paleoclimatic changes in the Neoproterozoic: Stable chromium isotopic results from the Arroyo del Soldado Group (Ediacaran, Uruguay)

NASA Astrophysics Data System (ADS)

Frei, R.; Gaucher, C.

2007-12-01

Positive δ13C carbonate values, combined with the occurrence of Fe-rich cherts (oxide-facies BIF) and organic-rich black shales within the late Ediacaran (ca. 580-560 Ma) Yerbal Fm. of the Arroyo del Soldato Group (Uruguay) are compatible with paleoclimatic models which postulate that enhanced bioproductivity due to higher availability of nutrient (P, N, Fe) was essential for controlling Neoproterozoic glaciations. Tracing of associated redox processes (f.e. linked to oxygenation of bottom waters in restricted basins) that might have been responsible for the deposition of Fe-rich cherts (BIFs) is therefore an important tool to better understand the seawater changes during cold-warm periods. Besides the traditionally used Fe and Mo isotopic systems, the redox-sensitive element Cr (Cr(III); Cr(IV)) and its stable isotopes offer another complementary system to trace paleo-redox processes. We have applied Cr stable isotope systematics to a sequence of samples from a late Ediacaran sedimentary sequence in Uruguay, using a 52Cr-54Cr double spike (Schoenberg et al., Chem..Geol., subm.). The middle Yerbal Fm. is dominated by organic-rich, black shales and black dolostones (δ53Cr = -0.05‰), followed by organic-rich cherts (δ53Cr = +1.83 - +4.49 ‰) and BIF (δ53Cr = -0.31 +0.90 ‰) gradually changing into Fe-bearing, organic-rich cherts and shales (δ53Cr = -0.28 - -0.01 ‰), and another sequence with BIF and organic-rich cherts topped by carbonates of the lower Polanco Fm. (δ53Cr = -0.17 to -0.27 ‰). The strongly positively fractionated Cr isotopic signatures in organic-rich and Fe-rich cherts in the Yerbal Fm. may point to significant oxidation processes either directly in the seawater column and/or during early diagenetic processes at the sediment-water interface. While these strongly positive δ53Cr values are the first to be reported from Neoproterozoic sedimentary sequence, the exact nature of the chemical process that produced these anomalies is not yet understood. However, the occurrence of these anomalies in organic-rich and Fe-rich chemical sediments that were deposited in a period following a glacial (Gaskiers?) event is compatible with "Snowball Earth" scenarios whereby impulsive oxidation of the upper seawater was in response to ice cover retraction which allowed booming of the biosphere and concomitant oxidation of accumulated Fe2+ and subsequent precipitation of the Fe-oxyhydroxides to form the "BIF" during such epochs. Schoenberg et al. (subm.) The stable Cr isotope inventory of solid earth reservoirs determined by double-spike MC-ICP-MS. Chemical Geology

Neodymium isotopes in authigenic phases, bottom waters and detrital sediments in the Gulf of Alaska and their implications for paleo-circulation reconstruction

NASA Astrophysics Data System (ADS)

Du, Jianghui; Haley, Brian A.; Mix, Alan C.

2016-11-01

The isotopic composition of neodymium (εNd) extracted from sedimentary Fe-Mn oxyhydroxide offers potential for reconstructing paleo-circulation, but its application depends on extraction methodology and the mechanisms that relate authigenic εNd to bottom water. Here we test methods to extract authigenic εNd from Gulf of Alaska (GOA) sediments and assess sources of leachate Nd, including potential contamination from trace dispersed volcanic ash. We show that one dominant phase is extracted via leaching of core-top sediments. Major and trace element geochemistry demonstrate that this phase is authigenic Fe-Mn oxyhydroxide. Contamination of leachate (authigenic) Nd from detrital sources is insignificant (<1%); our empirical results are consistent with established kinetic mineral dissolution rates and theory. Contamination of extracted εNd from leaching of volcanic ash is below analytical uncertainty. However, the εNd of core-top leachates in the GOA is consistently more radiogenic than bottom water. We infer that authigenic phases record pore water εNd, and the relationships of εNd among bottom waters, pore waters, authigenic phases and detrital sediments are primarily governed by the exposure time of bottom water to sea-floor sediments, rate of exchange across the sediment-water interface and the reactivity and composition of detrital sediments. We show that this conceptual model is applicable on the Pacific basin scale and provide a new framework to understand the role of authigenic phases in both modern and paleo-applications, including the use of authigenic εNd as a paleo-circulation tracer.

Stable isotope, chemical, and mineral compositions of the Middle Proterozoic Lijiaying Mn deposit, Shaanxi Province, China

USGS Publications Warehouse

Yeh, Hsueh-Wen; Hein, James R.; Ye, Jie; Fan, Delian

1999-01-01

The Lijiaying Mn deposit, located about 250 km southwest of Xian, is a high-quality ore characterized by low P and Fe contents and a mean Mn content of about 23%. The ore deposit occurs in shallow-water marine sedimentary rocks of probable Middle Proterozoic age. Carbonate minerals in the ore deposit include kutnahorite, calcite, Mn calcite, and Mg calcite. Carbon (−0.4 to −4.0‰) and oxygen (−3.7 to −12.9‰) isotopes show that, with a few exceptions, those carbonate minerals are not pristine low-temperature marine precipitates. All samples are depleted in rare earth elements (REEs) relative to shale and have negative Eu and positive Ce anomalies on chondrite-normalized plots. The Fe/Mn ratios of representative ore samples range from about 0.034 to <0.008 and P/Mn from 0.0023 to <0.001. Based on mineralogical data, the low ends of those ranges of ratios are probably close to ratios for the pure Mn minerals. Manganese contents have a strong positive correlation with Ce anomaly values and a moderate correlation with total REE contents. Compositional data indicate that kutnahorite is a metamorphic mineral and that most calcites formed as low-temperature marine carbonates that were subsequently metamorphosed. The braunite ore precursor mineral was probably a Mn oxyhydroxide, similar to those that formed on the deep ocean-floor during the Cenozoic. Because the Lijiaying precursor mineral formed in a shallow-water marine environment, the atmospheric oxygen content during the Middle Proterozoic may have been lower than it has been during the Cenozoic.

Electron transfer and atom exchange between aqueous Fe(II) and structural Fe(III) in clays. Role in U and Hg(II) transformations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherer, Michelle

2016-08-31

During this project, we investigated Fe electron transfer and atom exchange between aqueous Fe(II) and structural Fe(III) in clay minerals. We used selective chemical extractions, enriched Fe isotope tracer experiments, computational molecular modeling, and Mössbauer spectroscopy. Our findings indicate that structural Fe(III) in clay minerals is reduced by aqueous Fe(II) and that electron transfer occurs when Fe(II) is sorbed to either basal planes and edge OH-groups of clay mineral. Findings from highly enriched isotope experiments suggest that up to 30 % of the Fe atoms in the structure of some clay minerals exhanges with aqueous Fe(II). First principles calculations usingmore » a small polaron hopping approach suggest surprisingly fast electron mobility at room temperature in a nontronite clay mineral and are consistent with temperature dependent Mössbauer data Fast electron mobility suggests that electrons may be able to conduct through the mineral fast enough to enable exchange of Fe between the aqueous phase and clay mineral structure. over the time periods we observed. Our findings suggest that Fe in clay minerals is not as stable as previously thought.« less

Generation of syntectonic calc-alkaline, magnesian granites through remelting of pre-tectonic igneous sources - U-Pb zircon ages and Sr, Nd and Pb isotope data from the Donkerhoek granite (southern Damara orogen, Namibia)

NASA Astrophysics Data System (ADS)

Schwark, L.; Jung, S.; Hauff, F.; Garbe-Schönberg, D.; Berndt, J.

2018-06-01

The 541 ± 4 Ma-old magnesian, weakly peraluminous, calc-alkalic Donkerhoek Onanis granite is part of the ca. 6000 km2 large Donkerhoek batholith in the Southern Zone of the Damara orogen of Namibia. Linear major and trace element variations and decreasing MgO, FeO, Al2O3, CaO, K2O, Na2O, Ba and Sr concentrations with increasing SiO2 indicate that this part of the batholith represent a coherent mass and underwent fractional crystallization processes. The Donkerhoek Onanis granites are isotopically evolved (initial εNd: -4.7 to -12.3, initial 87Sr/86Sr: 0.7099-0.7157) with moderately radiogenic Pb isotope ratios (206Pb/204Pb: 17.26-18.22; 207Pb/204Pb: 15.59-15.67; 208Pb/204Pb: 37.60-38.06). Beside heterogeneities imparted by the sources, an evaluation of LREE fractionation and Nd isotope data suggests that AFC processes also modified some samples. Based on the chemical and isotope data, the Donkerhoek Onanis granites cannot be derived by partial melting of Al- and Fe-rich metasedimentary rocks of the Kuiseb formation in which they intruded. Instead, melting of meta-igneous crustal sources with Proterozoic crustal residence ages is more likely. Three igneous to meta-igneous rock suites from the area (Matchless amphibolites, Proterozoic mafic to felsic gneisses from the southern Kalahari craton basement, syn-tectonic Salem granodiorites to granites) are potential sources. An evaluation of chemical and isotope data suggests that remelting of early syn-orogenic Salem-type granites is the most likely process which would also explain the existence of ca. 563 ± 4 Ma-old zircon in the Donkerhoek Onanis granites. Comparison of the Donkerhoek Onanis granites with experimentally derived melt compositions from an intermediate igneous parent indicates temperatures between 800 and 850 °C. It is suggested that the Pan-African igneous activity in this part of the Damara Belt was a moderate-temperature intra-crustal event. Although there are some compositional similarities with juvenile granites generated in subduction zones, unradiogenic Pb isotope ratios and moderately radiogenic Sr and unradiogenic Nd isotopes suggest that reprocessed crustal rocks are more likely sources. Previously obtained high δ18O values of the Donkerhoek Onanis granites ranging from 11.8 to 13.6‰, covering the range of δ18O values obtained on Salem-type granites from the area (12.5-13.3‰) confirm this view. In contrast to igneous processes along active continental margins that produce juvenile batholiths with calc-alkaline affinities, this igneous event was not a major crust-forming episode and the Donkerhoek Onanis granites represent reprocessed crustal material.

A Multi-Proxy Paradigm in the Pursuit of Ocean Paleoredox

NASA Astrophysics Data System (ADS)

Anbar, A. D.; Duan, Y.; Kendall, B.; Reinhard, C.; Severmann, S.; Lyons, T. W.

2011-12-01

The geologic record provides abundant evidence for variations in ocean oxygenation throughout Earth history. Expansion of ocean anoxic zones is expected in the future as a consequence of global climate change, with attendant effects on global nutrient inventories, carbon cycling and fluxes of trace greenhouse gases to the atmosphere. Therefore, studying ancient ocean redox variations not only teaches us about the history of the Earth system, but also provides insights into how the system may respond to analogous human perturbations. However, the extent, duration, causes, and consequences of most past variations are poorly understood. This problem motivates the development of paleoredox proxies, including novel stable isotope systems such as Mo, Fe, U and Tl. Experience with these emerging isotope systems demonstrates great promise but also many challenges. The Mo isotope system is illustrative. To first order, the geochemical cycling and isotope systematics of this element are straightforward, making it a useful proxy. However, critical unresolved issues include: (a) uncertainties in the ocean inputs through time; (b) ambiguities about fractionation mechanisms; (c) inadequate understanding of how modern analogs map to ancient systems. Similar challenges confront all the novel isotope systems. The way forward requires integration of multiple isotopic proxies, as well as information gleaned from careful analyses of element concentrations. For example, an episode of Mo enrichment in the 2.5 Ga Mt. McRae Shale is generally interpreted as resulting from buildup of Mo in seawater due to oxidative weathering. This enrichment is therefore thought to indicate a "whiff" of O2 in the environment prior to the Great Oxidation Event that began at 2.4 Ga. Molybdenum isotopes are consistent with this interpretation. However, Mo enrichment due to enhanced input from low-T hydrothermal sources in an anoxic regime cannot be completely excluded given the current state of knowledge of Mo isotope systematics from such sources. By considering sedimentary Fe enrichments together with Fe isotopes, we find that the Mo enrichment correlates with the telltale signature of a shelf-to-basin Fe redox "shuttle". Uranium isotopes also exhibit variations indicative of redox transformations. This multi-proxy dataset therefore paints a robust picture of trace metal redox cycling consistent with the "whiff" interpretation.

Enhanced collectivity along the N = Z line: lifetime measurements in 44Ti, 48Cr, and 52Fe

NASA Astrophysics Data System (ADS)

Arnswald, K.; Reiter, P.; Coraggio, L.; Birkenbach, B.; Blazhev, A.; Braunroth, T.; Dewald, A.; Fransen, C.; Fu, B.; Gargano, A.; Hess, H.; Hirsch, R.; Itaco, N.; Lenzi, S. M.; Lewandowski, L.; Litzinger, J.; Müller-Gatermann, C.; Queiser, M.; Rosiak, D.; Schneiders, D.; Seidlitz, M.; Siebeck, B.; Steinbach, T.; Vogt, A.; Wolf, K.; Zell, K. O.

2018-02-01

Lifetimes of the {2}1+ states in 44Ti, 48,50Cr, and 52Fe were determined with high accuracy exploiting the recoil distance Doppler-shift method. The reduced E2 transition strengths of 44Ti and 52 Fe differ considerably from previously known values. A systematic increase in collectivity is found for the N = Z nuclei compared to neighboring isotopes. The B(E2) values along the Ti, Cr, and Fe isotopic chains are compared to shell-model calculations employing established interactions for the 0f 1p shell, as well as a novel effective shell-model Hamiltonian starting from a realistic nucleon-nucleon potential. The theoretical approaches underestimate the B(E2) values for the lower-mass Ti isotopes. Strong indication is found for particle-hole cross-shell configurations, recently corroborated by similar results for the neighboring isotone 42 Ca. A detailed manuscript has meanwhile been published in Physics Letters B [1].

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis

NASA Astrophysics Data System (ADS)

VanStone, Nancy; Przepiora, Andrzej; Vogan, John; Lacrampe-Couloume, Georges; Powers, Brian; Perez, Ernesto; Mabury, Scott; Sherwood Lollar, Barbara

2005-08-01

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. > 9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and δ13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched δ13C values compared to the upgradient mean. In addition, δ13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis.

PubMed

VanStone, Nancy; Przepiora, Andrzej; Vogan, John; Lacrampe-Couloume, Georges; Powers, Brian; Perez, Ernesto; Mabury, Scott; Sherwood Lollar, Barbara

2005-08-01

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. >9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and delta13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched delta13C values compared to the upgradient mean. In addition, delta13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.

Shape coexistence in neutron-rich nuclei near N=40

NASA Astrophysics Data System (ADS)

Carpenter, M. P.; Janssens, R. V. F.; Zhu, S.

2013-04-01

Recent data show that both the 2+ and 4+ levels in the even neutron-rich Cr and Fe isotopes decrease in excitation energy toward N=40. This observation, along with Coulomb excitation and lifetime data, strongly indicates an increase in collectivity near N=40 in contradiction with expectations based on first principles. A straightforward two-band mixing model is used to investigate the structure of these neutron-rich Cr and Fe nuclei. The approach takes advantage of the extensive data available for 60Fe to provide the parameter values with which to reproduce the experimental observations in the 58-64Cr and 60-68Fe isotopic chains. Comparisons between the model and the data suggest marked structural differences for the ground-state configurations of N=40 Cr and Fe.

Silicon Isotopic Fractionation in a Tropical Soil-Plant System

NASA Astrophysics Data System (ADS)

Opfergelt, S.; Delstanche, S.; Cardinal, D.; Andre, L.; Delvaux, B.

2006-12-01

Silica fluxes to soil solutions and water streams are controlled by both abiotic and biotic processes occurring in a Si soil-plant cycle that can be significant in comparison with Si weathering input and hydrological output. The quantification of Si-isotopic fractionation by these processes is highly promising to study the Si soil-plant cycle. Therein, the fate of aqueous monosilicic acid H4SiO4, as produced by silicate weathering, may take four paths: (1) uptake by plants and recycling through falling litter, (2) formation of clay minerals, (3) specific adsorption onto Al and Fe oxides, (4) leaching in drainage waters and export from watersheds. Here we report on detailed Si-isotopic compositions of various Si pools in a tropical soil-plant system involving old stands of banana (Musa acuminata Colla, cv Grande Naine) cropped on a weathering sequence of soils derived from andesitic volcanic ash and pumice deposits in Cameroon, West Africa. Si-isotopic compositions were measured by MC-ICP-MS in dry plasma mode with external Mg doping with a reproducibility of 0.08 permil (2stdev). Results were expressed as delta29Si vs NBS28. The compositions were determined in plant parts, bulk soils, clay fractions (less than 2um) and stream waters used for crop irrigation. Of the weathering sequence, we selected young (Y) and old (O) volcanic soils (vs). Yvs are rich in weatherable minerals, and contain large amounts of pumice gravels; their clay fraction (10-35 percent) contains allophane, halloysite and ferrihydrite. Oppositely, Ovs are strongly weathered and fine clayey soils (75-96 percent clay) rich in halloysite, kaolinite, gibbsite and goethite. Intra-plant fractionation between roots and shoots and within shoots confirmed our previous data measured on banana plants grown in hydroponics. The bulk plant isotopic composition was heavier at Ovs than at Yvs giving a fractionation factor per atomic mass unit between plants and their irrigation water Si source (+0.61 permil) of -0.33 (Ovs) and -0.56 permil (Yvs), close to the fractionation factor previously measured in hydroponics (-0.40 permil). The average delta29Si of phytoliths in banana plants was +0.17 permil. In the topsoil, the isotopic composition of Yvs ( 0.21 permil) was close to that of unweathered pumice (-0.20 permil). The Ovs were significantly lighter (-0.73 permil), confirming published data pointing to lighter isotopic composition with increased weathering. Heavier bulk plants at Ovs might be related to a heavier residual soil solution due to: (i) the formation of lighter clay minerals at Ovs (clay fraction: -0.94 permil) than at Yvs (-0.60 permil), and (ii) the quantitative adsorption of silica onto iron oxides (see Delstanche et al., 2006, AGU), more abundant in weathered Ovs. Our data support the view that plants can induce a strong imprint on the continental cycle of silicon, just as clay formation and possibly Si adsorption onto iron oxides can do. The quantification of Si-isotopic fractionation in the soil-plant system requires, however, further studies involving all the Si pools to achieve a comprehensive understanding of this cycle.

Variation of mineralogy and organic material during the early stages of aqueous activity recorded in Antarctic micrometeorites

NASA Astrophysics Data System (ADS)

Noguchi, T.; Yabuta, H.; Itoh, S.; Sakamoto, N.; Mitsunari, T.; Okubo, A.; Okazaki, R.; Nakamura, T.; Tachibana, S.; Terada, K.; Ebihara, M.; Imae, N.; Kimura, M.; Nagahara, H.

2017-07-01

Micrometeorites (MMs) recovered from surface snow near the Dome Fuji Station, Antarctica are almost free from terrestrial weathering and contain very primitive materials, and are suitable for investigation of the evolution and interaction of inorganic and organic materials in the early solar system. We carried out a comprehensive study on seven porous and fluffy MMs [four Chondritic porous (CP) MMs and three fluffy fine-grained (Fluffy Fg) MMs] and one fine-grained type 1 (Fg C1) MM for comparison with scanning electron microscope, transmission electron microscope, X-ray absorption near-edge structure analysis, and secondary ion mass spectrometer. They show a variety of early aqueous activities. Four out of the seven CP MMs contain glass with embedded metal and sulfide (GEMS) and enstatite whiskers/platelets and do not have hydrated minerals. Despite the same mineralogy, organic chemistry of the CP MMs shows diversity. Two of them contain considerable amounts of organic materials with high carboxyl functionality, and one of them contains nitrile (Ctbnd N) and/or nitrogen heterocyclic groups with D and 15N enrichments, suggesting formation in the molecular cloud or a very low temperature region of the outer solar system. Another two CP MMs are poorer in organic materials than the above-mentioned MMs. Organic material in one of them is richer in aromatic C than the CP MMs mentioned above, being indistinguishable from those of hydrated carbonaceous chondrites. In addition, bulk chemical compositions of GEMS in the latter organic poor CP MMs are more homogeneous and have higher Fe/(Si + Mg + Fe) ratios than those of GEMS in the former organic-rich CP MMs. Functional group of the organic materials and amorphous silicate in GEMS in the organic-poor CP MMs may have transformed in the earliest stage of aqueous alteration, which did not form hydrated minerals. Three Fluffy Fg MMs contain abundant phyllosilicates, showing a clear evidence of aqueous alteration. Phyllosilicates in thee MMs are richer in Fe than those in hydrated IDPs, typical fine-grained hydrated (Fg C1) MMs, and hydrated carbonaceous chondrites. One of the Fluffy Fg MMs contains amorphous silicate, which is richer in Fe than GEMS and contains little or no nanophase Fe metal but contains Fe sulfide. Because the chemical compositions of the amorphous silicate are within the compositional field of GEMS in CP IDPs, the amorphous silicate may be alteration products of GEMS. The entire compositional field of GEMS in the CP MMs and the amorphous silicate in the Fluffy Fg MM matches that of the previously reported total compositional range of GEMS in IDPs. One Fluffy Fg MM contains Mg-rich phyllosilicate along with Fe-rich phyllosilicate and Mg-Fe carbonate. Mg-rich phyllosilicate and Mg-Fe carbonate may have been formed through the reaction of Fe-rich phyllosilicate, Mg-rich olivine and pyroxene, and water with C-bearing chemical species. These data indicate that CP MMs and Fluffy Fg MMs recovered from Antarctic surface snow contain materials that throw a light on the earliest stages of aqueous alteration on very primitive solar system bodies. Because mineralogy and isotopic and structural features of organic materials in D10IB009 are comparable with isotopically primitive IDPs, its parent body could be comets or icy asteroids showing mass ejection (active asteroids). By contrast, organic-poor CP MMs may have experienced the earliest stage of aqueous alteration and Fluffy Fg MMs experienced weak aqueous alteration. The precursor materials of the parent bodies of Fluffy Fg MMs probably contained abundant GEMS or GEMS-like materials like CP IDPs, which is common to fine-grained matrices of very primitive carbonaceous chondrites such as CR3s. However, highly porous nature of organic-poor CP MMs and Fluffy Fg MMs suggests that parent bodies of these MMs must have been much more porous than the parent bodies of primitive carbonaceous chondrites. Given no phyllosilicate among the returned samples of 81P/Wild 2 comet, the MMs may have been derived from porous icy asteroids such as active asteroids as well as P- and D-type asteroids rather than comets.

Stable isotopes and iron oxide mineral products as markers of chemodenitrification.

PubMed

Jones, L Camille; Peters, Brian; Lezama Pacheco, Juan S; Casciotti, Karen L; Fendorf, Scott

2015-03-17

When oxygen is limiting in soils and sediments, microorganisms utilize nitrate (NO3-) in respiration--through the process of denitrification--leading to the production of dinitrogen (N2) gas and trace amounts of nitrous (N2O) and nitric (NO) oxides. A chemical pathway involving reaction of ferrous iron (Fe2+) with nitrite (NO2-), an intermediate in the denitrification pathway, can also result in production of N2O. We examine the chemical reduction of NO2- by Fe(II)--chemodenitrification--in anoxic batch incubations at neutral pH. Aqueous Fe2+ and NO2- reacted rapidly, producing N2O and generating Fe(III) (hydr)oxide mineral products. Lepidocrotite and goethite, identified by synchrotron X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy, were produced from initially aqueous reactants, with two-line ferrihydrite increasing in abundance later in the reaction sequence. Based on the similarity of apparent rate constants with different mineral catalysts, we propose that the chemodenitrification rate is insensitive to the type of Fe(III) (hydr)oxide. With stable isotope measurements, we reveal a narrow range of isotopic fractionation during NO2- reduction to N2O. The location of N isotopes in the linear N2O molecule, known as site preference, was also constrained to a signature range. The coexistence of Fe(III) (hydr)oxide, characteristic 15N and 18O fractionation, and N2O site preference may be used in combination to qualitatively distinguish between abiotic and biogenically emitted N2O--a finding important for determining N2O sources in natural systems.

General classification of ``hot`` particles from the nearest Chernobyl contaminated areas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shabalev, S.I.; Burakov, B.E.; Anderson, E.B.

1997-12-31

The morphology and composition both chemical and radionuclide of the main types of the solid-phase hot particles formed following the accident on the Chernobyl NPP have been studied by SEM, electron microprobe and gamma-spectrometry methods. Differences in many isotopes including: {sup 106}Ru, {sup 134}Cs, {sup 137}Cs dependent upon the hot particle matrix chemical composition was observed. The classification of hot particles based upon the chemical composition of their matrices has been done. It includes three main types: (1) fuel particles with UO{sub x} matrix; (2) fuel-constructional particles with Zr-U-O matrix, (3) hot particles with metallic inclusions of Fe-Cr-Ni. Moreover, theremore » are more rare types of hot particles with silicate or metal matrices. It was shown that only metallic inclusions of Fe-Cr-Ni are concentrators of {sup 106}Ru, which caused this nuclides assimilation in the molten stainless steel during the initial stages of the accident. Soils contamination of non-radioactive lead oxide particles in the Chernobyl NPP region were noticed. It was supposed that part of metallic lead, dropped from helicopters into burning reactor during first days of accident, was evaporated and oxidized accompanying solid oxide particles formation.« less

Contributions of the [NiFe]- and [FeFe]-hydrogenase to H2 production in Shewanella oneidensis MR-1 as revealed by isotope ratio analysis of evolved H2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kreuzer, Helen W.; Hill, Eric A.; Moran, James J.

2014-03-01

Shewanella oneidensis MR-1 encodes both a [NiFe]- and an [FeFe]-hydrogenase. While the output of these proteins has been characterized in mutant strains expressing only one of the enzymes, the contribution of each to H2 synthesis in the wild-type organism is not clear. Here we use stable isotope analysis of H2 in the culture headspace, along with transcription data and measurements of the concentrations of gases in the headspace, to characterize H2 production in the wild-type strain. After most of the O2 in the headspace had been consumed, H2 was produced and then consumed by the bidirectional [NiFe]-hydrogenase. Once the culturesmore » were completely anaerobic, a new burst of H2 synthesis catalyzed by both enzymes took place. Our data is consistent with the hypothesis that at this point in the culture cycle, a pool of electrons is shunted toward both hydrogenases in the wild-type organism, but that in the absence of one of the hydrogenases, the flux is redirected to the available enzyme. To our knowledge, this is the first use of stable isotope analysis of a metabolic product to elucidate substrate flux through two alternative enzymes in the same cellular system.« less

The Mineralogy of Circumstellar Silicates Preserved in Cometary Dust

NASA Technical Reports Server (NTRS)

Keller, L. P.; Messenger, S.

2010-01-01

Interplanetary dust particles (IDPs) contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula. Cometary IDPs have remained relatively unaltered since their accretion because of the lack of parent body thermal and aqueous alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these particles because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars. Five circumstellar grains have been identified including three amorphous silicate grains and two polycrystalline aggregates. All of these grains are between 0.2 and 0.5 micrometers in size. The isotopic compositions of all five presolar silicate grains fall within the range of presolar oxides and silicates, having large (17)O-enrichments and normal (18)O/(16)O ratios (Group 1 grains from AGB and RG stars). The amorphous silicates are chemically heterogeneous and contain nanophase FeNi metal and FeS grains in a Mg-silicate matrix. Two of the amorphous silicate grains are aggregates with subgrains showing variable Mg/Si ratios in chemical maps. The polycrystalline grains show annealed textures (equilibrium grains boundaries, uniform Mg/Fe ratios), and consist of 50-100 nm enstatite and pyrrhotite grains with lesser forsterite. One of the polycrystalline aggregates contains a subgrain of diopside. The polycrystalline aggregates form by subsolidus annealing of amorphous precursors. The bulk compositions of the five grains span a wide range in Mg/Si ratios from 0.4 to 1.2 (avg. 0.86). The average Fe/Si (0.40) and S/Si (0.21) ratios show a much narrower range of values and are approximately 50% of their solar abundances. The latter observation may indicate a decoupling of the silicate and sulfide components in grains that condense in stellar outflows. The amorphous silicate grains described here were not extensively affected by irradiation, sputtering, or thermal processing and may represent relatively pristine circumstellar grains. They are strong candidates for the "dirty silicates" in astronomical observations of circumstellar dust shells. The polycrystalline grains were originally amorphous silicate grains that were likely annealed in the early solar nebula but the processing was not sufficient to erase their anomalous oxygen isotopic compositions.

Condensation and mixing in supernova ejecta

NASA Astrophysics Data System (ADS)

Fedkin, A. V.; Meyer, B. S.; Grossman, L.

2010-06-01

Low-density graphite spherules from the Murchison carbonaceous chondrite contain TiC grains and possess excess 28Si and 44Ca (from decay of short-lived 44Ti). These and other isotopic anomalies indicate that such grains formed by condensation from mixtures of ejecta from the interior of a core-collapse supernova with those from the exterior. Using homogenized chemical and isotopic model compositions of the eight main burning zones as end-members, Travaglio et al. (1999) attempted to find mixtures whose isotopic compositions match those observed in the graphite spherules, subject to the condition that the atomic C/O ratio = 1. They were partially successful, but this chemical condition does not guarantee condensation of TiC at a higher temperature than graphite, which is indicated by the spherule textures. In the present work, model compositions of relatively thin layers of ejecta within the main burning zones computed by Rauscher et al. (2002) for Type II supernovae of 15, 21 and 25 M ʘ are used to construct mixtures whose chemical compositions cause equilibrium condensation of TiC at a higher temperature than graphite in an attempt to match the textures and isotopic compositions of the spherules simultaneously. The variation of pressure with temperature and the change in elemental abundances with time due to radioactive decay were taken into account in the condensation calculations. Layers were found within the main Ni, O/Ne, He/C and He/N zones that, when mixed together, simultaneously match the carbon, nitrogen and oxygen isotopic compositions, 44Ti/ 48Ti ratios and inferred initial 26Al/ 27Al ratios of the low-density graphite spherules, even at subsolar 12C/ 13C ratios. Due to the relatively large proportion of material from the Ni zone and the relative amounts of the two layers of the Ni zone required to meet these conditions, predicted 28Si excesses are larger than observed in the low-density graphite spherules, and large negative δ46Ti/ 48Ti, δ47Ti/ 48Ti, δ49Ti/ 48Ti and δ50Ti/ 48Ti are produced, in contrast to the observed normal δ46Ti/ 48Ti and δ47Ti/ 48Ti, large positive δ49Ti/ 48Ti and smaller positive δ50Ti/ 48Ti. Although better matches to the observed δ46Ti/ 48Ti, δ47Ti/ 48Ti and 28Si excesses can be found using much smaller amounts of Ni zone material and some Si/S zone material, it is very difficult to match simultaneously the Ti and Si isotopic compositions in any mixtures of material from these deep layers with He/C and He/N zone material, regardless of the condensation sequence. The occurrence of Fe-rich, Si-poor metal grains inside the graphite spherules does not have a satisfactory explanation.

Petrogenesis and provenance of ungrouped achondrite Northwest Africa 7325 from petrology, trace elements, oxygen, chromium and titanium isotopes, and mid-IR spectroscopy

NASA Astrophysics Data System (ADS)

Goodrich, Cyrena A.; Kita, Noriko T.; Yin, Qing-Zhu; Sanborn, Matthew E.; Williams, Curtis D.; Nakashima, Daisuke; Lane, Melissa D.; Boyle, Shannon

2017-04-01

Northwest Africa (NWA) 7325 is an ungrouped achondrite that has recently been recognized as a sample of ancient differentiated crust from either Mercury or a previously unknown asteroid. In this work we augment data from previous investigations on petrography and mineral compositions, mid-IR spectroscopy, and oxygen isotope compositions of NWA 7325, and add constraints from Cr and Ti isotope compositions on the provenance of its parent body. In addition, we identify and discuss notable similarities between NWA 7325 and clasts of a rare xenolithic lithology found in polymict ureilites. NWA 7325 has a medium grained, protogranular to poikilitic texture, and consists of 10-15 vol.% Mg-rich olivine (Fo 98), 25-30 vol.% diopside (Wo 45, Mg# 98), 55-60 vol.% Ca-rich plagioclase (An 90), and trace Cr-rich sulfide and Fe,Ni metal. We interpret this meteorite to be a cumulate that crystallized at ⩾1200 °C and very low oxygen fugacity (similar to the most reduced ureilites) from a refractory, incompatible element-depleted melt. Modeling of trace elements in plagioclase suggests that this melt formed by fractional melting or multi-stage igneous evolution. A subsequent event (likely impact) resulted in plagioclase being substantially remelted, reacting with a small amount of pyroxene, and recrystallizing with a distinctive texture. The bulk oxygen isotope composition of NWA 7325 plots in the range of ureilites on the CCAM line, and also on a mass-dependent fractionation line extended from acapulcoites. The ε54Cr and ε50Ti values of NWA 7325 exhibit deficits relative to terrestrial composition, as do ordinary chondrites and most achondrites. Its ε54Cr value is distinct from that of any analyzed ureilite, but is not resolved from that of acapulcoites (as represented by Acapulco). In terms of all these properties, NWA 7325 is unlike any known achondrite. However, a rare population of clasts found in polymict ureilites ("the magnesian anorthitic lithology") are strikingly similar to NWA 7325 in mineralogy and mineral compositions, oxygen isotope compositions, and internal textures in plagioclase. These clasts are probably xenolithic in polymict ureilites, and could be pieces of NWA 7325-like meteorites. Using constraints from chromium, titanium and oxygen isotopes, we discuss two possible models for the provenance of the NWA 7325 parent body: (1) accretion in the inner solar system from a reservoir similar to that of acapulcoites in Δ17O, ε54Cr and ε50Ti; or (2) early (<1 Ma after CAI formation) accretion in the outer solar system (beyond the snow line), before 54Cr and 50Ti anomalies were introduced to this region of the solar system. The mid-IR emission spectrum of NWA 7325 obtained in this work matches its modal mineralogy, and so can be compared with spectra of new meteorites or asteroids/planets to help identify similar materials and/or the parent body of NWA 7325.

Isotopy of the hydrosphere

NASA Astrophysics Data System (ADS)

Ferronskii, V. I.; Poliakov, V. A.

This book is concerned with the natural relations regarding the distribution of the stable isotopes of hydrogen and oxygen in the hydrosphere, taking into account the most important problems with respect to the dynamics and the origin of waters. The solution of these problems on an isotopic basis is considered. The physicochemical principles of isotope separation are discussed along with the isotopic composition of atmospheric moisture, the isotopic composition of surface continental waters, the hydrogen and oxygen isotopic composition of minerals of magmatic and metamorphic rocks and fluid inclusions, the isotopic composition of groundwaters of modern volcanic regions, and the origin of the earth's hydrosphere in the light of isotopic, cosmochemical, and theoretical studies. Attention is also given to the separation of hydrogen and oxygen isotopes of waters in the underground cycle, the isotopic composition of the deep-formation waters of sedimentary basins, the relationship between surface and ground waters, and the groundwater residence time in an aquifer.

The novel approach to the biomonitor survey using one- and two-dimensional Kohonen networks.

PubMed

Deljanin, Isidora; Antanasijević, Davor; Urošević, Mira Aničić; Tomašević, Milica; Perić-Grujić, Aleksandra; Ristić, Mirjana

2015-10-01

To compare the applicability of the leaves of horse chestnut (Aesculus hippocastanum) and linden (Tilia spp.) as biomonitors of trace element concentrations, a coupled approach of one- and two-dimensional Kohonen networks was applied for the first time. The self-organizing networks (SONs) and the self-organizing maps (SOMs) were applied on the database obtained for the element accumulation (Cr, Fe, Ni, Cu, Zn, Pb, V, As, Cd) and the SOM for the Pb isotopes in the leaves for a multiyear period (2002-2006). A. hippocastanum seems to be a more appropriate biomonitor since it showed more consistent results in the analysis of trace elements and Pb isotopes. The SOM proved to be a suitable and sensitive tool for assessing differences in trace element concentrations and for the Pb isotopic composition in leaves of different species. In addition, the SON provided more clear data on seasonal and temporal accumulation of trace elements in the leaves and could be recommended complementary to the SOM analysis of trace elements in biomonitoring studies.

Formation and Evolution of the Continental Lithospheric Mantle: Perspectives From Radiogenic Isotopes of Silicate and Sulfide Inclusions in Macrodiamonds

NASA Astrophysics Data System (ADS)

Shirey, S. B.; Richardson, S. H.

2007-12-01

Silicate and sulfide inclusions that occur in diamonds comprise the oldest (>3 Ga), deepest (>140 km) samples of mantle-derived minerals available for study. Their relevance to the evolution of the continental lithosphere is clear because terrestrial macrodiamonds are confined to regions of the Earth with continental lithospheric mantle keels. The goals of analytical work on inclusions in diamond are to obtain paragenesis constraints, radiogenic ages, and initial isotopic compositions. The purpose is to place diamond formation episodes into the broader framework of the geological processes that create and modify the continental lithosphere and to relate the source of the C and N in diamond-forming fluids to understanding the Earth's C and N cycles in the Archean. Although sulfide and silicate inclusions rarely occur in the same diamond, they both can be grouped according to their geochemical similarity with the chief rock types that comprise the mantle keel: peridotite and eclogite. Silicate inclusions are classified as harzburgitic (depleted; olivine > Fo91, garnet Cr2O3 > 3 wt% and CaO from 0 to 5 wt%), lherzolitic (fertile), or eclogitic (basaltic; garnet Cr2O3 < 2 wt% and CaO from 3 to 15 wt%, clinopyroxene with higher Na2O, Al2O3, and FeO); they are amenable for trace element study by SIMS and for Sm-Nd and Rb-Sr analysis by conventional P-TIMS after grouping by mineralogical similarity. Sulfide inclusions (chiefly FeS with lesser Ni, Cu, and Co) are classified as peridotitic (Ni > 14 wt%; Os > 2 ppm) versus eclogitic (Ni < 10 wt%; Os < 200 ppb); single sulfides are amenable for S isotopic study by SIMS or TIMS, and Re-Os analysis by N-TIMS. Work on inclusions in diamonds depends on the distribution of mined, diamond-bearing kimberlites, and the generosity of mining companies because of the extreme rarity of inclusions in suites of mostly gem-quality diamonds. Most isotopic work has been on the Kaapvaal-Zimbabwe craton with lesser work on the Slave, Siberian, and Australian cratons. Sm-Nd ages on silicate suites and Re-Os ages on sulfide suites confirm diamond formation from the Mesoarchean though the Neoproterozoic. Most important are the systematics across cratons in the context of crustal geology that lead to generalities about craton evolution. Inclusion suites date mantle keels as Mesoarchean and clearly point to subduction as the major process to form the earliest continental nuclei and to amalgamate the cratons in their present form. This is evident from the elevated initial Os isotopic compositions in 3.5 Ga Slave (Panda) and 2.9 Ga Kaapvaal (Kimberley) sulfides, the low Sm/Nd and elevated initial Sr isotopic compositions of 3.4 Ga Kaapvaal (Kimberley) harzburgitic garnets, the preponderance of 2.9 Ga eclogitic sulfides in every western Kaapvaal craton locality, and the occurrence of surficial, volcanogenic S in Kaapvaal (Orapa) sulfides. The continental lithosphere was accessible to melts and fluids from the asthenosphere throughout the Proterozoic as evident from silicate and sulfide inclusion suites of 0.9 to 2.0 Ga age in every locality studied in the Kaapvaal craton. The correspondence of silicate inclusion type with current seismic velocity structure of the Kaapvaal mantle keel shows that its structure is at least Bushveld age (2 Ga) and due to compositional differences. Seismic velocity structures of continental mantle keels may be more a function of their geologic history than current temperature distribution.

Preservation of REE and Fe isotopes in altered stromatolites and the paleo-environmental record

NASA Astrophysics Data System (ADS)

Nies, S. M.; Shapiro, R. S.; Lalonde, S.

2015-12-01

Geochemical proxies are increasingly being used to unravel ancient ecosystems and environmental perturbations back to the earliest rock record on Earth. Along with more traditional fossils (stromatolites) and other biosignatures (e.g., lipids), the geochemical record is used specifically to evaluate biogenecity and to understand oxygenation of the atmosphere and ocean in the Archean and Paleoproterozoic. However, the effects of diagenesis, metamorphism, and other modes of secondary alteration are still poorly constrained, particularly as technological advances allow us to expand farther across the periodic table. Our study focused on the robustness and preservation of rare earth element (REE) and Fe isotope compositions of two stromatolitic units that have undergone contact and regional metamorphism. 18 samples were collected from cores, open pit mines, and field locations in Minnesota and Ontario from silicified iron formation (Biwabik-Gunflint formations). The samples were carefully constrained to one of two meter-scale stromatolitic units. Metamorphic grade ranged from essentially unmetamorphosed through prehnite-pumpellyite up to amphibolite (fayalite+hypersthene). Samples were also collected that represented deep secondary weathering, likely related to Cretaceous climatic extremes. Polished samples were first analyzed by electron microprobe and selected samples were further analyzed via laser ablation HR-ICP-MS to constrain trace element (n=13) and Fe isotopic variations (n=8). Preliminary results indicate that transition metal concentrations are surprisingly resilient to high-temperature metamorphic recrystallization. REE concentrations were analyzed in individual iron oxide grains, with full resolution (La to Lu) achieved for some samples and partial resolution (La to Nd) achieved for all samples. Core samples exhibited a relatively stable positive Ce anomaly occurring from low to extremely high alteration. Outcrop and mine samples indicate a shift from a negative Ce anomaly in less altered samples, to a positive Ce anomaly in highly altered samples. Collectively, our results imply that caution is warranted when making paleo-environmental inferences from samples with significantly different alteration histories.

Speciation and isotopic composition of sulfur in sediments from Jellyfish Lake, Palau

USGS Publications Warehouse

Bates, A.L.; Spiker, E. C.; Orem, W.H.; Burnett, W.C.

1993-01-01

Jellyfish Lake, Palau, is a meromictic marine lake with high organic productivity, low reactive Fe content, and anoxic bottom waters. Sediment samples from Jellyfish Lake were examined for the distribution of sulfur species and their isotopic signatures in order to gain a better understanding of sedimentary sulfur incorporation in Fe-poor environments. Surface samples were taken along a transect from a near-shore site to the center of the lake, and include a sample below oxic water, a sample below the chemocline layer, and samples below anoxic waters. Three additional samples were taken from a core, 2 m long, collected near the lake center. Sulfur to organic carbon weight ratios in all samples were lower than the expected value of 0.36 for normal marine sediment, probably because the lake water is deficient in reactive Fe to form iron sulfides. Total sulfur contents in the surface sediments indicated no changes with distance from shore; however, the sulfur content of the surface sample at the chemocline layer may be slightly higher. Total sulfur content increased with depth in the core and is inversely related to organic carbon content. Organic sulfur is the major sulfur species in the samples, followed in descending order by sulfate, disulfides and monosulfides. Sulfate sulfur isotope ??34S-values are positive (from +20.56 to +12.04???), reflecting the marine source of sulfate in Jellyfish Lake. Disulfide and monosulfide ??34S-values are negative (from -25.07 to -7.60???), because of fractionation during bacterial reduction of sulfate. Monosulfide ??34S-values are somewhat higher than those of disulfides, and they are close to the ??34S-values of organic sulfur. These results indicate that most of the organic sulfur is formed by reaction of bacteriogenic monosulfides, or possibly monosulfide-derived polysulfides, with organic matter in the sediment. ?? 1993.

Iron and zinc isotope fractionation during uptake and translocation in rice (Oryza sativa) grown in oxic and anoxic soils

NASA Astrophysics Data System (ADS)

Arnold, Tim; Markovic, Tamara; Kirk, Guy J. D.; Schönbächler, Maria; Rehkämper, Mark; Zhao, Fangjie J.; Weiss, Dominik J.

2015-11-01

Stable isotope fractionation is emerging quickly as a powerful novel technique to study metal uptake and translocation in plants. Fundamental to this development is a thorough understanding of the processes that lead to isotope fractionation under differing environmental conditions. In this study, we investigated Zn and Fe isotope fractionation in rice grown to maturity in anaerobic and aerobic soils under greenhouse conditions. The overall Zn isotope fractionation between the soil and above ground plant material was negligible in aerobic soil but significant in anaerobic soil with isotopically lighter Zn in the rice plant. The observed range of fractionation is in line with previously determined fractionations of Zn in rice grown in hydroponic solutions and submerged soils and emphasizes the effect of taking up different chemical forms of Zn, most likely free and organically complexed Zn. The Zn in the grain was isotopically lighter than in the rest of the above ground plant in rice grown in aerobic and anaerobic soils alike. This suggests that in the course of the grain loading and during the translocation within the plant important biochemical and/or biophysical processes occur. The isotope fractionation observed in the grains would be consistent with an unidirectional controlled transport from shoot to grain with a fractionation factor of α ≈ 0.9994. Iron isotopes showed an isotopic lighter signature in shoot and grain compared to the bulk soil or the leachate in aerobic and anaerobic soils alike. The negative direction of isotopic fractionation is consistent with possible changes in the redox state of Fe occurring during the uptake and translocation processes. The isotope fractionation pattern between shoots and grain material are different for Zn and Fe which finally suggests that different mechanisms operate during translocation and grain-loading in rice for these two key micronutrients.

Subduction-modified oceanic crust in the sources of continental picrite dikes from the Karoo LIP?

NASA Astrophysics Data System (ADS)

Heinonen, J. S.; Carlson, R. W.; Riley, T. R.; Luttinen, A. V.; Horan, M. F.

2013-12-01

The Ahlmannryggen mountain range in East Antarctica hosts unusual LILE-depleted, but Fe- and Ti-enriched ultramafic dikes (Group 3) that belong to the Jurassic (~180 Ma) Karoo continental flood basalt (CFB) province. Their high initial ɛNd (+5 to +9) indicates their origin within the sublithospheric mantle beneath the Gondwana supercontinent. Using the new Pb and Os isotopic data and previously published geochemical and mineral chemical data, we try to constrain their mantle sources. The dikes that lack evidence of crustal contamination exhibit very radiogenic ɛNd (+8.6 to +9.0), relatively radiogenic 206Pb/204Pb (18.2-18.4) and 87Sr/86Sr (0.7035-0.7037), and unradiogenic 187Os/188Os (0.124-0.125) at 180 Ma. These isotopic compositions are unlike those typical of MORBs, excluding depleted mantle as the sole source contributor. The Pb isotopic composition of the dikes plots close to the 4.43 Ga geochron and hence is compatible with derivation from an early-depleted reservoir (EDR), recently suggested to be a major source component in CFBs. However, the high ɛNd of the dikes exceeds the ɛNd estimated for EDR (+4.9 to +8.5 at 180 Ma) and the relative Nb, Fe, and Ti enrichment (pyroxenite fingerprint) of the dikes is not readily ascribed to EDR source. Based on our isotopic and trace element modeling, we regard that the mantle source of the picrite dikes contained seawater-altered and subduction-modified MORB with a recycling age of 0.8 Ga. Such a source component would explain the unusual combination of elevated initial 87Sr/86Sr, ɛNd, and 206Pb/204Pb, relative depletion in fluid-mobile LILE, U, Th, Pb, and LREE, and relative enrichment in Nb, Fe, Ti, and other HFSE. Behavior of Re and Os in subduction environments is not well constrained, but loss of Re from recycled MORB, as observed in some subduction-associated eclogites and blueschists, and predominant contribution of Os from depleted peridotite matrix could have produced the observed low 187Os/188Os. Pyroxenite sources also are consistent with mineral chemical data (e.g., high-Ni olivine) for the picrite dikes. Such peculiar sources were likely not a predominant component in Karoo magmatism in general. Nevertheless, less subduction-modified or more enriched (e.g., additional sediment component) recycled crustal signatures would be difficult to distinguish from the 'lithospheric signatures' of many common CFBs. In addition to depleted mantle or EDR components that have been identified in the high-Mg dikes of the adjacent Vestfjella mountain range, a variety of recycled source components could thus be hiding in the geochemical jungle of the Karoo (and other) CFBs.

Iron Isotope Systematics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dauphas, Nicolas; John, Seth G.; Rouxel, Olivier

Iron is a ubiquitous element with a rich (i.e., complex) chemical behavior. It possesses three oxidation states, metallic iron (Fe0), ferrous iron (Fe2+) and ferric iron (Fe3+). The distribution of these oxidation states is markedly stratified in the Earth.

Mn-Cr isotopic systematics of Chainpur chondrules and bulk ordinary chondrites

NASA Technical Reports Server (NTRS)

Nyquist, L.; Lindstrom, D.; Wiesmann, H.; Bansal, B.; Shih, C.-Y.; Mittlefehldt, D.; Martinez, R.; Wentworth, S.

1994-01-01

We report on ongoing study of the Mn-Cr systematics of individual Chainpur (LL3.4) chondrules and compare the results to those for bulk ordinary chondrites. Twenty-eight chondrules were surveyed for abundances of Mn, Cr, Na, Fe, Sc, Hf, Ir, and Zn by INAA. Twelve were chosen for SEM/EDX and high-precision Cr-isotopic studies on the basis of LL-chondrite-normalized Mn(LL), Sc(LL), (Mn/Fe)(LL), and (Sc/Fe)(LL) as well as their Mn/Cr ratios. Classification into textural types follows from SEM/EDX examination of interior surfaces.

Osmium isotopic homogeneity in the CK carbonaceous chondrites

NASA Astrophysics Data System (ADS)

Goderis, Steven; Brandon, Alan D.; Mayer, Bernhard; Humayun, Munir

2017-11-01

Variable proportions of isotopically diverse presolar components are known to account for nucleosynthetic isotopic anomalies for a variety of elements (e.g., Ca, Ti, Cr, Ni, Sr, Zr, Mo, Ru, Pd, Ba, Nd, and Sm) in both bulk chondrites and achondrites. However, although large Os isotopic anomalies have been measured in acid leachates and residues of unequilibrated chondrites, bulk chondrites of various groups, iron meteorites, and pallasites exhibit Os isotopic compositions that are indistinguishable from terrestrial or bulk solar isotopic abundances. Since the magnitude of nucleosynthetic anomalies is typically largest in the carbonaceous chondrites, this study reports high-precision Os isotopic compositions and highly siderophile element (HSE) concentrations for ten CK chondrites. The isotope dilution concentration data for HSE and high-precision Os isotope ratios were determined on the same digestion aliquots, to precisely correct for radiogenic contributions to 186Os and 187Os. While acid leached bulk unequilibrated carbonaceous chondrites show deficits of s-process Os components to the same extent as revealed by unequilibrated enstatite, ordinary, and Rumuruti chondrites, equilibrated bulk CK chondrites exhibit no resolvable Os isotopic anomalies. These observations support the idea that acid-resistant, carbon-rich presolar grains, such as silicon carbide (SiC) or graphite, are major carriers for nucleosynthetic isotopic anomalies of Os. The destruction of these presolar grains, which are omnipresent in unequilibrated meteorites, must have occurred during aqueous alteration and thermal metamorphism, early in the CK chondrite parent body history. The dispersal of CK chondrites along the IIIAB iron meteorite isochron on a 187Os/188Os versus 187Re/188Os diagram, with Re/Os ratios from 0.032 to 0.083, in combination with the observed redistribution of other HSE (e.g., Pt, Pd), highlights the influence of parent body processes, overprinted by effects of recent terrestrial alteration. Under the oxidizing conditions prevalent on the CK parent body, evident from high abundances of magnetite and limited Fe-Ni metal in CK chondrites, these parent body processes made all isotopically anomalous Os, originally hosted in reduced presolar grains, accessible. The absence of Os isotopic anomalies in ordinary, enstatite, and now also carbonaceous chondrites, implies that the carriers of s- and r-process Os must have been effectively homogenized across the region of chondrite formation, and possibly even the entire solar protoplanetary nebula, as suggested by the Os isotopic compositions of iron meteorites and non-anomalous ureilites. Except for a limited number of ureilites, the relative proportions of presolar s- and r-process carriers of Os (and other elements such as W) in chondrites, and most other planetary bodies, must have remained constant during all subsequent nebular and planetary processes, which appears not to have been the case for other siderophile elements, including Mo, Ru, and Pd. The existence of Mo, Ru, Pd and other siderophile element isotopic anomalies thus appears to be in part controlled by the chemical properties of these elements (e.g., volatility), their host phase(s) (e.g., SiC, graphite, metal, sulfides), and the nature of the nebular or planetary processes experienced in the early solar system.

Studies of the reactivity of the ferrihydrite surface by iron isotopic exchange and Mossbauer spectroscopy

USGS Publications Warehouse

Rea, Brigid A.; Davis, James A.; Waychunas , Glenn A.

1994-01-01

Two-line ferrihydrite is an important adsorbent of many toxics in natural and anthropogenic systems; however, the specific structural sites responsible for the high adsorption capacity are not well understood. A combination of chemical and spectroscopic techniques have been employed in this study to gain further insight into the structural nature of sites at the ferrihydrite surface. The kinetics of iron isotopic exchange demonstrated that there are at least two types of iron sites in ferrihydrite. One population of sites, referred to as labile sites, approached iron isotopic equilibrium within 24 hr in 59Fe-NTA solutions, while the second population of sites, referred to as non-labile, exhibited a much slower rate of isotopic exchange. Adsorbed arsenate reduced the degree of exchange by labile sites, indicating that the anion blocked or greatly inhibited the rate of exchange of these sites. Mössbauer spectra were collected from a variety of samples including 56Fe-ferrihydrite samples with 57Fe in labile sites, samples containing 57Fe throughout the structure, and samples with 57Fe in non-labile sites. The spectra showed characteristic broad doublets signifying poor structural order. Refined fits of the spectra indicated that labile sites have larger quadrupole splitting, hence more local distortion, than non-labile sites. In all cases, the spectra demonstrated some degree of asymmetry, indicating a distribution of Fe environments in ferrihydrite. Overall spectral findings, combined with recent EXAFS results (Waychunas et al., 1993), indicate that labile sites likely are more reactive (with respect to iron isotopic exchange) because they have fewer neighboring Fe octahedra and are therefore bound less strongly to the ferrihydrite structure. The labile population of sites probably is composed of end sites of the dioctahedral chain structure of 2-line ferrihydrite, which is a subset of the entire population of surface sites. Mössbauer spectra of samples containing adsorbed arsenate indicated that the anion may slightly decrease the distortion of labile sites and stabilized the structure as a whole by bidentate bonding.

Charge Radii of Neutron Deficient Fe,5352 Produced by Projectile Fragmentation

NASA Astrophysics Data System (ADS)

Minamisono, K.; Rossi, D. M.; Beerwerth, R.; Fritzsche, S.; Garand, D.; Klose, A.; Liu, Y.; Maaß, B.; Mantica, P. F.; Miller, A. J.; Müller, P.; Nazarewicz, W.; Nörtershäuser, W.; Olsen, E.; Pearson, M. R.; Reinhard, P.-G.; Saperstein, E. E.; Sumithrarachchi, C.; Tolokonnikov, S. V.

2016-12-01

Bunched-beam collinear laser spectroscopy is performed on neutron deficient Fe,5352 prepared through in-flight separation followed by a gas stopping. This novel scheme is a major step to reach nuclides far from the stability line in laser spectroscopy. Differential mean-square charge radii δ ⟨r2⟩ of Fe,5352 are determined relative to stable 56Fe as δ ⟨r2⟩56 ,52=-0.034 (13 ) fm2 and δ ⟨r2⟩56 ,53=-0.218 (13 ) fm2 , respectively, from the isotope shift of atomic hyperfine structures. The multiconfiguration Dirac-Fock method is used to calculate atomic factors to deduce δ ⟨r2⟩. The values of δ ⟨r2⟩ exhibit a minimum at the N =28 neutron shell closure. The nuclear density functional theory with Fayans and Skyrme energy density functionals is used to interpret the data. The trend of δ ⟨r2⟩ along the Fe isotopic chain results from an interplay between single-particle shell structure, pairing, and polarization effects and provides important data for understanding the intricate trend in the δ ⟨r2⟩ of closed-shell Ca isotopes.

Isotopic evidence for oxygenated Mesoarchaean shallow oceans

NASA Astrophysics Data System (ADS)

Eickmann, Benjamin; Hofmann, Axel; Wille, Martin; Bui, Thi Hao; Wing, Boswell A.; Schoenberg, Ronny

2018-02-01

Mass-independent fractionation of sulfur isotopes (MIF-S) in Archaean sediments results from photochemical processing of atmospheric sulfur species in an oxygen-depleted atmosphere. Geological preservation of MIF-S provides evidence for microbial sulfate reduction (MSR) in low-sulfate Paleoarchaean (3.8-3.2 billion years ago (Ga)) and Neoarchaean (2.8-2.5 Ga) oceans, but the significance of MSR in Mesoarchaean (3.2-2.8 Ga) oceans is less clear. Here we present multiple sulfur and iron isotope data of early diagenetic pyrites from 2.97-Gyr-old stromatolitic dolomites deposited in a tidal flat environment of the Nsuze Group, Pongola Supergroup, South Africa. We identified consistently negative Δ33S values in pyrite, which indicates photochemical reactions under anoxic atmospheric conditions, but large mass-dependent sulfur isotope fractionations of 30‰ in δ34S, identifying active MSR. Negative pyrite δ56Fe values (-1.31 to -0.88‰) record Fe oxidation in oxygen-bearing shallow oceans coupled with biogenic Fe reduction during diagenesis, consistent with the onset of local Fe cycling in oxygen oases 3.0 Ga. We therefore suggest the presence of oxygenated near-shore shallow-marine environments with ≥5 μM sulfate at this time, in spite of the clear presence of an overall reduced Mesoarchaean atmosphere.

Sulfur and Oxygen Isotopic Analysis of a Cosmic Symplectite from a Comet Wild 2 Stardust Terminal Particle

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Berger, E. L.; Nakamura-Messenger, K.; Messenger, S.

2015-01-01

Introduction: Analyses of comet 81P/Wild 2 samples re-turned from the Stardust mission have uncovered surprising simi-larities to meteoritic material, including the identification of inner solar system grains [1-3]. The TEM characterization of terminal particle (TP) 4 from Stardust track #147 revealed an assemblage consisting of symplectically intergrown pentlandite and nanocrys-talline maghemite coexisting with high-Ca pyroxene [4]. Mineral-ogically similar cosmic symplectites (COS) containing pentlandite and magnetite in the primitive Acfer 094 meteorite are highly de-pleted in 16O (?17O, ?18O 180 per mille) [5-7]. This isotopic signature is proposed to record alteration with primordial solar nebula water. Conversely, the normal O isotopic composition of the Stardust COS indicates alteration by a different aqueous reservoir, perhaps on the comet [8]. In this study, we analyzed the Wild 2 COS for S isotopes to further constrain its origin. Experimental: Thin sections of TP4 (12 ?m) were produced and their mineralogy was thoroughly characterized by TEM. Two of the sections were analyzed for O isotopes by isotopic imaging in the JSC NanoSIMS 50L. The sample in one of the slices was completely consumed. The remaining material in the adjacent slice was analyzed simultaneously for 16O, 32S, 33S, 34S, and 56Fe16O in electron multipliers using a Cs+ primary ion beam. Quasi-simulta-neous arrival (QSA) can have a significant effect on S isotopic ra-tios when using electron multipliers, resulting in undercounting of 32S [9]. Canyon Diablo troilite (CDT) was measured numerous times to deduce a correction factor for QSA and ensure measure-ment reproducibility. Isotopic ratios are reported relative to CDT. Results and Discussion: The Wild 2 COS is enriched in the heavy S isotopes relative to CDT (?33S = 6.5 +/- 1.6 per mille; ?34S = 5.1 +/- 0.7 per mille; 1?). The degree of 33S enrichment indicates mass-inde-pendent fractionation (MIF) with ?33S = 3.9 +/- 1.7 per mille. MIF of S has been observed in some chondrules (?33S up to 0.11per mille) [10], but this effect has not been identified in sulfides from carbonaceous chondrites [11] or IDPs [12]. S isotopic analysis of Stardust impact craters also did not reveal MIF or anomalies, save for one potential 32S-rich presolar sulfide [13]. Measurement errors on these impact craters were much larger than those in this study, however. MIF of S has been proposed to result from heterogeneities in the solar neb-ula from nucleosynthetic components [14] or photochemical irra-diation of solar nebula gas [10]. Presolar SiC grains are observed to have 32S enrichments [15, 16] contrary to the S isotopic compo-sition of the cometary COS. The S isotopic composition more likely reflects irradiation of nebular gas.

Cenozoic History of the Equatorial Indian Ocean Recorded by Nd Isotopes: The Closure of the Indonesian Gateway

NASA Astrophysics Data System (ADS)

Gourlan, A. T.; Meynadier, L.; Allegre, C. J.

2005-12-01

The northward tectonic motion of the Australian plate and the evolution of the Indonesian Island Arcs through the last 20 Ma, generate changes in the flow and the origin of the circulation between the Pacific and the Southern Indian Oceans. Indeed, the emergence of the Indonesian Archipelago and probably the rapid uplift of the island of Halmahera have dramatically reduced the Indonesian Gateway. However, the precise dating of this event is still a matter of debate. The Neodymium isotopic composition of marine sediments is an extremely good proxy to reconstruct the major changes in the past ocean circulation. The residence time of Nd is shorter than the circulation time of the global ocean. Therefore, the Nd isotopic composition varies between the different ocean basins and is function of changes in source provenances, paleocirculation, orogenic processes, and intensity of weathering on the continents as well as on the volcanic arcs. To reconstruct the evolution of the oceanic flow from the Pacific to the equatorial Indian Ocean since the Miocene, we have applied on high carbonates content sediments a leaching technique using acetic acid. The reliability of our technique has been assessed by comparison with the Hydroxylamine hydrochloride technique developed by Bayon et al (1). The Nd isotopic composition is determinated in the past seawater from the record in Fe-Mn oxides. The sedimentary sequences are accurately dated using bio and chimiostratigraphy. Three ODP Sites were chosen in the Indian Ocean with a water depth ranging from 1600 to 2800 m and mutually distant by about 3000 km. From West to East: Site 761 which is at the western edge of the Indonesian Gateway on the central northeastern part of the Wombat Plateau off NW Australia, Site 757 is located on the south of the Ninetyeast ridge and Site 707 is located in the western tropical Indian Ocean near the Seychelles Islands. Our data are compared with the first results from Site 807 located in the Pacific Ocean on the northern rim of the Ontong Java Plateau. Results on the seawater signal of the Indian sites show a similar pattern in ɛNd for the last 20 Ma with a continous increase in ɛNd from -8 to -4.5 followed by an abrupt change of the ɛNd values (decreasing at -6.5) which occurred around 3-4 Ma. Comparing our results with the Nd isotopic composition of three Fe-Mn crusts dragged close to the Indian sites (SS63, DODO 232D and VA16 13KD-1 (2,3)), we confirm a throughflow travelling west, with pacific waters entering across the Indonesian arcs, to the east of African coast since at least 15 Ma and support the idea of the rapid closure of the Indonesian seaway around 3-4 million years ago in less than 2 Ma. (1) Bayon et al, 2001, Chem. Geology 187,179 -199 (2) Franck et al, Chem. Geology 2005 submitted (3) O'Nions et al, 1998, EPSL, 155, 15-28

Iron(II)-Catalyzed Iron Atom Exchange and Mineralogical Changes in Iron-rich Organic Freshwater Flocs: An Iron Isotope Tracer Study.

PubMed

ThomasArrigo, Laurel K; Mikutta, Christian; Byrne, James; Kappler, Andreas; Kretzschmar, Ruben

2017-06-20

In freshwater wetlands, organic flocs are often found enriched in trace metal(loid)s associated with poorly crystalline Fe(III)-(oxyhydr)oxides. Under reducing conditions, flocs may become exposed to aqueous Fe(II), triggering Fe(II)-catalyzed mineral transformations and trace metal(loid) release. In this study, pure ferrihydrite, a synthetic ferrihydrite-polygalacturonic acid coprecipitate (16.7 wt % C), and As- (1280 and 1230 mg/kg) and organic matter (OM)-rich (18.1 and 21.8 wt % C) freshwater flocs dominated by ferrihydrite and nanocrystalline lepidocrocite were reacted with an isotopically enriched 57 Fe(II) solution (0.1 or 1.0 mM Fe(II)) at pH 5.5 and 7. Using a combination of wet chemistry, Fe isotope analysis, X-ray absorption spectroscopy (XAS), 57 Fe Mössbauer spectroscopy and X-ray diffraction, we followed the Fe atom exchange kinetics and secondary mineral formation over 1 week. When reacted with Fe(II) at pH 7, pure ferrihydrite exhibited rapid Fe atom exchange at both Fe(II) concentrations, reaching 76 and 89% atom exchange in experiments with 0.1 and 1 mM Fe(II), respectively. XAS data revealed that it transformed into goethite (21%) at the lower Fe(II) concentration and into lepidocrocite (73%) and goethite (27%) at the higher Fe(II) concentration. Despite smaller Fe mineral particles in the coprecipitate and flocs as compared to pure ferrihydrite (inferred from Mössbauer-derived blocking temperatures), these samples showed reduced Fe atom exchange (9-30% at pH 7) and inhibited secondary mineral formation. No release of As was recorded for Fe(II)-reacted flocs. Our findings indicate that carbohydrate-rich OM in flocs stabilizes poorly crystalline Fe minerals against Fe(II)-catalyzed transformation by surface-site blockage and/or organic Fe(II) complexation. This hinders the extent of Fe atom exchange at mineral surfaces and secondary mineral formation, which may consequently impair Fe(II)-activated trace metal(loid) release. Thus, under short-term Fe(III)-reducing conditions facilitating the fast attainment of solid-solution equilibria (e.g., in stagnant waters), Fe-rich freshwater flocs are expected to remain an effective sink for trace elements.

Reconstruction of deglacial Antarctic Intermediate Water variations in the subtropical North Atlantic

NASA Astrophysics Data System (ADS)

Xie, R. C.; Marcantonio, F.; Schmidt, M. W.

2012-12-01

Understanding intermediate water circulation across the last deglaciation is critical in assessing the role of oceanic heat transport associated with Atlantic Meridional Overturning Circulation (AMOC) variability across abrupt climate events. Abrupt changes in the northward flow of Antarctic Intermediate Water (AAIW) associated with AMOC reduction during the Younger Dryas (YD) and Heinrich Event 1 (H1) have been hypothesized, suggesting a potential connection between the Southern Ocean and high-latitude North Atlantic climate change. However, controversy persists as to whether the northward flow of AAIW is stronger or weaker during these abrupt cold events. One school maintains that there is an increase in the northward penetration of AAIW associated with weaker AMOC during both the YD and H1 cold events (e.g., [1-2]). However, each of these previous studies analyzed sediment cores retrieved from depths deeper than the modern depth range of AAIW (500-1100 m in the tropical and subtropical North Atlantic). Another school comes to the opposite conclusion, namely that there is a weakening of AAIW at least during one of the deglacial events (e.g., [3-4]). Here, we reconstruct deglacial AAIW variations using authigenic Nd isotope ratios from sediment recovered from core VM12-107 (11.33°N, 66.63°W; 1079 m) in the Southern Caribbean Sea. VM12-107 lies at the boundary between modern AAIW and modern upper NADW and thus is ideal for investigating the shoaling/deepening of the competing water masses as well as the variations of AAIW across abrupt climate events during the last deglaciation. We measured authigenic Nd isotope compositions in three different fractions in core VM12-107: the Fe-Mn oxyhydroxide leachate of the bulk sediment, the uncleaned planktonic foraminifera (mixed species), and fish debris wherever possible. Preliminary authigenic Nd isotope results from the Fe-Mn leachate show little variability in the ɛNd values, ranging from -9.6 to -10.6, during the last deglaciation. No discernable long-term trend is suggested. The small variation in authigenic ɛNd values may suggest little change in the northward penetration of AAIW at our study site during the last deglaciation. On the other hand, shoaling of the glacial analogue of NADW (i.e., Glacial North Atlantic Intermediate Water), with a more radiogenic ɛNd signature during the YD and H1, can also explain our authigenic ɛNd record from the Fe-Mn leachates. Comparing our authigenic Nd isotope record with those recently published from the Florida Straits [4] and those from the Tobago Basin [1], we propose that sediment cores retrieved from depths below the modern AAIW depth range are not suitable in tracing deglacial AAIW variability. Because the Nd isotope record from authigenic Fe-Mn leachate fraction can be biased by excess leaching of the detrital fraction of the sediment, ɛNd values from uncleaned planktonic foraminifera (mixed species) and fish debris will be presented to test the Nd isotope record from authigenic Fe-Mn leachates. [1] Pahnke et al. (2008) Nature Geoscience 1, 870-874 [2] Thornalley et al. (2011) Science 331(6014), 202-205; [3] Came et al. (2008) Paleoceanography 23, PA1217; [4] Xie et al. (in press) Paleoceanography, doi:10.1029/2012PA002337

Chondrites and the Protoplanetary Disk, Part 3

NASA Technical Reports Server (NTRS)

2004-01-01

Contents include the following: Ca-, Al-Rich Inclusions and Ameoboid Olivine Aggregates: What We Know and Don t Know About Their Origin. Aluminium-26 and Oxygen Isotopic Distributions of Ca-Al-rich Inclusions from Acfer 214 CH Chondrite. The Trapping Efficiency of Helium in Fullerene and Its Implicatiion to the Planetary Science. Constraints on the Origin of Chondritic Components from Oxygen Isotopic Compositions. Role of Planetary Impacts in Thermal Processing of Chondrite Materials. Formation of the Melilite Mantle of the Type B1 CAIs: Flash Heating or Transport? The Iodine-Xenon System in Outer and Inner Portions of Chondrules from the Unnamed Antarctic LL3 Chondrite. Nucleosynthesis of Short-lived Radioactivities in Massive Stars. The Two-Fluid Analysis of the Kelvin-Helmholtz Instability in the Dust Layer of a Protoplanetary Disk: A Possible Path to the Planetesimal Formation Through the Gravitational Instability. Shock-Wave Heating Model for Chonodrule Formation: Heating Rate and Cooling Rate Constraints. Glycine Amide Hydrolysis with Water and OH Radical: A Comparative DFT Study. Micron-sized Sample Preparation for AFM and SEM. AFM, FE-SEM and Optical Imaging of a Shocked L/LL Chondrite: Implications for Martensite Formation and Wave Propagation. Infrared Spectroscopy of Chondrites and Their Components: A Link Between Meteoritics and Astronomy? Mid-Infrared Spectroscopy of CAI and Their Mineral Components. The Origin of Iron Isotope Fractionation in Chondrules, CAIs and Matrix from Allende (CV3) and Chainpur (LL3) Chondrites. Protoplanetary Disk Evolution: Early Results from Spitzer. Kinetics of Evaporation-Condensation in a Melt-Solid System and Its Role on the Chemical Composition and Evolution of Chondrules. Oxygen Isotope Exchange Recorded Within Anorthite Single Crystal in Vigarano CAI: Evidence for Remelting by High Temperature Process in the Solar Nebula. Chondrule Forming Shock Waves in Solar Nebula by X-Ray Flares. Organic Globules with Anormalous Nitrogen Isotopic Compositions in the Tagish Lake Meteorite: Products of Primitive Organic Reactions. Yet Another Chondrule Formation Scenario. CAIs are Not Supernova Condensates. Microcrystals and Amorphous Material in Comets and Primitive Meteorites: Keys to Understanding Processes in the Early Solar System. A Nearby Supernova Injected Short-lived Radionuclides into Our Protoplanetary Disk. REE+Y Systematics in CC and UOC Chondrules. Meteoritic Constraints on Temperatures, Pressures, Cooling Rates, Chemical Compositions, and Modes of Condensation in the Solar Nebula. The I-Xe Record of Long Equilibration in Chondrules from the Unnamed Antarctic Meteorite L3/LL3. Early Stellar Evolution.

Petrogenesis of nephelinites from the Tarim Large Igneous Province, NW China: Implications for mantle source characteristics and plume-lithosphere interaction

NASA Astrophysics Data System (ADS)

Cheng, Zhiguo; Zhang, Zhaochong; Hou, Tong; Santosh, M.; Zhang, Dongyang; Ke, Shan

2015-04-01

The nephelinite exposed in the Wajilitage area in the northwestern margin of the Tarim large igneous province (TLIP), Xinjiang, NW China display porphyritic textures with clinopyroxene, nepheline and olivine as the major phenocryst phases, together with minor apatite, sodalite and alkali feldspar. The groundmass typically has cryptocrystalline texture and is composed of crystallites of clinopyroxene, nepheline, Fe-Ti oxides, sodalite, apatite, rutile, biotite, amphibole and alkali feldspar. We report rutile SIMS U-Pb age of 268 ± 30 Ma suggesting that the nephelinite may represent the last phase of the TLIP magmatism, which is also confirmed by the field relation. The nephelinite shows depleted Sr-Nd isotopic compositions with age-corrected 87Sr/86Sr and εNd(t) values of 0.70348-0.70371 and + 3.28 to + 3.88 respectively indicating asthenospheric mantle source. Based on the reconstructed primary melt composition, the depth of magma generation is estimated as 115-140 km and the temperatures of mantle melting as 1540-1575 °C. The hotter than normal asthenospheric mantle temperature suggests the involvement of mantle thermal plume. The Mg isotope values display a limited range of δ26Mg from - 0.35 to - 0.55‰, which are lower than the mantle values (- 0.25‰). The Mg isotopic compositions, combined with the Sr-Nd isotopes and major and trace element data suggest that the Wajilitage nephelinite was most likely generated by low-degree partial melting of the hybridized carbonated peridotite/eclogite source, which we correlate with metasomatism by subducted carbonates within the early-middle Paleozoic convergent regime. A plume-lithosphere model is proposed with slight thinning of the lithosphere and variable depth and degree of melting of the carbonated mantle during the plume-lithosphere interaction. This model also accounts for the variation in lithology of the TLIP.

The Role of Microbial Iron Reduction in the Formation of Proterozoic Molar Tooth Structures

NASA Astrophysics Data System (ADS)

Hodgskiss, M. S. W.; Kunzmann, M.; Halverson, G. P.; Poirier, A.

2016-12-01

Molar tooth structures are poorly understood early diagenetic, microspar-filled voids in clay-rich carbonate sediments. They are a common structure in sedimentary successions dating from 2600-720 Ma, but do not occur in rocks older or younger. Despite being volumetrically significant in carbonate rocks of this age, their formation and disappearance are poorly understood. Here, we present iron isotope data, supported by carbon and oxygen isotopes, major and minor element concentrations, and total organic carbon and pyrite contents for samples from ten regions spanning 1870-635 Ma. The iron isotopic composition of molar tooth structures is almost always lighter (modal depletion of 2‰) than the carbonate or siliciclastic components in the host sediment, whereas carbon isotopes are indistinguishable. We interpret the isotopically light iron in molar tooth structures to have been produced by microbial iron reduction utilising Fe-oxyhydroxides and smectites. The microbial conversion of smectite to illite results in a volume reduction of clay minerals ( 30%), while locally increasing pore water alkalinity. Therefore, this biogeochemical process is a viable mechanism to produce voids and subsequently precipitate carbonate minerals. The disappearance of molar tooth structures is likely linked to a combination of a decrease in smectite abundance, a decline in the marine DIC reservoir, and increase in the concentration of O2 in shallow seawater in the mid-Neoproterozoic.

Variations in Urine Calcium Isotope: Composition Reflect Changes in Bone Mineral Balance in Humans

NASA Technical Reports Server (NTRS)

Skulan, Joseph; Anbar, Ariel; Bullen, Thomas; Puzas, J. Edward; Shackelford, Linda; Smith, Scott M.

2004-01-01

Changes in bone mineral balance cause rapid and systematic changes in the calcium isotope composition of human urine. Urine from subjects in a 17 week bed rest study was analyzed for calcium isotopic composition. Comparison of isotopic data with measurements of bone mineral density and metabolic markers of bone metabolism indicates the calcium isotope composition of urine reflects changes in bone mineral balance. Urine calcium isotope composition probably is affected by both bone metabolism and renal processes. Calcium isotope. analysis of urine and other tissues may provide information on bone mineral balance that is in important respects better than that available from other techniques, and illustrates the usefulness of applying geochemical techniques to biomedical problems.

A great volcanic eruption around AD 1300 recorded in lacustrine sediment from Dongdao Island, South China Sea

NASA Astrophysics Data System (ADS)

Yang, Zhongkang; Long, Nanye; Wang, Yuhong; Zhou, Xin; Liu, Yi; Sun, Liguang

2017-02-01

The contents of Ti, Al and Fe 2 O 3 in a lacustrine sediment core (DY6) collected from Dongdao Island, South China Sea (SCS), were determined to be much higher than those in the three major sediment end-members (coral sand, guano and plants), and their likely sources include terrigenous dust and volcanic ash. At 61 cm (˜AD 1300), the contents of Ti, Al and Fe 2 O 3 have an abnormally high spike, which cannot be explained by terrigenous dust. The Sr and Nd isotope compositions at 61 cm are in excellent agreement with those in volcanic materials, but they are significantly different from those in terrigenous dust, implying a possible material input from historical volcanic eruptions in the lacustrine sediment DY6. The documented great Samalas volcanic eruption at AD 1257 in Indonesia is likely the candidate for this volcanic eruption.

Evaluation on the Effect of Composition on Radiation Hardening and Embrittlement in Model FeCrAl Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Field, Kevin G.; Briggs, Samuel A.; Edmondson, Philip

2015-09-18

This report details the findings of post-radiation mechanical testing and microstructural characterization performed on a series of model and commercial FeCrAl alloys to assist with the development of a cladding technology with enhanced accident tolerance. The samples investigated include model alloys with simple ferritic grain structure and two commercial alloys with minor solute additions. These samples were irradiated in the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory (ORNL) up to nominal doses of 7.0 dpa near or at Light Water Reactor (LWR) relevant temperatures (300-400 C). Characterization included a suite of techniques including small angle neutron scatteringmore » (SANS), atom probe tomography (APT), and transmission based electron microscopy techniques. Mechanical testing included tensile tests at room temperature on sub-sized tensile specimens. The goal of this work was to conduct detailed characterization and mechanical testing to begin establishing empirical and/or theoretical structure-property relationships for radiation-induced hardening and embrittlement in the FeCrAl alloy class. Development of such relationships will provide insight on the performance of FeCrAl alloys in an irradiation environment and will enable further development of the alloy class for applications within a LWR environment. A particular focus was made on establishing trends, including composition and radiation dose. The report highlights in detail the pertinent findings based on this work. This report shows that radiation hardening in the alloys is primarily composition dependent due to the phase separation in the high-Cr FeCrAl alloys. Other radiation induced/enhanced microstructural features were less dependent on composition and when observed at low number densities, were not a significant contributor to the observed mechanical responses. Pre-existing microstructure in the alloys was found to be important, with grain boundaries and pre-existing dislocation networks acting as defect sinks, resulting in variations in the observed microstructures after irradiation. Dose trends were also observed, with increasing radiation dose promoting changes in the size and number density of the Cr-rich α' precipitates. Based on the microstructural analysis, performed tensile testing, and prior knowledge from FeCr literature it was hypothesized that the formation of the Cr-rich α' precipitates could lead to significant radiation-induced embrittlement in the alloys, and this could be composition dependent, a result which would mirror the trends observed for radiation-induced hardening. Due to the limited database on embrittlement in the FeCrAl alloy class after irradiation, a series of radiation experiments have been implemented. The overarching point of view within this report is the radiation tolerance of FeCrAl is complex, with many mechanisms and factors to be considered at once. Further development of the FeCrAl alloy class for enhanced accident tolerant applications requires detailed, single (or at least limited) variable experiments to fully comprehend and predict the performance of this alloy in LWRs. This report has been submitted as fulfillment of milestone M2FT-15OR0202321 titled, Summary report on the effect of composition on the irradiation embrittlement of Gen 1 ATF FeCrAl for the Department of Energy Office of Nuclear Energy, Advanced Fuel Campaign of the Fuel Cycle R&D program.« less

Gusev-Meridiani-Type Soil Component Dissolved in Some Shock Glasses in Shergottites

NASA Technical Reports Server (NTRS)

Ross, D. K.; Rao, M. N.; Nyquist, L. E.; Shi, C. Y.; Sutton, S.; Harrison, D. H.

2015-01-01

Modal analysis, based on APXS, MiniTES and Mossbauer results obtained at Gusev and Meridiani sites on Mars, indicates that Martian soils consist predominantly of igneous minerals such as olivine, pyroxene and feldspar (approximately70 - 80%), with the balance consisting of alteration minerals such as sulfates, silica and chlorides]. These studies also showed that soil alteration did not occur in-situ and igneous and alteration components are derived from different sources. Below, we analyse the chemical abundance data obtained from shock glasses in shergottites using mass balance mixing models. In these models, the two main end members used are (a) host rock chemical composition and (b) the GM soils average composition as the second component. Here, we consider the S-bearing phases as indicators of added alteration phases in the shock glasses and GM soils. Although the S-bearing phase in shock glasses occurs as micron sized sulfide blebs, we showed in earlier abstracts that sulfur was originally present as sulfate in impact glass-precursor materials and was subsequently reduced to sulfide during shock melting. This conclusion is based on results obtained from S-K XANES studies, Fe/S atomic ratios in sulfide blebs and 34S/32S isotopic measurements in these sulfide blebs. Additionally, sulfur in several EET79001 Lith. A glasses is found to correlate positively with Al2O3 and CaO (and negatively with FeO and MgO), suggesting the presence of Al- and Ca- sul-fate-bearing phases. The distribution of the 87Sr/86Sr iso-topic ratios determined in Lith. A glasses (,27 &,188 and,54) indicate that Martian soil gypsum and host rock material were mixed with each other in the glass precursors. In some vugs in Lith A glass,27 detected gypsum laths. Furthermore, the Martian regolith-de-rived component (where sulfur typically occurs as sul-fate) is identified in these glasses by determining neutron produced isotopic excesses/deficits in 80Kr and 149Sm isotopes. Moreover, the suggestion that the large amount of sulfur found in,507 was sourced from pyrrhotite in the host rock, would require that excessive quantities of host rock would need to be stripped of sulfur to make this sulfide-rich glass. These results provide ample evidence that S occurred as sulfate and was added to glass precursor materials prior to impact shock.

Effect of Monsoon on spatio-temporal variation of groundwater chemistry and stable isotopic signatures: insights for concomitant arsenic mobilization in West Bengal, India

NASA Astrophysics Data System (ADS)

Majumder, S.; Datta, S.; Nath, B.; Neidhardt, H.; Roman-Ross, G.; Berner, Z.; Hidalgo, M.; Chatterjee, D.; Sarkar, S.

2017-12-01

Large-scale groundwater abstraction was hypothesized to be one of the important factors controlling release and distribution of arsenic (As) in aquifers of Bengal Basin. In this study, we studied the groundwater/surface water geochemistry of two different geomorphic domains within the Chakdaha Block, West Bengal, to identify potential influences of groundwater withdrawal on the hydrochemical evolution of the aquifer. This has been done as a function of different water inputs (monsoon rain, irrigation and downward percolation from surface water impoundments) to the groundwater system and associated As mobilization. A low-land flood plain (with relatively more reducing aquifer) and a natural levee (less reducing aquifer) have been chosen for this purpose. The stable isotopic signatures of oxygen (δ18O) and hydrogen (δ2H) falls sub-parallel to the Global Meteoric Water Line (GMWL), with precipitation and subsequent evaporation seems to be the major controlling factor on the water isotopic composition. This shows a contribution of evaporation influenced water, derived from various surface water bodies, pointing at large-scale groundwater withdrawal helping drawdown of the evaporated surface water. In case of flood plain wells, the stable isotope composition and the Cl/Br molar ratio in local groundwater have revealed vertical recharge within the flood plain area to be the major recharge process, especially during the post-monsoon season. However, both evaporation and vertical mixing are visibly controlling the groundwater recharge in the natural levee area. A possible inflow of organic carbon to the aquifer during the monsoonal recharge process is noticeable, with an increase in dissolved organic carbon (DOC) concentration from 1.33 to 6.29 mg/L on passing from pre- to post-monsoon season. Concomitant increase in AsT, Fe(II) and HCO3- during the post monsoon season, being more pronounced in the flood plain samples, indicates a possible initial episode of reductive dissolution of As-rich Fe-oxihydroxides. The subsequent increase in As(III) (> 200%) proportions relative to the overall concentration of AsT (7%), may refer to anaerobic microbial degradation of DOC coupled with the reduction of As(V) to As(III) without triggering additional As release from the aquifer sediments.

Using lead isotopes and trace element records from two contrasting Lake Tanganyika sediment cores to assess watershed – Lake exchange

USGS Publications Warehouse

Odigie, Kingsley; Cohen, A.D.; Swarzenski, Peter W.; Flegal, R

2014-01-01

Lead isotopic and trace element records of two contrasting sediment cores were examined to reconstruct historic, industrial contaminant inputs to Lake Tanganyika, Africa. Observed fluxes of Co, Cu, Mn, Ni, Pb, and Zn in age-dated sediments collected from the lake varied both spatially and temporally over the past two to four centuries. The fluxes of trace elements were lower (up to 10-fold) at a mid-lake site (MC1) than at a nearshore site (LT-98-58), which is directly downstream from the Kahama and Nyasanga River watersheds and adjacent to the relatively pristine Gombe Stream National Park. Trace element fluxes at that nearshore site did not measurably change over the last two centuries (1815–1998), while the distal, mid-lake site exhibited substantial changes in the fluxes of trace elements – likely caused by changes in land use – over that period. For example, the flux of Pb increased by ∼300% from 1871 to 1991. That apparent accelerated weathering and detrital mobilization of lithogenic trace elements was further evidenced by (i) positive correlations (r = 0.77–0.99, p < 0.05) between the fluxes of Co, Cu, Mn, Ni, Pb, and Zn and those of iron (Fe) at both sites, (ii) positive correlations (r = 0.82–0.98, p < 0.01, n = 9) between the fluxes of elements (Al, Co, Cu, Fe, Mn, Ni, Pb, and Zn) and the mass accumulation rates at the offshore site, (iii) the low enrichment factors (EF < 5) of those trace elements, and (iv) the temporal consistencies of the isotopic composition of Pb in the sediment. These measurements indicate that accelerated weathering, rather than industrialization, accounts for most of the increases in trace element fluxes to Lake Tanganyika in spite of the development of mining and smelting operations within the lake’s watershed over the past century. The data also indicate that the mid-lake site is a much more sensitive and useful recorder of environmental changes than the nearshore site. Furthermore, the lead isotopic compositions of sediment at the sites differed spatially, indicating that the Pb (and other trace elements by association) originated from different natural sources at the two locations.

Oxygen isotope fractionation between chlorite and water from 170 to 350 C: A preliminary assessment based on partial exchange and fluid/rock experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cole, D.R.; Ripley, E.M.

1999-02-01

Oxygen isotope fractionations in laboratory systems have been determined between chlorite and water at 170--350 C. In one series of experiments, the Northrop-Clayton partial exchange method was used where three (sometimes four) isotopically different waters were reacted with chlorite. The percents of exchange determined for the four times from shortest to longest are 4.4, 6.5, 8.0, and 11.9. The fractionations calculated from the Northrop and Clayton method are in modest agreement for the four run durations: 0.13, 0.26, {minus}0.46, and {minus}0.55 per mil. Errors associated with each of these fractionations are quite large (e.g. {+-}1.2 per mil for the longestmore » run). The value determined for the longest run of {approximately}20 weeks is the most reliable of the group and compares very closely with a value of {approximately}{minus}0.7 per mil estimated by Wenner and Taylor based on natural chlorides. Good agreement is also observed with the estimates, {minus}1.2 and {minus}1.3% calculated at 350 C for chlorite compositions with [({Sigma}Fe)/{Sigma}Fe + Mg] = 0.313 and 0.444, respectively, from equations given by Savin and Lee based on their empirical bond-type method. Additional fractionation data have been estimated from hydrothermal granite-fluid experiments where chlorite formed from biotite. Detailed thin section, scanning electron microscope (SEM), x-ray diffraction (XRD), and electron microprobe analyses demonstrate that biotite is altered exclusively to chlorite in 13 granite-fluid experiments conducted at the following conditions: T = 170--300 C, P = vapor saturation - 200 b, salinity = H{sub 2}O, 0.1 and 1 m NaCl, fluid/biotite mass ratios = 3--44, run durations = 122--772 h. The amount of chlorite, quantified through point counting and XRD, increased with increasing temperature, salinity, and time. The isotope compositions of chlorite were calculated from mass balance and compared to the final measured {delta}{sup 18}O of the fluids. The 10{sup 3}ln {alpha} values averaged 0.14, 0.8 and 2.9 per mil for 300, 250, and 200 C, respectively. A least-squares regression model of the combined data set (all T`s) is presented.« less

Iron chemistry of Hawaiian rainforest soil solution: Biogeochemical implications of multiple Fe redox cycles

NASA Astrophysics Data System (ADS)

Thompson, A.; Chorover, J.; Chadwick, O.

2003-12-01

Iron (Fe)-oxides are important sorbents for nutrients, pollutants and natural organic matter (NOM). When flucutations in soil oxygen status exist, Fe can cycle through reduced and oxidized forms and thus greatly affect the aqueous conc. of nutrients and metals. We are examining the influence of oscillating oxic/anoxic conditions on Fe-oxide formation and biogeochemical processes (microbial community composition, and carbon, nutrient and trace metal availability). Our work makes use of a natural rainfall gradient ranging from 2.2 to 4.2 m mean annual precipitation (MAP) on the island of Maui, Hawaii, USA. All sites developed on a 400ky basaltic lava flow and comprise soils under similar vegetation. Solid phase Fe concentration and oxidation state vary systematically across this rainfall gradient with a sharp decrease in pedogenic Fe between 2.8 m and 3.5 m MAP that corresponds with an Eh of 330 mV (1-yr ave.). Fe isotopic composition and Fe-oxide associated rare earth elements (REE) also suggest a shift from ligand-promoted to redutive Fe dissolution with increasing rainfall. To examine the effects of multiple Fe oxidation/reduction cycles, we constructed a set of redox-stat reactors that maintain Eh values within a set range by small Eh-triggered additions of oxygen. Triplicate soil slurry reactors are subjected to redox (Eh) oscillations such that Fe is repeatedly cycled from oxidized to reduced forms. During our current experiment, we measure pH and Eh dynamics and monitor the distribution of Fe(II) and Fe(III), major ion and anion concentrations, a range of trace metals including the REE, and total organic carbon (TOC) in three Stokes-effective particle size fractions (<0.45 mm, <0.1 mm, and <0.02 mm) by cascade centrifugation and a <3000 MW fraction isolated via ultra-filtration. Each sample is then sequentially extracted in dilute (0.5 M) HCl and acid-ammonium oxalate. Concurrently, CO2 release is measured and DNA fingerprinting is used to track changes in the microbial community. Prior to implementing the rigorous sampling procedure above, we completed two preliminary reactor experiments focusing only on Fe distribution between aqueous, HCl, and oxalate extractions. These experiments illustrated (1) a distinct threshold for Fe oxidation at ~ 350 mV in the soils (pH 5) and (2) multiple redox cycles increased the HCl-extractable Fe(III) fraction relative to initial conditions. Unexpectedly, this increase occurred predominantly during reducing cycles-perhaps indicating a weakening of Fe-oxide structures during initiation of reducing conditions or oxidation of Fe(II) by NO3. By integrating Fe analysis with trace metal and microbial characterization in triplicate reactors, we will verify this increase in HCl-extractable Fe(III), and assess the impacts of Fe redox oscillation on biogeochemical processes.

Stratigraphic implications of trace element and strontium-isotope analyses of Kimmeridgian shell calcite from the Lower Saxony Basin, Germany

NASA Astrophysics Data System (ADS)

Zuo, Fanfan; Heimhofer, Ulrich; Huck, Stefan; Erbacher, Jochen; Bodin, Stephane

2017-04-01

Stratigraphic uncertainties due to the lack of open marine marker fossils (e.g. ammonites) hamper the precise age assignment and stratigraphic correlation of Kimmeridgian strata found in the Lower Saxony Basin of Northern Germany. Correlation of these deposits with the Jurassic standard ammonite zonation is still difficult, since the existing ostracod biostratigraphy is facies-controlled and of only limited stratigraphic precision. In this study, a chemostratigraphic approach has been chosen and biogenic shell material produced by brachiopods, oysters and lithiotids is evaluated for its reliability to act as proxy of the original Jurassic seawater strontium isotope composition. Low-Mg calcite shells have been collected from three stratigraphic sections accessible in open-cast quarries located in the Lower Saxony Basin of Northern Germany. In order to identify diagenetically altered shell calcite, trace element and stable isotope analysis of 227 calcite samples (oysters=101; brachiopods=60; Trichites=52) has been carried out. The geochemical results reveal that (1) concentration of different trace elements varies between the different groups of shell-forming organisms, which may be related to vital effects and (2) high strontium contents, low Mn and Fe contents and the lack of correlation between these elements indicate near-pristine calcite shells, and therefore shells are supposed to record the ambient sea water composition during the Late Jurassic. Strontium-isotope (87Sr/86Sr) analysis of diagenetically screened samples indicates an Early Kimmeridgian age of the studied deposits, which is in accordance with ostracod biostratigraphic data. An increasing trend in 87Sr/86Sr with stratigraphic height fits well with the global strontium-isotope curve. Besides, similar 87Sr/86Sr ratios derived from different organisms from a single stratigraphic level highlight the suitability of the shells for strontium-isotope stratigraphy. Despite the shallow-marine character of the studied deposits, no evidence for significant riverine influence on the strontium-isotope signature is observed. The new chemostratigraphic data will provide a more precise age assignment for Kimmeridgian strata in the Lower Saxony Basin and thus enable the establishment of a solid integrated stratigraphic scheme that can be used for correlation on both regional and global scale.

Asian dust input in the western Philippine Sea: Evidence from radiogenic Sr and Nd isotopes

NASA Astrophysics Data System (ADS)

Jiang, Fuqing; Frank, Martin; Li, Tiegang; Chen, Tian-Yu; Xu, Zhaokai; Li, Anchun

2013-05-01

The radiogenic strontium (Sr) and neodymium (Nd) isotope compositions of the detrital fraction of surface and subsurface sediments have been determined to trace sediment provenance and contributions from Asian dust off the east coast of Luzon Islands in the western Philippine Sea. The Sr and Nd isotope compositions have been very homogenous near the east coast of the Luzon Islands during the latest Quaternary yielding relatively least radiogenic Sr (87Sr/86Sr = 0.70453 to 0.70491) and more radiogenic Nd isotope compositions (ɛNd(0) = +5.3 to +5.5). These isotope compositions are similar to Luzon rocks and show that these sediments were mainly derived from the Luzon Islands. In contrast, the Sr and Nd isotope compositions of sediments on the Benham Rise and in the Philippine Basin are markedly different in that they are characterized by overall more variable and more radiogenic Sr isotope compositions (87Sr/86Sr = 0.70452 to 0.70723) and less radiogenic Nd isotope compositions (ɛNd(0) = -5.3 to +2.4). The Sr isotope composition in the Huatung Basin is intermediate between those of the east coast of Luzon and Benham Rise, but shows the least radiogenic Nd isotope compositions. The data are consistent with a two end-member mixing relationship between Luzon volcanic rocks and eolian dust from the Asian continent, which is characterized by highly radiogenic Sr and unradiogenic Nd isotope compositions. The results show that Asian continental dust contributes about 10-50% of the detrital fraction of the sediments on Benham Rise in the western Philippine Sea, which offers the potentials to reconstruct the climatic evolution of eastern Asia from these sediments and compare this information to the records from the central and northern Pacific.

Formation of Apollo 16 impactites and the composition of late accreted material: Constraints from Os isotopes, highly siderophile elements and sulfur abundances

NASA Astrophysics Data System (ADS)

Gleißner, Philipp; Becker, Harry

2017-03-01

Fe-Ni metal-schreibersite-troilite intergrowths in Apollo 16 impact melt rocks and new highly siderophile element (HSE) and S abundance data indicate that millimeter-scale closed-system fractional crystallization processes during cooling of impactor-derived metal melt droplets in impact-melts are the main reason for compositional variations and strong differences in abundances and ratios of HSE in multiple aliquots from Apollo 16 impact melt rocks. Element ratios obtained from linear regression of such data are therefore prone to error, but weighted averages take into account full element budgets in the samples and thus represent a more accurate estimate of their impactor contributions. Modeling of solid metal-liquid metal partitioning in the Fe-Ni-S-P system and HSE patterns in impactites from different landing sites suggest that bulk compositions of ancient lunar impactites should be representative of impact melt compositions and that large-scale fractionation of the HSE by in situ segregation of solid metal or sulfide liquid in impact melt sheets most likely did not occur. The compositional record of lunar impactites indicates accretion of variable amounts of chondritic and non-chondritic impactor material and the mixing of these components during remelting of earlier ejecta deposits. The non-chondritic composition appears most prominently in some Apollo 16 impactites and is characterized by suprachondritic HSE/Ir ratios which increase from refractory to moderately volatile HSE and exhibit a characteristic enrichment of Ru relative to Pt. Large-scale fractional crystallization of solid metal from sulfur and phosphorous rich metallic melt with high P/S in planetesimal or embryo cores is currently the most likely process that may have produced these compositions. Similar materials or processes may have contributed to the HSE signature of the bulk silicate Earth (BSE).

Isotopic studies of epigenetic features in metalliferous sediment, Atlantis II Deep, Red Sea

USGS Publications Warehouse

Zierenberg, Robert A.; Shanks, Wayne C.

1988-01-01

The unique depositional environment of the Atlantis II Deep brine pool in the Red Sea produces a stratiform metalliferous deposit of greater areal extent than deposits formed by buoyant-plume systems typical of the midocean ridges because of much more efficient metal entrapment. Isotopic analyses of strontium, sulfur, carbon, and oxygen from the metalliferous sediments indicate that three major sources contribute dissolved components to the hydrothermal system: seawater, Miocene evaporites, and rift-zone basalt. An areally restricted magnetite-hematite-pyroxene assemblage formed at high temperatures, possibly in response to hydrothermal convection initiated by intrusion of basalt into the metalliferous sediment. A correlation between smectite Fe/(Fe+Mg) ratios and oxygen isotope temperatures suggests that smectite is a potentially important chemical geothermometer, and confirms geochemical calculations indicating that Mg-rich smectite is more stable than Fe-rich smectite at elevated temperatures.

Sulfur Isotope Composition of Putative Primary Troilite in Chondrules

NASA Technical Reports Server (NTRS)

Tachibana, Shogo; Huss, Gary R.

2002-01-01

Sulfur isotope compositions of putative primary troilites in chondrules from Bishunpur were measured by ion probe. These primary troilites have the same S isotope compositions as matrix troilites and thus appear to be isotopically unfractionated. Additional information is contained in the original extended abstract.

Integrated Extraction Chromatographic Separation of the Lithophile Elements Involved in Long-Lived Radiogenic Isotope Systems (Rb-Sr, U-Th-Pb, Sm-Nd, La-Ce, and Lu-Hf) Useful in Geochemical and Environmental Sciences.

PubMed

Pin, Christian; Gannoun, Abdelmouhcine

2017-02-21

A fast and efficient sample preparation method in view of isotope ratio measurements is described, allowing the separation of 11 elements involved, either as "parent" or as "daughter" isotopes, in six radiogenic isotope systems used as chronometers and tracers in earth, planetary, and environmental sciences. The protocol is based on small extraction chromatographic columns, used either alone or in tandem, through which a single nitric acid solution is passed, without any intervening evaporation step. The columns use commercially available extraction resins (Sr resin, TRU resin, Ln resin, RE resin, and again Ln resin for isolating Sr and Pb, LREE then La-Ce-Nd-Sm, Lu(Yb), and Hf, Th, and U, respectively) along with an additional, in-house prepared resin for separating Rb. A simplified scheme is proposed for samples requiring the separation of Sr, Pb, Nd, and Hf only. Adverse effects of troublesome major elements (Fe 3+ , Ti) are circumvented by masking with ascorbic acid and hydrofluoric acid, respectively. Typical recoveries in the 85-95% range are achieved, with procedural blanks of 10-100 pg, negligible with regard to the amounts of analytes processed. The fractions separated are suitable for high precision isotope ratio measurements by TIMS or MC-ICP-MS, as demonstrated by the repeat analyses of several international reference materials of basaltic composition for 87 Sr/ 86 Sr, 208,207,206 Pb/ 204 Pb, 143 Nd/ 144 Nd, 176 Hf/ 177 Hf, and 230 Th/ 232 Th. Concentration data could be obtained by spiking and equilibrating the sample with appropriate isotopic tracers before the onset of the separation process and, finally, measuring the isotope ratios modified by the isotope dilution process.

Nucleosynthesis in Supernovae

NASA Astrophysics Data System (ADS)

Thielemann, Friedrich-Karl; Isern, Jordi; Perego, Albino; von Ballmoos, Peter

2018-04-01

We present the status and open problems of nucleosynthesis in supernova explosions of both types, responsible for the production of the intermediate mass, Fe-group and heavier elements (with the exception of the main s-process). Constraints from observations can be provided through individual supernovae (SNe) or their remnants (e.g. via spectra and gamma-rays of decaying unstable isotopes) and through surface abundances of stars which witness the composition of the interstellar gas at their formation. With a changing fraction of elements heavier than He in these stars (known as metallicity) the evolution of the nucleosynthesis in galaxies over time can be determined. A complementary way, related to gamma-rays from radioactive decays, is the observation of positrons released in β+-decays, as e.g. from ^{26}Al, ^{44}Ti, ^{56,57}Ni and possibly further isotopes of their decay chains (in competition with the production of e+e- pairs in acceleration shocks from SN remnants, pulsars, magnetars or even of particle physics origin). We discuss (a) the role of the core-collapse supernova explosion mechanism for the composition of intermediate mass, Fe-group (and heavier?) ejecta, (b) the transition from neutron stars to black holes as the final result of the collapse of massive stars, and the relation of the latter to supernovae, faint supernovae, and gamma-ray bursts/hypernovae, (c) Type Ia supernovae and their nucleosynthesis (e.g. addressing the ^{55}Mn puzzle), plus (d) further constraints from galactic evolution, γ-ray and positron observations. This is complemented by the role of rare magneto-rotational supernovae (related to magnetars) in comparison with the nucleosynthesis of compact binary mergers, especially with respect to forming the heaviest r-process elements in galactic evolution.

Atomic Weights and Isotopic Compositions

National Institute of Standards and Technology Data Gateway

SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

Magnesium isotopic composition of the Earth and chondrites

NASA Astrophysics Data System (ADS)

Teng, Fang-Zhen; Li, Wang-Ye; Ke, Shan; Marty, Bernard; Dauphas, Nicolas; Huang, Shichun; Wu, Fu-Yuan; Pourmand, Ali

2010-07-01

To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ 25Mg and ±0.07‰ on δ 26Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL). Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ 25Mg = -0.13 ± 0.05 (2SD) and δ 26Mg = -0.26 ± 0.07 (2SD) for global oceanic basalts ( n = 110) and δ 25Mg = -0.13 ± 0.03 (2SD) and δ 26Mg = -0.25 ± 0.04 (2SD) for global peridotite xenoliths ( n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ 25Mg = -0.15 ± 0.04 (2SD) and δ 26Mg = -0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes. Collectively, the Mg isotopic composition of the Earth's mantle, based on oceanic basalts and peridotites, is estimated to be -0.13 ± 0.04 for δ 25Mg and -0.25 ± 0.07 for δ 26Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites. The chondritic composition of the Earth implies that Mg isotopes were well mixed during accretion of the inner solar system.

Nickel and chromium isotopes in Allende inclusions

NASA Technical Reports Server (NTRS)

Birck, J. L.; Lugmair, G. W.

1988-01-01

High-precision nickel and chromium isotopic measurements were carried out on nine Allende inclusions. It is found that Ni-62, Ni-64, excesses are present in at least three of the samples. The results suggest that the most likely mechanism for the anomalies is a neutron-rich statistical equilibrium process. An indication of elevated Ni-60 is found in almost every inclusion measured. This effect is thought to be related to the decay of now extinct Fe-60. An upper limit of 1.6 X 10 to the -6th is calculated for the Fe-60/Fe-56 ratio at the time these Allende inclusions crystallized.

Coupled Fe and multiple-S isotope systematics of pyrite and evidence of increasing atmospheric oxygen in 2.5 Ga sediments of the Kaapvaal Craton

NASA Astrophysics Data System (ADS)

Bauer, A.; Ono, S.; Romaniello, S. J.; Anbar, A. D.

2017-12-01

Using combined iron and sulfur isotopic data from black shale-hosted pyrite grains of 2.5 Ga samples from the GKP-01 drill core of the Griqualand West Basin, South Africa, we untangle the pathways of pyrite formation for distinct morphologies of pyrite and evaluate the role of these pyrites as recorders of atmospheric S-MIF signals. The analysis of subsamples at stratigraphic intervals allows us to document the characteristic time scale of change in S-MIF signatures resulting from atmospheric photochemical reactions with respect to residence time of the seawater sulfate reservoir. Disseminated pyrite grains are characterized by a range of Δ33S (-1 to +8‰) and 56Fe (-2.5 to 0‰) values. Pyrite laminae are predominantly characterized by relatively homogeneous and negative Δ33S (-2 to 0 ‰) and 56Fe (-2 to -1‰) isotope signatures. These correlated Fe-S systematics suggest distinct pathways of pyrite formation: 1) pyrite laminae formed below the sediment-water interface via diffusion of dissolved oceanic Fe2+ and sulfate; and 2) disseminated pyrite formed at the chemocline by reaction of reduced and elemental sulfur with a reservoir of Fe2+ affected by removal of Fe oxides. Recognition of distinct mechanisms of pyrite formation for these morphologies is a critical step in deconstructing the pathways for S-MIF production, transfer, and preservation in the Archean sedimentary record. Our results have implications for mass balance and atmospheric modeling studies that rely on the Δ33S record as well as for studies attempting to document larger-scale, lithofacies-specific trends in sulfur isotopic signals. Finally, our results are consistent with locally increasing sulfate concentrations along this Archean continental shelf and may correspond to an increase in low-level O2 production prior to the Great Oxygenation Event.

s-process nucleosynthesis in massive stars: new results on {sup 60}Fe, {sup 62}Ni and {sup 64}Ni

DOE Office of Scientific and Technical Information (OSTI.GOV)

Domingo-Pardo, C.; Forschungszentrum Karlsruhe, Institut fuer Kernphysik, 76021 Karlsruhe; Dillmann, I.

2009-01-28

The s process synthesizes the elements between Fe and Sr in massive stars during two major evolutionary stages, convective core He burning and C shell burning. This scenario implies fascinating consequences for the chemical evolution of the star. For instance, the neutron capture rate at each isotope can have a big influence on the production of many of the subsequent higher mass isotopes. Correspondingly, one needs to know the (n,{gamma}) cross sections of the involved isotopes with high accuracy in order to determine the abundance pattern reliably and to obtain a consistent picture of this stage. This contribution gives anmore » overview on recent and future experiments for the Fe/Ni nucleosynthesis in massive stars. New results on {sup 60}Fe, {sup 62}Ni and {sup 64}Ni are reported. {sup 60}Fe is mostly produced during the short convective C shell burning phase, where peak densities of {approx}10{sup 11} cm{sup -3} are reached, prior to the SN explosion. The stellar (n,{gamma}) cross section of {sup 60}Fe could be measured with a 1 {mu}g sample obtained at PSI (Switzerland), which was sufficient for an activation measurement using the intense, quasi-stellar neutron field for a thermal energy of 25 keV at the Karlsruhe Van de Graaff accelerator. The FZK accelerator was also used for an activation of {sup 62}Ni, whereas in this case, the number of {sup 63}Ni nuclei produced were determined via accelerator mass spectroscopy at the Maier-Leibnitz-Laboratorium in Garching/Munich. The (n,{gamma}) cross section of {sup 64}Ni at a stellar temperature equivalent to 50 keV has been measured in a collaboration between FZK Karlsruhe and PTB Braunschweig. Finally, complementary time of flight measurements on the Fe and Ni isotopes over a broad energy range are planned at the white neutron source n lowbar TOF of CERN for the future campaign in 2009.« less

Kinetics of Fe Release from Organic Ligand Complexes: Implications for Fe Isotopes?

NASA Astrophysics Data System (ADS)

Nuester, J.; Liermann, L. J.; Brantley, S. L.

2006-12-01

Although iron is the fourth most abundant element in the earth's surface, its bioavailability is limited by its natural tendency to form insoluble iron (oxyhydr)oxides in terrestrial and marine environments. Paradoxically, iron is an essential nutrient for virtually all living cells, so in order to survive, organisms must develop mechanisms to solubilize iron. To acquire iron, organisms synthesize and release iron-specific chelators called siderophores. These siderophores facilitate the transformation of insoluble crystal-bound iron to organically ligand-bound dissolved iron. The reverse process whereby ferric iron is released from siderophores resulting in the precipitation of iron (oxyhydr)oxides or complexation by other iron chelators is an important but not well studied process in the B-horizon of soils. Fe mobility is documented in soils where Fe is often extracted at the top and precipitated at depth. Both the concentration and isotopic signature of Fe varies with depth due to dissolution, precipitation, sorption, and biological processes. Our study is focused on measurement of isotopic fractionation during this reverse process. In a first approach to understand iron liberation form organic ligands, we mimic this process using a reductive mechanism. We use acetohydroxamic acid (aha), EDTA and desferrioxamine B (DFMB) as test ligands to investigate iron release by sodium ascorbate at varying pH. Our first kinetic measurements showed significant differences in iron release depending on pH and stability of the iron complex. Within one hour all iron is released from aha with a small pH effect in the pH range between 4 and 6. In contrast, the pH has a major influence on the iron release from EDTA and DFMB. Depending on pH, total iron is released from EDTA within 24 hours, while only an incomplete iron release from DFMB could be observed within two weeks. These strong kinetic differences in iron release as a consequence of iron reduction are expected to result in significant iron isotope effects, and we are testing for these effects. For example, we expect to see enrichment of light isotopes in the early released fractions as iron is reduced (like effects observed by Wiederhold et al. (2006) for ligand-controlled and reductive dissolution of goethite). Such kinetic isotope effects should be particularly strong for iron release from siderophores with high Fe affinities like DFMB (log ß_(Fe(III)) = 30.60). We are also investigating other mechanisms to liberate iron from organic ligands including a pathway with extracellular iron reductases.

Geochemistry and origin of regional dolomites. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanson, G.N.; Meyers, W.J.

1995-05-01

The main goal of our research on dolomites has been to better understand the composition of the fluids and processes of the fluid-rock interaction responsible for the formation of massive dolostones occurring over regional scales within sedimentary sequences. Understanding the timing of dolomitization, the fluids responsible for the dolomitization and the timing of the development of porosity has major economic ramifications in that dolomites are major oil reservoirs often having better reservoir properties than associated limestones. Our approach has been to apply trace element, major element, petrographic, crystallographic, stable isotope and radiogenic isotope systems to test models for the originsmore » of dolomites and to give information that may allow us to develop new models. Fluid compositions and processes are evaluated through the use of numerical models which we have developed showing the simultaneous evolution of the trace element and isotope systems during dolomitization. Our research has included the application of B, O, C, Sr, Nd and Pb isotope systematics and the trace elements Mn, Fe St, rare earth elements, Rb, Ba, U, Th, Pb, Zn, Na, Cl, F and SO{sub 4}{sup 2-}. Analyses are possible on individual cements or dolomite types using micro-sampling or microprobe techniques. The microprobe techniques used include synchrotron X-ray microprobe analysis at Brookhaven National Laboratory or electron microprobe at Stony Brook. Lack of a modern analogue for ancient massive dolostones has limited the application of the uniformitarian concept to developing models for the ancient regional dolostones. In addition it has not been possible to synthesize dolomite in the laboratory under conditions similar to the sedimentary or diagenetic possible environments in which the dolomites must have formed.« less

Accretion and differentiation of carbon in the early Earth.

PubMed

Tingle, T N

1998-05-15

The abundance of C in carbonaceous and ordinary chondrites decreases exponentially with increasing shock pressure as inferred from the petrologic shock classification of Scott et al. [Scott, E.R.D., Keil, K., Stoffler, D., 1992. Shock metamorphism of carbonaceous chondrites. Geochim. Cosmochim. Acta 56, 4281-4293] and Stoffler et al. [Stoffler, D., Keil, K., Scott, E.R.D., 1991. Shock metamorphism of ordinary chondrites. Geochim. Cosmochim. Acta 55, 3845-3867]. This confirms the experimental results of Tyburczy et al. [Tyburczy, J.A., Frisch, B., Ahrens, T.J., 1986. Shock-induced volatile loss from a carbonaceous chondrite: implications for planetary accretion. Earth Planet. Sci. Lett. 80, 201-207] on shock-induced devolatization of the Murchison meteorite showing that carbonaceous chondrites appear to be completely devolatilized at impact velocities greater than 2 km s-1. Both of these results suggest that C incorporation would have been most efficient in the early stages of accretion, and that the primordial C content of the Earth was between 10(24) and 10(25) g C (1-10% efficiency of incorporation). This estimate agrees well with the value of 3-7 x 10(24) g C based on the atmospheric abundance of 36Ar and the chondritic C/36Ar (Marty and Jambon, 1987). Several observations suggest that C likely was incorporated into the Earth's core during accretion. (1) Graphite and carbides are commonly present in iron meteorites, and those iron meteorites with Widmanstatten patterns reflecting the slowest cooling rates (mostly Group I and IIIb) contain the highest C abundances. The C abundance-cooling rate correlation is consistent with dissolution of C into Fe-Ni liquids that segregated to form the cores of the iron meteorite parent bodies. (2) The carbon isotopic composition of graphite in iron meteorites exhibits a uniform value of -5% [Deines, P., Wickman, F.E. 1973. The isotopic composition of 'graphitic' carbon from iron meteorites and some remarks on the troilitic sulfur of iron meteorites. Geochim. Cosmochim. Acta 37, 1295-1319; Deines, P., Wickman, F.E., 1975. A contribution to the stable carbon isotope geochemistry of iron meteorites. Geochim. Cosmochim. Acta 39, 547-557] identical to the mode in the distribution found in diamonds, carbonatites and oceanic basalts [Mattey, D.P., 1987. Carbon isotopes in the mantle. Terra Cognita 7, 31-37]. (3) The room pressure solubility of C in molten iron is 4.3 wt% C. Phase equilibria confirm that the Fe-C eutectic persists to 12 GPa, and thermochemical calculations for the Fe-C-S system by Wood [Wood, B.J., 1993. Carbon in the core. Earth Planet. Sci. Lett. 117, 593-607] predict that C is soluble in Fe liquids at core pressures. The abundance of 36Ar in chondrites decreases exponentially with increasing shock pressure as observed for C. It is well known that noble gases are positively correlated and physically associated with C in meteorites [e.g. Otting, W., Zahringer J., 1967. Total carbon content and primordial rare gases in chondrites. Geochim. Cosmochim. Acta 31, 1949-1960; Reynolds, J.H., Frick, U., Niel, J.M., Phinney, D.L., 1978. Rare-gas-rich separates from carbonaceous chondrites. Geochim. Cosmochim. Acta, 42, 1775-1797]. This suggests a mechanism by which primordial He and other noble gases may have incorporated into the Earth during accretion. The abundance of He in the primordial Earth required to sustain the modern He flux for 4 Ga (assuming a planetary 3 He/4 He; Reynolds et al. [Reynolds, J.H., Frick, U., Niel, J.M., Phinney, D.L., 1978. Rare-gas-rich separates from carbonaceous chondrites. Geochim. Cosmochim. Acta 42, 1775-1797] is calculated to be > or = 10(-8) cm3 g-1. This minimum estimate is consistent with a 1-10% efficiency of noble gas retention during accretion and the observed abundance of He in carbonaceous chondrites (10(-5) to 10(-4) cm3 g-1 excluding spallogenic contributions).

High-precision isotopic characterization of USGS reference materials by TIMS and MC-ICP-MS

NASA Astrophysics Data System (ADS)

Weis, Dominique; Kieffer, Bruno; Maerschalk, Claude; Barling, Jane; de Jong, Jeroen; Williams, Gwen A.; Hanano, Diane; Pretorius, Wilma; Mattielli, Nadine; Scoates, James S.; Goolaerts, Arnaud; Friedman, Richard M.; Mahoney, J. Brian

2006-08-01

The Pacific Centre for Isotopic and Geochemical Research (PCIGR) at the University of British Columbia has undertaken a systematic analysis of the isotopic (Sr, Nd, and Pb) compositions and concentrations of a broad compositional range of U.S. Geological Survey (USGS) reference materials, including basalt (BCR-1, 2; BHVO-1, 2), andesite (AGV-1, 2), rhyolite (RGM-1, 2), syenite (STM-1, 2), granodiorite (GSP-2), and granite (G-2, 3). USGS rock reference materials are geochemically well characterized, but there is neither a systematic methodology nor a database for radiogenic isotopic compositions, even for the widely used BCR-1. This investigation represents the first comprehensive, systematic analysis of the isotopic composition and concentration of USGS reference materials and provides an important database for the isotopic community. In addition, the range of equipment at the PCIGR, including a Nu Instruments Plasma MC-ICP-MS, a Thermo Finnigan Triton TIMS, and a Thermo Finnigan Element2 HR-ICP-MS, permits an assessment and comparison of the precision and accuracy of isotopic analyses determined by both the TIMS and MC-ICP-MS methods (e.g., Nd isotopic compositions). For each of the reference materials, 5 to 10 complete replicate analyses provide coherent isotopic results, all with external precision below 30 ppm (2 SD) for Sr and Nd isotopic compositions (27 and 24 ppm for TIMS and MC-ICP-MS, respectively). Our results also show that the first- and second-generation USGS reference materials have homogeneous Sr and Nd isotopic compositions. Nd isotopic compositions by MC-ICP-MS and TIMS agree to within 15 ppm for all reference materials. Interlaboratory MC-ICP-MS comparisons show excellent agreement for Pb isotopic compositions; however, the reproducibility is not as good as for Sr and Nd. A careful, sequential leaching experiment of three first- and second-generation reference materials (BCR, BHVO, AGV) indicates that the heterogeneity in Pb isotopic compositions, and concentrations, could be directly related to contamination by the steel (mortar/pestle) used to process the materials. Contamination also accounts for the high concentrations of certain other trace elements (e.g., Li, Mo, Cd, Sn, Sb, W) in various USGS reference materials.

Multistage formation processes in the acapulcoite-lodranite parent body: Mineralogical study of anomalous lodranite, Yamato 983119

NASA Astrophysics Data System (ADS)

Yasutake, Masahiro; Yamaguchi, Akira

2017-12-01

Y 983119 is a coarse-grained rock consisting mainly of orthopyroxene (44-71 vol%, Wo3En94Fs4), olivine (4-30 vol%, Fo97), Fe, Ni metal (4-14 vol%) and interstitial plagioclase (9-14 vol%, Or2Ab67An29) and augite (2-5 vol%, Wo46En53Fs2). The modal abundance of orthopyroxene is higher than known acapulcoites and lodranites. Olivine grains show chemical zoning with higher Fe/Mn values along rims and cracks. Orthopyroxene and olivine contain melt inclusions that mainly consist of augite, feldspar and glass. Hornblende, biotite, rutile and baddeleyite were also found in melt inclusions. Based on the compositions of melt inclusions, the parent melt is felsic, and contains a significant amount of Na, K, Ti, Zr, F and OH. The major mineral and oxygen isotopic compositions indicate that Y 983119 is a lodranite. However, the high abundance of orthopyroxene and the presence of melt inclusions indicate that Y 983119 is not a residue in contrast to other lodranites. We suggest that Y 983119 formed by more complex formation processes than the other lodranites.

Evaluation of Neutron Reactions on Iron Isotopes for CIELO and ENDF/B-VIII.0

DOE PAGES

Herman, M.; Trkov, A.; Capote, R.; ...

2018-02-01

A new suite of evaluations for 54,56,57,58Fe has been developed in the framework of the CIELO international collaboration. New resolved resonance ranges were evaluated for 54Fe and 57Fe, while modifications were applied to resonances in 56Fe. The low energy part of the 56Fe file is almost totally based on measurements. At higher energies in 56Fe and in the whole fast neutron range for minor isotopes the evaluation consists of model predictions carefully adjusted to available experimental data. We also make use of the high quality and well experimentally-constrained dosimetry evaluations from the IRDFF library. Special attention was dedicated to themore » elastic angular distributions, which were found to affect results of the integral benchmarking. The new set of iron evaluations was developed in concert with other CIELO evaluations and they were tested together in the integral experiments before being adopted for the ENDF/B-VIII.0 library.« less

Evaluation of Neutron Reactions on Iron Isotopes for CIELO and ENDF/B-VIII.0

NASA Astrophysics Data System (ADS)

Herman, M.; Trkov, A.; Capote, R.; Nobre, G. P. A.; Brown, D. A.; Arcilla, R.; Danon, Y.; Plompen, A.; Mughabghab, S. F.; Jing, Q.; Zhigang, G.; Tingjin, L.; Hanlin, L.; Xichao, R.; Leal, L.; Carlson, B. V.; Kawano, T.; Sin, M.; Simakov, S. P.; Guber, K.

2018-02-01

A new suite of evaluations for 54,56,57,58Fe has been developed in the framework of the CIELO international collaboration. New resolved resonance ranges were evaluated for 54Fe and 57Fe, while modifications were applied to resonances in 56Fe. The low energy part of the 56Fe file is almost totally based on measurements. At higher energies in 56Fe and in the whole fast neutron range for minor isotopes the evaluation consists of model predictions carefully adjusted to available experimental data. We also make use of the high quality and well experimentally-constrained dosimetry evaluations from the IRDFF library. Special attention was dedicated to the elastic angular distributions, which were found to affect results of the integral benchmarking. The new set of iron evaluations was developed in concert with other CIELO evaluations and they were tested together in the integral experiments before being adopted for the ENDF/B-VIII.0 library.

Evaluation of Neutron Reactions on Iron Isotopes for CIELO and ENDF/B-VIII.0

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herman, M.; Trkov, A.; Capote, R.

A new suite of evaluations for 54,56,57,58Fe has been developed in the framework of the CIELO international collaboration. New resolved resonance ranges were evaluated for 54Fe and 57Fe, while modifications were applied to resonances in 56Fe. The low energy part of the 56Fe file is almost totally based on measurements. At higher energies in 56Fe and in the whole fast neutron range for minor isotopes the evaluation consists of model predictions carefully adjusted to available experimental data. We also make use of the high quality and well experimentally-constrained dosimetry evaluations from the IRDFF library. Special attention was dedicated to themore » elastic angular distributions, which were found to affect results of the integral benchmarking. The new set of iron evaluations was developed in concert with other CIELO evaluations and they were tested together in the integral experiments before being adopted for the ENDF/B-VIII.0 library.« less

Oxygen isotope reservoirs in the outer asteroid belt inferred from oxygen isotope systematics of chondrule olivines and isolated forsterite and olivine grains in Tagish Lake-type carbonaceous chondrites, WIS 91600 and MET 00432

NASA Astrophysics Data System (ADS)

Yamanobe, Masakuni; Nakamura, Tomoki; Nakashima, Daisuke

2018-03-01

To understand oxygen isotope ratios and redox conditions of the chondrule formation environments of the outer rigions of the asteroid belt, we analyzed major element concentrations and oxygen isotope ratios of olivine grains in chondrules, isolated forsterite, and isolated olivine from the WIS 91600 and MET 00432 carbonaceous chondrites, which are thought to have originated from D-type asteroids located in the outer asteroid belt. The oxygen isotope ratios of individual chondrules and isolated grains show a wide variation in δ18O from -9.9‰ to +9.1‰ along the carbonaceous chondrite anhydrous mineral (CCAM) and primitive chondrule mineral (PCM) lines. The Δ17O (= δ17O - 0.52 × δ18O) values of the measured objects increase with decreasing Mg#; i.e., FeO-poor objects (Mg# > 90; type I chondrules and isolated forsterites) mainly have Δ17O values of ca. -6‰, and FeO-rich objects (Mg# < 90; type II chondrules and isolated olivines) have Δ17O values ranging from -3‰ to +2‰. Similar trends are observed for ferromagnesian silicate particles from comet Wild2 and CR chondrite chondrules, particularly in terms of FeO-rich objects with Δ17O values ranging from -3‰ to +2‰. It is suggested that FeO-rich objects formed in the outer regions of the asteroid belt and were transported to the outer solar nebular regions where comet Wild2 formed.

Biogenic Magnetite Formation through Anaerobic Biooxidation of Fe(II)

PubMed Central

Chaudhuri, Swades K.; Lack, Joseph G.; Coates, John D.

2001-01-01

The presence of isotopically light carbonates in association with fine-grained magnetite is considered to be primarily due to the reduction of Fe(III) by Fe(III)-reducing bacteria in the environment. Here, we report on magnetite formation by biooxidation of Fe(II) coupled to denitrification. This metabolism offers an alternative environmental source of biogenic magnetite. PMID:11375205

Weathering fluxes to the Gulf of Mexico from the Pliocene to Holocene based on radiogenic isotopes

NASA Astrophysics Data System (ADS)

Portier, A. M.; Martin, E. E.; Hemming, S. R.; Thierens, M. M.; Raymo, M. E.

2014-12-01

Chemical weathering of the continents plays a key role in the global carbon cycle and delivers solutes to the ocean. Past studies, documented using radiogenic isotopes of detrital and seawater samples, show the intensity of weathering varies with climate over a range of time scales.. We analyzed Pb and Nd isotopic values of seawater extracted from dispersed Fe-Mn oxides, <2μm (clay) and <63μm (silt) detrital fractions of Pliocene to Holocene sediment from Gulf of Mexico ODP Site 625B to evaluate long term variations in weathering fluxes for three time slices: the Pliocene/early Pleistocene, Mid Pleistocene Transition (MPT), and late Pleistocene/Holocene. We also examine short term glacial/interglacial variations. Little variation is seen in Nd isotopes of detrital fractions with age, suggesting little change in the average age of material delivered to the Gulf. Seawater Nd values become less radiogenic over the Pleistocene, consistent with observed changes in Caribbean seawater. Pb isotopes of silt fractions are also relatively constant through time, but clay fractions are more radiogenic at the MPT and dispersed Fe-Mn oxides trend to more radiogenic values in the late Pleistocene. Consequently, the Pb isotopes of dispersed Fe-Mn oxides tend to be less radiogenic than the detrital fractions in samples older than 2000 ka and more radiogenic than the detrital fractions, particularly clays, at the MPT. This may reflect greater incongruent silicate weathering during the MPT, a change in weathering conditions that could be consistent with the Regolith Hypothesis. Over glacial/interglacial timescales, dispersed Fe-Mn oxides Pb isotopes become more radiogenic than detrital fractions, and clay fractions become more radiogenic than silt fractions, during glacial periods. However, all fractions have similar values during interglacials. This pattern is distinct from previous studies that found enhanced incongruent silicate weathering during warm intervals, but is consistent with recent work finding a correlation with carbonate content, whereby low carbonate during glacials at Site 625 corresponds to a greater offset between leachate and detrital Pb isotopes. Biases from "heavy mineral effects" and changes in circulation during periods of lower sea level also need to be considered.

Converting isotope ratios to diet composition - the use of mixing models - June 2010

EPA Science Inventory

One application of stable isotope analysis is to reconstruct diet composition based on isotopic mass balance. The isotopic value of a consumer’s tissue reflects the isotopic values of its food sources proportional to their dietary contributions. Isotopic mixing models are used ...

Charge radii of neutron deficient Fe 52 , 53 produced by projectile fragmentation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minamisono, K.; Rossi, D. M.; Beerwerth, R.

Bunched-beam collinear laser spectroscopy is performed on neutron deficient 52,53Fe prepared through in-flight separation followed by a gas stopping. This novel scheme is a major step to reach nuclides far from the stability line in laser spectroscopy. Differential mean-square charge radii δmore » $$\\langle$$r 2$$\\rangle$$ of 52,53Fe are determined relative to stable 56Fe as δ$$\\langle$$r2$$\\rangle$$ 56,52=$-$0.034(13) fm 2 and δ$$\\langle$$r 2$$\\rangle$$56,53=$-$0.218(13) fm 2, respectively, from the isotope shift of atomic hyperfine structures. The multiconfiguration Dirac-Fock method is used to calculate atomic factors to deduce δ$$\\langle$$r 2$$\\rangle$$. The values of δ$$\\langle$$r 2$$\\rangle$$ exhibit a minimum at the N=28 neutron shell closure. The nuclear density functional theory with Fayans and Skyrme energy density functionals is used to interpret the data. As a result, the trend of δ$$\\langle$$r 2$$\\rangle$$ along the Fe isotopic chain results from an interplay between single-particle shell structure, pairing, and polarization effects and provides important data for understanding the intricate trend in the δ$$\\langle$$r 2$$\\rangle$$ of closed-shell Ca isotopes« less

Charge radii of neutron deficient Fe 52 , 53 produced by projectile fragmentation

DOE PAGES

Minamisono, K.; Rossi, D. M.; Beerwerth, R.; ...

2016-12-15

Bunched-beam collinear laser spectroscopy is performed on neutron deficient 52,53Fe prepared through in-flight separation followed by a gas stopping. This novel scheme is a major step to reach nuclides far from the stability line in laser spectroscopy. Differential mean-square charge radii δmore » $$\\langle$$r 2$$\\rangle$$ of 52,53Fe are determined relative to stable 56Fe as δ$$\\langle$$r2$$\\rangle$$ 56,52=$-$0.034(13) fm 2 and δ$$\\langle$$r 2$$\\rangle$$56,53=$-$0.218(13) fm 2, respectively, from the isotope shift of atomic hyperfine structures. The multiconfiguration Dirac-Fock method is used to calculate atomic factors to deduce δ$$\\langle$$r 2$$\\rangle$$. The values of δ$$\\langle$$r 2$$\\rangle$$ exhibit a minimum at the N=28 neutron shell closure. The nuclear density functional theory with Fayans and Skyrme energy density functionals is used to interpret the data. As a result, the trend of δ$$\\langle$$r 2$$\\rangle$$ along the Fe isotopic chain results from an interplay between single-particle shell structure, pairing, and polarization effects and provides important data for understanding the intricate trend in the δ$$\\langle$$r 2$$\\rangle$$ of closed-shell Ca isotopes« less

Origin of enormous trace metal enrichments in weathering mantles of Jurassic carbonates: evidence from Sr, Nd and Pb isotopes

NASA Astrophysics Data System (ADS)

Hissler, C.; Stille, P.; Juilleret, J.; Iffly, J.; Perrone, T.; Morvan, G.

2013-12-01

Weathering mantels are widespread worldwide and include lateritic, sandy and kaolinite-rich saprolites and residuals of partially dissolved carbonate rocks. These old regolith systems have a complex history of formation and may present a polycyclic evolution due to successive geological and pedogenetic processes that affected the profile. Until now, only few studies highlighted the unusual content of associated trace elements in this type of weathering mantle. For instance, these enrichments can represent about five times the content of the underlying Bajocian to Oxfordian limestone/marl complexes, which have been relatively poorly studied compared to weathering mantle developed on magmatic bedrocks. Up to now, neither soil, nor saprolite formation has to our knowledge been geochemically elucidated. Therefore, the aim of this study was to examine more closely the soil forming dynamics and the relationship of the chemical soil composition to potential sources (saprolite, Bajocian silty marls and limestones, atmospheric particles deposition...). Of special interest has also been the origin of trace metals and the processes causing their enrichments. Especially Rare Earth Element (REE) distribution patterns and Sr, Nd and Pb isotope ratios are particularly well suited to identify trace element migration, to recognize origin and mixing processes and, in addition, to decipher possible anthropogenic and/or "natural" atmosphere-derived contributions to the soil. Moreover, leaching experiments shall help to identify mobile phases in the soil system. This may inform on the stability of trace elements and especially on their behaviour in these Fe-enriched carbonate systems. Trace metal migration and enrichments were studied on a cambisol developing on an underlying Jurassic limestone. The base is strongly enriched among others in rare earth elements (ΣREE: 2640ppm) or redox-sensitive elements such as Fe (44 wt.%), V (920ppm), Cr (700ppm), Zn (550ppm), As (260ppm), Co (45ppm) and Cd (2.4ppm). The underlying limestone and marl show, compared to average world carbonates, enrichments in the same elements and trace element distribution patterns similar to the soil suggesting their close genetic relationship. Pb, Sr and Nd isotope data allow to identify three principal components in the soil: a silicate-rich phase at close to the surface, a strongly trace metal enriched component at the bottom of the soil profile and an anthropogenic, atmosphere- derived component detected in the soil leachates. The isotopic mixing curves defined by the soil samples point to the close genetic connection between upper and lowermost soil horizons. The Nd isotopic composition of the leachates of all soil horizons are in contrast to the untreated soil and residual soil samples very homogeneous suggesting that the leachable phases of the upper and lower soil horizons are genetically connected. The downward migration of the trace metals is stopped at this soil level due to the presence of important secondary calcite precipitations, smectite and Fe-oxide accumulations. Mass balance calculations indicate that the enrichment process goes along with a volume increase relative to the bottom soil horizons.

High Magnetic Susceptibility in a Highly Saline Sulfate-Rich Aquifer Undergoing Biodegradation of Hydrocarbon Results from Sulfate Reduction.

NASA Astrophysics Data System (ADS)

Atekwana, E. A.; Enright, A.; Ntarlagiannis, D.; Slater, L. D.; Bernier, R.; Beaver, C. L.; Rossbach, S.

2016-12-01

We investigated the chemical and stable carbon isotope composition of groundwater in a highly saline aquifer contaminated with hydrocarbon. Our aim to evaluate hydrocarbon degradation and to constrain the geochemical conditions that generated high anomalous magnetic susceptibility (MS) signatures observed at the water table interface. The occurrence of high MS in the water table fluctuating zone has been attributed to microbial iron reduction, suggesting the use of MS as a proxy for iron cycling. The highly saline aquifer had total dissolved solids concentrations of 3.7 to 29.3 g/L and sulfate concentrations of 787 to 37,100 mg/L. We compared our results for groundwater locations with high hydrocarbon contamination (total petroleum hydrocarbon (TPH) >10 mg/L), at lightly contaminated (TPH <10 mg/L) and locations with no contaminations. Our results for the terminal electron acceptors (TEAs) dissolved oxygen (DO), nitrate (NO3-), dissolved iron (Fe2+) , dissolved manganese (Mn2+), sulfate (SO42-) and methane (CH4) suggest a chemically heterogeneous aquifer, probably controlled by heterogeneous distribution of TEAs and contamination (type of hydrocarbon, phase and age of contamination). The concentrations of dissolved inorganic carbon (DIC) ranged from 67 to 648 mg C/L and the stable carbon isotope (δ13CDIC) ranged from -30.0‰ to 1.0 ‰ and DIC-δ13CDIC modeling indicates that the carbon in the DIC is derived primarily from hydrocarbon degradation. The concentrations of Fe2+ in the aquifer ranged from 0.1 to 55.8 mg/L, but was mostly low, averaging 2.7+10.9 mg/L. Given the low Fe2+ [AE1] in the aqueous phase and the high MS at contaminated locations, we suggest that the high MS observed does not arise from iron reduction but rather from sulfate reduction. Sulfate reduction produces H2S which reacts with Fe2+ to produce ferrous sulfide (Fe2+S) or the mixed valence greigite (Fe2+Fe3+2S4). We conclude that in highly saline aquifers with high concentrations of sulfate and contaminated with hydrocarbon, dominance of sulfate reduction as the TEA is responsible for iron cycling and therefore the high MS associated with biodegradation. [AE1]What about sulfate concentrations? And the range in salinity? You need to add these values to the bastrcat

Dual element (CCl) isotope approach to distinguish abiotic reactions of chlorinated methanes by Fe(0) and by Fe(II) on iron minerals at neutral and alkaline pH.

PubMed

Rodríguez-Fernández, Diana; Heckel, Benjamin; Torrentó, Clara; Meyer, Armin; Elsner, Martin; Hunkeler, Daniel; Soler, Albert; Rosell, Mònica; Domènech, Cristina

2018-05-07

A dual element CCl isotopic study was performed for assessing chlorinated methanes (CMs) abiotic transformation reactions mediated by iron minerals and Fe(0) to further distinguish them in natural attenuation monitoring or when applying remediation strategies in polluted sites. Isotope fractionation was investigated during carbon tetrachloride (CT) and chloroform (CF) degradation in anoxic batch experiments with Fe(0), with FeCl 2 (aq), and with Fe-bearing minerals (magnetite, Mag and pyrite, Py) amended with FeCl 2 (aq), at two different pH values (7 and 12) representative of field and remediation conditions. At pH 7, only CT batches with Fe(0) and Py underwent degradation and CF accumulation evidenced hydrogenolysis. With Py, thiolytic reduction was revealed by CS 2 yield and is a likely reason for different Λ value (Δδ 13 C/Δδ 37 Cl) comparing with Fe(0) experiments at pH 7 (2.9 ± 0.5 and 6.1 ± 0.5, respectively). At pH 12, all CT experiments showed degradation to CF, again with significant differences in Λ values between Fe(0) (5.8 ± 0.4) and Fe-bearing minerals (Mag, 2 ± 1, and Py, 3.7 ± 0.9), probably evidencing other parallel pathways (hydrolytic and thiolytic reduction). Variation of pH did not significantly affect the Λ values of CT degradation by Fe(0) nor Py. CF degradation by Fe(0) at pH 12 showed a Λ (8 ± 1) similar to that reported at pH 7 (8 ± 2), suggesting CF hydrogenolysis as the main reaction and that CF alkaline hydrolysis (13.0 ± 0.8) was negligible. Our data establish a base for discerning the predominant or combined pathways of CMs natural attenuation or for assessing the effectiveness of remediation strategies using recycled minerals or Fe(0). Copyright © 2018 Elsevier Ltd. All rights reserved.

The sources and evolution of mineralising fluids in iron oxide-copper-gold systems, Norrbotten, Sweden: Constraints from Br/Cl ratios and stable Cl isotopes of fluid inclusion leachates

NASA Astrophysics Data System (ADS)

Gleeson, S. A.; Smith, M. P.

2009-10-01

We have analysed the halogen concentrations and chlorine stable isotope composition of fluid inclusion leachates from three spatially associated Fe-oxide ± Cu ± Au mineralising systems in Norrbotten, Sweden. Fluid inclusions in late-stage veins in Fe-oxide-apatite deposits contain saline brines and have a wide range of Br/Cl molar ratios, from 0.2 to 1.1 × 10 -3 and δ 37Cl values from -3.1‰ to -1.0‰. Leachates from saline fluid inclusions from the Greenstone and Porphyry hosted Cu-Au prospects have Br/Cl ratios that range from 0.2 to 0.5 × 10 -3 and δ 37Cl values from -5.6‰ to -1.3‰. Finally, the Cu-Au deposits hosted by the Nautanen Deformation Zone (NDZ) have Br/Cl molar ratios from 0.4 to 1.1 × 10 -3 and δ 37Cl values that range from -2.4‰ to +0.5‰, although the bulk of the data fall within 0‰ ± 0.5‰. The Br/Cl ratios of leachates are consistent with the derivation of salinity from magmatic sources or from the dissolution of halite. Most of the isotopic data from the Fe-oxide-apatite and Greenstone deposits are consistent with a mantle derived source of the chlorine, with the exception of the four samples with the most negative values. The origin of the low δ 37Cl values in these samples is unknown but we suggest that there may have been some modification of the Cl-isotope signature due to fractionation between the mineralising fluids and Cl-rich silicate assemblages found in the alteration haloes around the deposits. If such a process has occurred then a modified crustal source of the chlorine for all the samples cannot be ruled out although the amount of fractionation necessary to generate the low δ 37Cl values would be significantly larger. The source of Cl in the NDZ deposits has a crustal signature, which suggests the Cl in this system may be derived from (meta-) evaporites or from input from crustal melts such as granitic pegmatites of the Lina Suite.