Uniformity in sulfur isotope composition in the orogenic gold deposits from the Dharwar Craton, southern India

NASA Astrophysics Data System (ADS)

Sakthi Saravanan, C.; Mishra, B.

2009-07-01

The sulfur isotope composition of sulfides (mainly pyrite and arsenopyrite) from gold deposits/prospects of the Dharwar Craton such as Hutti, Hira-Buddini, Uti, Kolar (Chigargunta), Ajjanahalli, and Jonnagiri has a narrow range (δ34S = +1.1 to +7.1‰). Such craton-scale uniformity of the above gold camps is noteworthy, in spite of the wide diversity in host rock compositions and their metamorphic conditions, and suggests a magmatic or average crustal source of sulfur for all deposits studied. In addition, our study points towards gold precipitation from reduced ore fluids, with near-homogeneous sulfur isotope compositions.

Modes of planetary-scale Fe isotope fractionation

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; von Blanckenburg, Friedhelm

2006-12-01

A comprehensive set of high-precision Fe isotope data for the principle meteorite types and silicate reservoirs of the Earth is used to investigate iron isotope fractionation at inter- and intra-planetary scales. 14 chondrite analyses yield a homogeneous Fe isotope composition with an average δ56Fe/ 54Fe value of - 0.015 ± 0.020‰ (2 SE) relative to the international iron standard IRMM-014. Eight non-cumulate and polymict eucrite meteorites that sample the silicate portion of the HED (howardite-eucrite-diogenite) parent body yield an average δ56Fe/ 54Fe value of - 0.001 ± 0.017‰, indistinguishable to the chondritic Fe isotope composition. Fe isotope ratios that are indistinguishable to the chondritic value have also been published for SNC meteorites. This inner-solar system homogeneity in Fe isotopes suggests that planetary accretion itself did not significantly fractionate iron. Nine mantle xenoliths yield a 2 σ envelope of - 0.13‰ to + 0.09‰ in δ56Fe/ 54Fe. Using this range as proxy for the bulk silicate Earth in a mass balance model places the Fe isotope composition of the outer liquid core that contains ca. 83% of Earth's total iron to within ± 0.020‰ of the chondritic δ56Fe/ 54Fe value. These calculations allow to interprete magmatic iron meteorites ( δ56Fe/ 54Fe = + 0.047 ± 0.016‰; N = 8) to be representative for the Earth's inner metallic core. Eight terrestrial basalt samples yield a homogeneous Fe isotope composition with an average δ56Fe/ 54Fe value of + 0.072 ± 0.016‰. The observation that terrestrial basalts appear to be slightly heavier than mantle xenoliths and that thus partial mantle melting preferentially transfers heavy iron into the melt [S. Weyer, A.D. Anbar, G.P. Brey, C. Munker, K. Mezger and A.B. Woodland, Iron isotope fractionation during planetary differentiation, Earth and Planetary Science Letters 240(2), 251-264, 2005.] is intriguing, but also raises some important questions: first it is questionable whether the Fe isotope composition of lithospheric mantle xenoliths are representative for an undisturbed melt source, and second, HED and SNC meteorites, representing melting products of 4Vesta and Mars silicate mantles would be expected to show a similar fractionation towards heavy isotope compositions. This is not observed. Four international granitoid standards with SiO 2 contents between 60 and 70 wt.% yield δ56Fe/ 54Fe values between 0.118‰ and 0.132‰. An investigation of the alpine Bergell igneous rock suite revealed a positive correlation between Fe isotope compositions and SiO 2 contents — from gabbros and tonalites ( δ56Fe/ 54Fe ≈ 0.03 to 0.09‰) to granodiorites and silicic dykes ( δ56Fe/ 54Fe ≈ 0.14 to 0.23‰). Although in this suite δ56Fe/ 54Fe correlates with δ18O values and radiogenic isotopes, open-system behavior to explain the heavy iron is not undisputed. This is because an obvious assimilant with the required heavy Fe isotope composition has so far not been identified. Alternatively, the relatively heavy granite compositions might be obtained by fractional crystallisation of the melt. Ultimately, further detailed studies on natural rocks and the experimental determination of mineral/melt fractionation factors at magmatic conditions are required to unravel whether or not iron isotope fractionation takes place during partial mantle melting and crystal fractionation.

Origin of petroporphyrins. 2. Evidence from stable carbon isotopes

NASA Technical Reports Server (NTRS)

Boreham, C. J.; Fookes, C. J.; Popp, B. N.; Hayes, J. M.

1990-01-01

Compared with the carbon-13 isotopic composition of the ubiquitous C32DPEP (DPEP, deoxophylloerythroetioporphyrin) the heavy but equivalent carbon-13 isotopic composition for the porphyrin structures 15(2)-methyl-15,17-ethano-17-nor-H-C30DPEP and 15,17-butano-, 13,15-ethano-13(2),17-propano-, and 13(1)-methyl-13,15-ethano-13(2),17-propanoporphyrin suggests a common precursor, presumably chlorophyll c, for these petroporphyrins isolated from the marine Julia Creek oil shale and the lacustrine Condor oil shale. Similarly, the heavy but variable carbon-13 isotopic composition of 7-nor-H-C31DPEP compared with C32DPEP is consistent with an origin from both chlorophyll b and chlorophyll c3. The equivalent carbon-13 isotopic composition for 13(2)-methyl-C33DPEP compared with C32DPEP suggests a common origin resulting from a weighted average of chlorophyll inputs.

Isotopic Evidence of Unaccounted for Fe and Cu Erythropoietic Pathways

NASA Astrophysics Data System (ADS)

Albarede, F.; Telouk, P.; Lamboux, A.; Jaouen, K.; Balter, V.

2011-12-01

Despite its potential importance for understanding perturbations in the Fe-Cu homeostatic pathways, the natural isotopic variability of these metals in the human body remains unexplored. We measured the Fe, Cu, and Zn isotope compositions of total blood, serum, and red blood cells of ~50 young blood donors by multiple-collector ICP-MS after separation and purification by anion exchange chromatography. Zn is on average 0.2 permil heavier in erythrocytes (δ 66Zn=0.44±0.33 permil) with respect to serum but shows much less overall isotopic variability than Fe and Cu, which indicates that isotope fractionation depends more on redox conditions than on ligand coordination. On average, Fe in erythrocytes (δ 56Fe=-2.59±0.47 permil) is isotopically light by 1-2 permil with respect to serum, whereas Cu in erythrocytes (δ 65Cu=0.56±0.50 permil) is 0.8 percent heavier. Fe and Cu isotope compositions clearly separate erythrocytes of men and women. Fe and Cu from B-type men erythrocytes are visibly more fractionated than all the other blood types. Isotope compositions provide an original method for evaluating metal mass balance and homeostasis. Natural isotope variability shows that the current models of Fe and Cu erythropoiesis, which assume that erythropoiesis is restricted to bone marrow, violate mass balance requirements. It unveils unsuspected major pathways for Fe, with erythropoietic production of isotopically heavy ferritin and hemosiderin, and for Cu, with isotopically light Cu being largely channeled into blood and lymphatic circulation rather than into superoxide dismutase-laden erythrocytes. Iron isotopes provide an intrinsic measuring rod of the erythropoietic yield, while Cu isotopes seem to gauge the relative activity of erythropoiesis and lymphatics.

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.

Isotope effects on the optical spectra of semiconductors

NASA Astrophysics Data System (ADS)

Cardona, Manuel; Thewalt, M. L. W.

2005-10-01

Since the end of the cold war, macroscopic amounts of separated stable isotopes of most elements have been available “off the shelf” at affordable prices. Using these materials, single crystals of many semiconductors have been grown and the dependence of their physical properties on isotopic composition has been investigated. The most conspicuous effects observed have to do with the dependence of phonon frequencies and linewidths on isotopic composition. These affect the electronic properties of solids through the mechanism of electron-phonon interaction, in particular, in the corresponding optical excitation spectra and energy gaps. This review contains a brief introduction to the history, availability, and characterization of stable isotopes, including their many applications in science and technology. It is followed by a concise discussion of the effects of isotopic composition on the vibrational spectra, including the influence of average isotopic masses and isotopic disorder on the phonons. The final sections deal with the effects of electron-phonon interaction on energy gaps, the concomitant effects on the luminescence spectra of free and bound excitons, with particular emphasis on silicon, and the effects of isotopic composition of the host material on the optical transitions between the bound states of hydrogenic impurities.

Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale

NASA Technical Reports Server (NTRS)

Chicarelli, M. I.; Hayes, J. M.; Popp, B. N.; Eckardt, C. B.; Maxwell, J. R.

1993-01-01

The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

Spacecraft measurements of the elemental and isotopic composition of solar energetic particles

NASA Technical Reports Server (NTRS)

Mewaldt, R. A.

1980-01-01

Within the past few years, instruments flown on satellites and space probes have made significant progress in measuring the elemental and isotopic composition of energetic heavy nuclei accelerated in solar flares. These new observations are discussed, focusing on: (1) the energy dependence of the elemental composition at energies not greater than 1 MeV/nucleon; (2) flare to flare variations in the composition; and (3) comparisons of the average solar particle abundances (Z not less than 2 and not greater than 28) with other measures of the solar composition, including photospheric, coronal, and solar wind observations. These comparisons have led to the suggestion that solar flares sample the composition of the corona. Isotopic measurements of heavy solar flare nuclei have recently added a new dimension to these studies. In particular, the isotopic composition of solar flare neon has been found to be significantly different from that measured in the solar wind, but consistent with the meteoritic component neon-A.

[High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

PubMed

Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

2013-05-01

In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

The neodymium stable isotope composition of the silicate Earth and chondrites

NASA Astrophysics Data System (ADS)

McCoy-West, Alex J.; Millet, Marc-Alban; Burton, Kevin W.

2017-12-01

The non-chondritic neodymium (Nd) 142Nd/144Nd ratio of the silicate Earth potentially provides a key constraint on the accretion and early evolution of the Earth. Yet, it is debated whether this offset is due to the Earth being formed from material enriched in s-process Nd isotopes or results from an early differentiation process such as the segregation of a late sulfide matte during core formation, collisional erosion or a some combination of these processes. Neodymium stable isotopes are potentially sensitive to early sulfide segregation into Earth's core, a process that cannot be resolved using their radiogenic counterparts. This study presents the first comprehensive Nd stable isotope data for chondritic meteorites and terrestrial rocks. Stable Nd measurements were made using a double spike technique coupled with thermal ionisation mass spectrometry. All three of the major classes of chondritic meteorites, carbonaceous, enstatite and ordinary chondrites have broadly similar isotopic compositions allowing calculation of a chondritic mean of δ146/144Nd = -0.025 ± 0.025‰ (±2 s.d.; n = 39). Enstatite chondrites yield the most uniform stable isotope composition (Δ146/144Nd = 26 ppm), with considerably more variability observed within ordinary (Δ146/144Nd = 72 ppm) and carbonaceous meteorites (Δ146/144Nd = 143 ppm). Terrestrial weathering, nucleosynthetic variations and parent body thermal metamorphism appear to have little measurable effect on δ146/144Nd in chondrites. The small variations observed between ordinary chondrite groups most likely reflect inherited compositional differences between parent bodies, with the larger variations observed in carbonaceous chondrites being linked to varying modal proportions of calcium-aluminium rich inclusions. The terrestrial samples analysed here include rocks ranging from basaltic to rhyolitic in composition, MORB glasses and residual mantle lithologies. All of these terrestrial rocks possess a broadly similar Nd isotope composition giving an average composition for the bulk silicate Earth of δ146/144Nd = -0.022 ± 0.034‰ (n = 30). In the samples here magmatic differentiation appears to only have an effect on stable Nd in highly evolved magmas with heavier δ146/144Nd values observed in samples with >70 wt% SiO2. The average stable Nd isotope composition of chondrites and the bulk silicate Earth are indistinguishable at the 95% confidence level. However, mantle samples do possess variable stable Nd isotope compositions (Δ146/144Nd = 75 ppm) with an average δ 146 / 144Nd value of -0.008‰. If these heavier values represent the true composition of pristine mantle then it is not possible to completely rule out some role for core formation in accounting for some of the offset between the mantle and chondrites. Overall, these results indicate that the mismatch of 142Nd between the Earth and chondrites is best explained by a higher proportion of s-process Nd in the Earth, rather than partitioning into sulfide or S-rich metal in the core.

Controls on the barium isotope compositions of marine sediments

NASA Astrophysics Data System (ADS)

Bridgestock, Luke; Hsieh, Yu-Te; Porcelli, Donald; Homoky, William B.; Bryan, Allison; Henderson, Gideon M.

2018-01-01

The accumulation of barium (Ba) in marine sediments is considered to be a robust proxy for export production, although this application can be limited by uncertainty in BaSO4 preservation and sediment mass accumulation rates. The Ba isotope compositions of marine sediments could potentially record insights into past changes in the marine Ba cycle, which should be insensitive to these limitations, enabling more robust interpretation of sedimentary Ba as a proxy. To investigate the controls on the Ba isotope compositions of marine sediments and their potential for paleo-oceanographic applications, we present the first Ba isotope compositions results for sediments, as well as overlying seawater depth profiles collected in the South Atlantic. Variations in Ba isotope compositions of the sediments predominantly reflect changes in the relative contributions of detrital and authigenic Ba sources, with open-ocean sediments constraining the isotope composition of authigenic Ba to be δ 138/134Ba ≈ + 0.1 ‰. This value is consistent with the average isotope composition inferred for sinking particulate Ba using simple mass balance models of Ba in the overlying water column and is hypothesized to reflect the removal of Ba from the upper water column with an associated isotopic fractionation of Δ diss-part 138/134Ba ≈ + 0.4 to +0.5. Perturbations to upper ocean Ba cycling, due to changes in export production and the supply of Ba via upwelling, should therefore be recorded by the isotope compositions of sedimentary authigenic Ba. Such insights will help to improve the reliable application of Ba accumulation rates in marine sediments as a proxy for past changes in export production.

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.

Linking the isotopic composition of monthly precipitation, cave drip water and tree ring cellulose - 15 years of monitoring and data-model comparison

NASA Astrophysics Data System (ADS)

Labuhn, Inga; Genty, Dominique; Daux, Valérie; Bourges, François; Hoffmann, Georg

2013-04-01

The isotopic composition of proxies used for palaeoclimate reconstruction, like tree ring cellulose or speleothem calcite, is controlled to a large extent by the isotopic composition of precipitation. In order to calibrate and interpret these proxies in terms of climate, it is necessary to study water isotopes in rainfall and their link with the proxies' source water. We present 10 to 15-year series of stable hydrogen and oxygen isotopes in monthly precipitation from three sites in the south of France, along with corresponding REMOiso model simulations, a monitoring of cave drip water from two of these sites (Villars cave in the south-west and Chauvet cave in the south-east), as well as measurements of oxygen isotopes in tree ring cellulose from oak trees growing in the same area. The isotopic composition of monthly precipitation at the three sites displays a typical annual cycle. At the south-west sites, under Atlantic influence, the interannual variability is much more pronounced during the winter months than during the summer, whereas the south-eastern Mediterranean site shows the same variability throughout the year. The model simulations are able to reproduce the annual cycle of monthly precipitation δ18O as well as the intra-seasonal variability. Compared to the data, however, the modelled average isotopic values and the seasonal amplitude are overestimated. Correlations between temperature and precipitation δ18O are generally weak at all our sites, on both the monthly and the annual scale, even when using temperature averages weighted by the amount of precipitation. Consequently, a proxy which is controlled by the δ18O of precipitation cannot be directly interpreted in terms of temperature in this region. The isotopic composition of cave drip water in both caves remains stable throughout the monitoring period. By calculating different weighted averages of precipitation δ18O for time periods ranging from months to years, we demonstrate that the cave drip water isotopic composition is the result of several years of rainfall mixing. The precipitation of every month must be considered in order to attain the drip water values, which means that rain water infiltrates throughout the year. There is no modification of the soil water isotopic composition by evaporation and no seasonal bias introduced by transpiring plants; they use water from reserves which represents several months or years of mixing. For the interpretation of tree ring cellulose δ18O, this implies that - at least for the monitoring period of 15 years - the source water signal is more or less constant. Therefore, the variability of cellulose δ18O must be mainly due to evaporation at the leaf level, which is strongly dependent on summer temperature. Insights on the variability and temperature correlations of stable isotopes in precipitation and on the origin and composition of cave drip water are important for the interpretation of proxies. Long-term monitoring is needed for model validation, and the locally validated and corrected model can provide longer time series for a reliable proxy calibration.

Magnesium stable isotope composition of Earth's upper mantle

NASA Astrophysics Data System (ADS)

Handler, Monica R.; Baker, Joel A.; Schiller, Martin; Bennett, Vickie C.; Yaxley, Gregory M.

2009-05-01

The mantle is Earth's largest reservoir of Mg containing > 99% of Earth's Mg inventory. However, no consensus exists on the stable Mg isotope composition of the Earth's mantle or how variable it is and, in particular, whether the mantle has the same stable Mg isotope composition as chondrite meteorites. We have determined the Mg isotope composition of olivine from 22 mantle peridotites from eastern Australia, west Antarctica, Jordan, Yemen and southwest Greenland by pseudo-high-resolution MC-ICP-MS on Mg purified to > 99%. The samples include fertile lherzolites, depleted harzburgites and dunites, cryptically metasomatised ('dry') peridotites and modally metasomatised apatite ± amphibole-bearing harzburgites and wehrlites. Olivine from these samples of early Archaean through to Permian lithospheric mantle have δ25Mg DSM-3 = - 0.22 to - 0.08‰. These data indicate the bulk upper mantle as represented by peridotite olivine is homogeneous within current analytical uncertainties (external reproducibility ≤ ± 0.07‰ [2 sd]). We find no systematic δ25Mg variations with location, lithospheric age, peridotite fertility, or degree or nature of mantle metasomatism. Although pyroxene may have slightly heavier δ25Mg than coexisting olivine, any fractionation between mantle pyroxene and olivine is also within current analytical uncertainties with a mean Δ25Mg pyr-ol = +0.06 ± 0.10‰ (2 sd; n = 5). Our average mantle olivine δ25Mg DSM-3 = - 0.14 ± 0.07‰ and δ26Mg DSM-3 = - 0.27 ± 0.14‰ (2 sd) are indistinguishable from the average of data previously reported for terrestrial basalts, confirming that basalts have stable Mg isotope compositions representative of the mantle. Olivine from five pallasite meteorites have δ25Mg DSM-3 = - 0.16 to - 0.11‰ that are identical to terrestrial olivine and indistinguishable from the average δ25Mg previously reported for chondrites. These data provide no evidence for measurable heterogeneity in the stable Mg isotope composition of the source material in the proto-planetary disc from which Earth and chondrite and pallasite parent bodies accreted.

Sr isotopic tracer study of the Samail ophiolite, Oman.

USGS Publications Warehouse

Lanphere, M.A.; Coleman, R.G.; Hopson, C.A.

1981-01-01

Rb and Sr concentrations and Sr-isotopic compositions were measured in 41 whole-rock samples and 12 mineral separates from units of the Samail ophiolite, including peridotite, gabbro, plagiogranite, diabase dykes, and gabbro and websterite dykes within the metamorphic peridotite. Ten samples of cumulate gabbro from the Wadir Kadir section and nine samples from the Wadi Khafifah section have 87Sr/86Sr ratios of 0.70314 + or - 0.00030 and 0.70306 + or - 0.00034, respectively. The dispersion in Sr- isotopic composition may reflect real heterogeneities in the magma source region. The average Sr-isotopic composition of cumulate gabbro falls in the range of isotopic compositions of modern MORB. The 87Sr/86Sr ratios of noncumulate gabbro, plagiogranite, and diabase dykes range 0.7034-0.7047, 0.7038-0.7046 and 0.7037- 0.7061, respectively. These higher 87Sr/86Sr ratios are due to alteration of initial magmatic compositions by hydrothermal exchange with sea-water. Mineral separates from dykes that cut harzburgite tectonite have Sr-isotopic compositions which agree with that of cumulate gabbro. These data indicate that the cumulate gabbro and the different dykes were derived from partial melting of source regions that had similar long-term histories and chemical compositions.-T.R.

A Carbon Source Apportionment Shift in Mexico City Atmospheric Particles During 2003-2004 as Determined with Stable Carbon Isotopes

NASA Astrophysics Data System (ADS)

Lopez-Veneroni, D. G.; Vega, E.

2013-05-01

The stable carbon isotope composition of atmospheric particles (PM2.5) was measured at La Merced (MER), a commercial site in the eastern sector, and at Xalostoc (XAL) an industrial site in the NE sector of Mexico City, during three sampling periods in autumn 2003, and spring and autumn 2004. At each site and sampling campaign particle samples were collected daily with minivol samplers during two week periods. Ancillary data included organic and elemental carbon, trace elements and ionic species. This data base was complement with air quality data from the RAMA (Automatic Atmospheric Monitoring Network). In general, particle concentrations, ionic species and some air quality species showed higher concentrations in autumn and lowest values in spring. Moreover, the concentrations of these chemical species were highest at XAL compared to MER. The stable carbon isotope composition of PM2.5 during autumn 2003 and spring 2004 had and average value of -26.04 (± 1.54) ‰ vs. PDB. Differences in the isotopic composition between the two sites were non significant. The average δ13C during these seasons were 1 ‰ lighter relative to data collected previously at these sites during 2000 and 2001, and is consistent with a predominant source of hydrocarbon combustion. In autumn 2004, however, average δ13C at XAL and MER increased to -22.8 (± 0.9) and -20.6 (± 3.1) ‰, respectively. Organic carbon concentrations during this period increased concomitantly at these sites. The shift in the isotopic composition in ambient particles suggests a predominance of soil-derived carbon during this period. The possible causes and implications of this are discussed.

Lead isotopes and trace metals in dust at Yucca Mountain

USGS Publications Warehouse

Kwak, Loretta; Neymark, Leonid A.; Peterman, Zell E.

2008-01-01

Lead (Pb)-isotope compositions and trace-metal concentrations were determined for samples of dust collected from underground and surface locations at and near the proposed radioactive waste repository at Yucca Mountain, Nevada. Rare earth element concentrations in the dust samples from the underground tunnels are similar to those in wholerock samples of the repository host rocks (Miocene Tiva Canyon Tuff and Topopah Spring Tuff), supporting interpretation that the subsurface dust is mainly composed of rock comminuted during tunnel construction. Other trace metals (arsenic, cadmium, cobalt, chromium, copper, manganese, nickel, lead, antimony, thallium, and zinc) are variably enriched in the subsurface dust samples relative to the average concentrations in the host rocks. Average concentrations of arsenic and lead in dust samples, high concentrations of which can cause corrosion of waste canisters, have enrichment factors from 1.2 to 1.6 and are insignificant relative to the range of concentrations for these metals observed in the host rock samples. Most dust samples from surface sites also are enriched in many of these trace metals relative to average repository host rocks. At least some of these enrichments may be artifacts of sampling. Plotted on a 208Pb/206Pb-207Pb/206Pb graph, Pb-isotope compositions of dust samples from underground sites form a mixing line extending from host-rock Pb-isotope compositions towards compositions of many of the dust samples from surface sites; however, combined Pb concentration and isotope data indicate the presence of a Pbenriched component in the subsurface dust that is not derived from host rock or surface dust and may derive from anthropogenic materials introduced into the underground environment.

Lead isotope compositions of Late Cretaceous and early Tertiary igneous rocks and sulfide minerals in Arizona: Implications for the sources of plutons and metals in porphyry copper deposits

USGS Publications Warehouse

Bouse, R.M.; Ruiz, J.; Titley, S.R.; Tosdal, R.M.; Wooden, J.L.

1999-01-01

Porphyry copper deposits in Arizona are genetically associated with Late Cretaceous and early Tertiary igneous complexes that consist of older intermediate volcanic rocks and younger intermediate to felsic intrusions. The igneous complexes and their associated porphyry copper deposits were emplaced into an Early Proterozoic basement characterized by different rocks, geologic histories, and isotopic compositions. Lead isotope compositions of the Proterozoic basement rocks define, from northwest to southeast, the Mojave, central Arizona, and southeastern Arizona provinces. Porphyry copper deposits are present in each Pb isotope province. Lead isotope compositions of Late Cretaceous and early Tertiary plutons, together with those of sulfide minerals in porphyry copper deposits and of Proterozoic country rocks, place important constraints on genesis of the magmatic suites and the porphyry copper deposits themselves. The range of age-corrected Pb isotope compositions of plutons in 12 Late Cretaceous and early Tertiary igneous complexes is 206Pb/204Pb = 17.34 to 22.66, 207Pb/204Pb = 15.43 to 15.96, and 208Pb/204Pb = 37.19 to 40.33. These Pb isotope compositions and calculated model Th/U are similar to those of the Proterozoic rocks in which the plutons were emplaced, thereby indicating that Pb in the younger rocks and ore deposits was inherited from the basement rocks and their sources. No Pb isotope differences distinguish Late Cretaceous and early Tertiary igneous complexes that contain large economic porphyry copper deposits from less rich or smaller deposits that have not been considered economic for mining. Lead isotope compositions of Late Cretaceous and early Tertiary plutons and sulfide minerals from 30 metallic mineral districts, furthermore, require that the southeastern Arizona Pb province be divided into two subprovinces. The northern subprovince has generally lower 206Pb/204Pb and higher model Th/U, and the southern subprovince has higher 206Pb/204Pb and lower model Th/U. These Pb isotope differences are inferred to result from differences in their respective post-1.7 Ga magmatic histories. Throughout Arizona, Pb isotope compositions of Late Cretaceous and early Tertiary plutons and associated sulfide minerals are distinct from those of Jurassic plutons and also middle Tertiary igneous rocks and sulfide minerals. These differences most likely reflect changes in tectonic setting and magmatic sources. Within Late Cretaceous and early Tertiary igneous complexes that host economic porphyry copper deposits, there is commonly a decrease in Pb isotope composition from older to younger plutons. This decrease in Pb isotope values with time suggests an increasing involvement of crust with lower U/Pb than average crust in the source(s) of Late Cretaceous and early Tertiary magmas. Lead isotope compositions of the youngest porphyries in the igneous complexes are similar to those in most sulfide minerals within the associated porphyry copper deposit. This Pb isotope similarity argues for a genetic link between them. However, not all Pb in the sulfide minerals in porphyry copper deposits is magmatically derived. Some sulfide minerals, particularly those that are late stage, or distal to the main orebody, or in Proterozoic or Paleozoic rocks, have elevated Pb isotope compositions displaced toward the gross average Pb isotope composition of the local country rocks. The more radiogenic isotopic compositions argue for a contribution of Pb from those rocks at the site of ore deposition. Combining the Pb isotope data with available geochemical, isotopic, and petrologic data suggests derivation of the young porphyry copper-related plutons, most of their Pb, and other metals from a hybridized lower continental crustal source. Because of the likely involvement of subduction-related mantle-derived basaltic magma in the hybridized lower crustal source, an indiscernible mantle contribution is probable in the porphyry magmas. Clearly, in addition

The calcium isotope evolution of Lake Lisan, the Dead Sea glacial precursor

NASA Astrophysics Data System (ADS)

Bradbury, H. J.; Turchyn, A. V.; Wong, K.; Torfstein, A.

2016-12-01

Calcium is a stoichiometric component of carbonate minerals whose calcium isotopic composition reflects changes in the calcium isotope composition of the water from which it precipitates as well as the calcium isotope fractionation factor during precipitation. The lacustrine deposits of the last glacial Dead Sea (Lisan Formation) are dominated by carbonate minerals (aragonite) that record the geochemical history of the lake. The sediment sequence comprises alternating laminae of aragonite and clay-rich marls, interspersed with primary gypsum beds and disseminated secondary gypsum crystals. The aragonite precipitated annually during high lake stands associated with wet periods, while the primary gypsum precipitated during low lake conditions (arid periods). We report the calcium isotopic composition (δ44Ca in ‰ relative to bulk silicate earth) of primary aragonite laminae, primary gypsum and secondary gypsum at 1-5kyr resolution throughout the Lisan Formation sampled at the Masada section (70 - 14.5 ka). The δ44Ca of the primary gypsum averages +0.29‰, and displays smaller temporal variations than the aragonite, which averages -0.35‰ but ranges between +0.18‰ and -0.68‰. The aragonite δ44Ca changes temporally in sync with the previously reconstructed lake level suggesting the aragonite δ44Ca reflects changes in the lake calcium balance during lake level changes. The secondary gypsum composition (-0.3‰) corresponds to coeval aragonite samples. For the secondary gypsum to have a similar δ44Ca to the aragonite it is likely that the calcium derived from the aragonite in a near quantitative fashion through recrystallization of the aragonite to gypsum. A numerical box model is used to explore the effect of changing lake water levels on the calcium isotope composition of the aragonite and gypsum over the time interval studied.

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.

Observations of hydrogen and helium isotopes in solar cosmic rays. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Hurford, G. J.

1974-01-01

The isotopic composition of hydrogen and helium in solar cosmic rays provides a means of studying solar flare particle acceleration mechanisms since the enhanced relative abundance of rare isotopes, such as H-2, H-3, and He-3, is due to their production by inelastic nuclear collisions in the solar atmosphere during the flare. Electron isotope spectrometer on an IMP spacecraft was used to measure this isotopic composition. The response of the dE/dx-E particle telescope is discussed, and alpha particle channeling in thin detectors is identified as an important background source affecting measurement of low values of (He-3/He-4). The flare-averaged results obtained for the period October, 1972 November, 1973 are given.

Evidence for supernova injection into the solar nebula and the decoupling of r-process nucleosynthesis

PubMed Central

Brennecka, Gregory A.; Borg, Lars E.; Wadhwa, Meenakshi

2013-01-01

The isotopic composition of our Solar System reflects the blending of materials derived from numerous past nucleosynthetic events, each characterized by a distinct isotopic signature. We show that the isotopic compositions of elements spanning a large mass range in the earliest formed solids in our Solar System, calcium–aluminum-rich inclusions (CAIs), are uniform, and yet distinct from the average Solar System composition. Relative to younger objects in the Solar System, CAIs contain positive r-process anomalies in isotopes A < 140 and negative r-process anomalies in isotopes A > 140. This fundamental difference in the isotopic character of CAIs around mass 140 necessitates (i) the existence of multiple sources for r-process nucleosynthesis and (ii) the injection of supernova material into a reservoir untapped by CAIs. A scenario of late supernova injection into the protoplanetary disk is consistent with formation of our Solar System in an active star-forming region of the galaxy. PMID:24101483

Evidence for supernova injection into the solar nebula and the decoupling of r-process nucleosynthesis.

PubMed

Brennecka, Gregory A; Borg, Lars E; Wadhwa, Meenakshi

2013-10-22

The isotopic composition of our Solar System reflects the blending of materials derived from numerous past nucleosynthetic events, each characterized by a distinct isotopic signature. We show that the isotopic compositions of elements spanning a large mass range in the earliest formed solids in our Solar System, calcium-aluminum-rich inclusions (CAIs), are uniform, and yet distinct from the average Solar System composition. Relative to younger objects in the Solar System, CAIs contain positive r-process anomalies in isotopes A < 140 and negative r-process anomalies in isotopes A > 140. This fundamental difference in the isotopic character of CAIs around mass 140 necessitates (i) the existence of multiple sources for r-process nucleosynthesis and (ii) the injection of supernova material into a reservoir untapped by CAIs. A scenario of late supernova injection into the protoplanetary disk is consistent with formation of our Solar System in an active star-forming region of the galaxy.

Magnesium isotopic composition of the mantle

NASA Astrophysics Data System (ADS)

Teng, F.; Li, W.; Ke, S.; Marty, B.; Huang, S.; Dauphas, N.; Wu, F.; Helz, R. L.

2009-12-01

Studies of Mg isotopic composition of the Earth not only are important for understanding its geochemistry but also can shed light on the accretion history of the Earth as well as the evolution of the Earth-Moon system. However, to date, the Mg isotopic composition of the Earth is still poorly constrained and highly debated. There is uncertainty in the magnitude of Mg isotope fractionation at mantle temperatures and whether the Earth has a chondritic Mg isotopic composition or not. To constrain further the Mg isotopic composition of the mantle and investigate the behavior of Mg isotopes during igneous differentiation, we report >200 high-precision (δ26Mg < 0.1‰, 2SD) analyses of Mg isotopes on 1) global mid-ocean ridge basalts covering major ridge segments of the world and spanning a broad range in latitudes, chemical and radiogenic isotopic compositions; 2) ocean island basalts from Hawaiian (Koolau, Kilauea and Loihi) and French Polynesian volcanoes (Society island and Cook Austral chain); 3) olivine grains from Hawaiian volcanoes (Kilauea, Koolau and Loihi) and 4) peridotite xenoliths from Australia, China, France, Tanzania and USA. Global oceanic basalts and peridotite xenoliths have a limited (<0.2 ‰) variation in Mg isotopic composition, with an average δ26Mg = -0.25 relative to DSM3. Olivines from Hawaiian lavas have δ26Mg ranging from -0.43 to +0.03, with most having compositions identical to basalts and peridotites. Therefore, the mantle’s δ26Mg value is estimated to be ~ -0.25 ± 0.1 (2SD), different from that reported by Wiechert and Halliday (2007; δ26Mg = ~ 0) but similar to more recent studies (δ26Mg = -0.27 to -0.33) (Teng et al. 2007; Handler et al. 2009; Yang et al., 2009). Moreover, we suggest the Earth, as represented by the mantle, has a Mg isotopic composition similar to chondrites (δ26Mg = ~-0.33). The need for a model such as that of Wiechert and Halliday (2007) that involves sorting of chondrules and calcium-aluminum-rich inclusions in the proto planetary disc is thus not required to explain the Mg isotopic composition of the Earth.

Stable water isotope patterns in a climate change hotspot: the isotope hydrology framework of Corsica (western Mediterranean).

PubMed

van Geldern, Robert; Kuhlemann, Joachim; Schiebel, Ralf; Taubald, Heinrich; Barth, Johannes A C

2014-06-01

The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (δP) with values of-8.6(± 0.2) ‰ for δ(18)O and-58(± 2) ‰ for δ(2)H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of-0.17(± 0.02) ‰ per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.

Potassium isotope abundances in Australasian tektites and microtektites.

NASA Astrophysics Data System (ADS)

Herzog, G. F.; O'D. Alexander, C. M.; Berger, E. L.; Delaney, J. S.; Glass, B. P.

2008-10-01

We report electron microprobe determinations of the elemental compositions of 11 Australasian layered tektites and 28 Australasian microtektites; and ion microprobe determinations of the 41K/39K ratios of all 11 tektites and 13 of the microtektites. The elemental compositions agree well with literature values, although the average potassium concentrations measured here for microtektites, 1.1 1.6 wt%, are lower than published average values, 1.9 2.9 wt%. The potassium isotope abundances of the Australasian layered tektites vary little. The average value of δ41K, 0.02 ± 0.12‰ (1σ mean), is indistinguishable from the terrestrial value (= 0 by definition) as represented by our standard, thereby confirming four earlier tektite analyses of Humayun and Koeberl (2004). In agreement with those authors, we conclude that evaporation has significantly altered neither the isotopic nor the elemental composition of Australasian layered tektites for elements less volatile than potassium. Although the average 41K/39K ratio of the microtektites, 1.1 ± 1.7‰ (1σ mean), is also statistically indistinguishable from the value for the standard, the individual ratios vary over a very large range, from -10.6 ± 1.4‰ to +13.8 ± 1.5‰ and at least three of them are significantly different from zero. We interpret these larger variations in terms of the evaporation of isotopically light potassium; condensation of potassium in the vapor plume; partial or complete stirring and quenching of the melts; and the possible uptake of potassium from seawater. That the average 41K/39K ratio of the microtektites equals the terrestrial value suggests that the microtektite-forming system was compositionally closed with respect to potassium and less volatile elements. The possibility remains open that 41K/39K ratios of microtektites vary systematically with location in the strewn field.

Intra-event isotope and raindrop size data of tropical rain reveal effects concealed by event averaged data

NASA Astrophysics Data System (ADS)

Managave, S. R.; Jani, R. A.; Narayana Rao, T.; Sunilkumar, K.; Satheeshkumar, S.; Ramesh, R.

2016-08-01

Evaporation of rain is known to contribute water vapor, a potent greenhouse gas, to the atmosphere. Stable oxygen and hydrogen isotopic compositions (δ18O and, δD, respectively) of precipitation, usually measured/presented as values integrated over rain events or monthly mean values, are important tools for detecting evaporation effects. The slope ~8 of the linear relationship between such time-averaged values of δD and δ18O (called the meteoric water line) is widely accepted as a proof of condensation under isotopic equilibrium and absence of evaporation of rain during atmospheric fall. Here, through a simultaneous investigation of the isotopic and drop size distributions of seventeen rain events sampled on an intra-event scale at Gadanki (13.5°N, 79.2°E), southern India, we demonstrate that the evaporation effects, not evident in the time-averaged data, are significantly manifested in the sub-samples of individual rain events. We detect this through (1) slopes significantly less than 8 for the δD-δ18O relation on intra-event scale and (2) significant positive correlations between deuterium excess ( d-excess = δD - 8*δ18O; lower values in rain indicate evaporation) and the mass-weighted mean diameter of the raindrops ( D m ). An estimated ~44 % of rain is influenced by evaporation. This study also reveals a signature of isotopic equilibration of rain with the cloud base vapor, the processes important for modeling isotopic composition of precipitation. d-excess values of rain are modified by the post-condensation processes and the present approach offers a way to identify the d-excess values least affected by such processes. Isotope-enabled global circulation models could be improved by incorporating intra-event isotopic data and raindrop size dependent isotopic effects.

New insights into Mo and Ru isotope variation in the nebula and terrestrial planet accretionary genetics

NASA Astrophysics Data System (ADS)

Bermingham, K. R.; Worsham, E. A.; Walker, R. J.

2018-04-01

When corrected for the effects of cosmic ray exposure, Mo and Ru nucleosynthetic isotope anomalies in iron meteorites from at least nine different parent bodies are strongly correlated in a manner consistent with variable depletion in s-process nucleosynthetic components. In contrast to prior studies, the new results show no significant deviations from a single correlation trend. In the refined Mo-Ru cosmic correlation, a distinction between the non-carbonaceous (NC) group and carbonaceous chondrite (CC) group is evident. Members of the NC group are characterized by isotope compositions reflective of variable s-process depletion. Members of the CC group analyzed here plot in a tight cluster and have the most s-process depleted Mo and Ru isotopic compositions, with Mo isotopes also slightly enriched in r- and possibly p-process contributions. This indicates that the nebular feeding zone of the NC group parent bodies was characterized by Mo and Ru with variable s-process contributions, but with the two elements always mixed in the same proportions. The CC parent bodies sampled here, by contrast, were derived from a nebular feeding zone that had been mixed to a uniform s-process depleted Mo-Ru isotopic composition. Six molybdenite samples, four glacial diamictites, and two ocean island basalts were analyzed to provide a preliminary constraint on the average Mo isotope composition of the bulk silicate Earth (BSE). Combined results yield an average μ97Mo value of +3 ± 6. This value, coupled with a previously reported μ100Ru value of +1 ± 7 for the BSE, indicates that the isotopic composition of the BSE falls precisely on the refined Mo-Ru cosmic correlation. The overlap of the BSE with the correlation implies that there was homogeneous accretion of siderophile elements for the final accretion of 10 to 20 wt% of Earth's mass. The only known cosmochemical materials with an isotopic match to the BSE, with regard to Mo and Ru, are some members of the IAB iron meteorite complex and enstatite chondrites.

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.

On the progressive enrichment of the oxygen isotopic composition of water along a leaf.

PubMed

Farquhar, G. D.; Gan, K. S.

2003-06-01

A model has been derived for the enrichment of heavy isotopes of water in leaves, including progressive enrichment along the leaf. In the model, lighter water is preferentially transpired leaving heavier water to diffuse back into the xylem and be carried further along the leaf. For this pattern to be pronounced, the ratio of advection to diffusion (Péclet number) has to be large in the longitudinal direction, and small in the radial direction. The progressive enrichment along the xylem is less than that occurring at the sites of evaporation in the mesophyll, depending on the isolation afforded by the radial Péclet number. There is an upper bound on enrichment, and effects of ground tissue associated with major veins are included. When transpiration rate is spatially nonuniform, averaging of enrichment occurs more naturally with transpiration weighting than with area-based weighting. This gives zero average enrichment of transpired water, the modified Craig-Gordon equation for average enrichment at the sites of evaporation and the Farquhar and Lloyd (In Stable Isotopes and Plant Carbon-Water Relations, pp. 47-70. Academic Press, New York, USA, 1993) prediction for mesophyll water. Earlier results on the isotopic composition of evolved oxygen and of retro-diffused carbon dioxide are preserved if these processes vary in parallel with transpiration rate. Parallel variation should be indicated approximately by uniform carbon isotope discrimination across the leaf.

2H and 18O depletion of water close to organic surfaces

NASA Astrophysics Data System (ADS)

Chen, Guo; Auerswald, Karl; Schnyder, Hans

2016-06-01

Hydrophilic surfaces influence the structure of water close to them and may thus affect the isotope composition of water. Such an effect should be relevant and detectable for materials with large surface areas and low water contents. The relationship between the volumetric solid : water ratio and the isotopic fractionation between adsorbed water and unconfined water was investigated for the materials silage, hay, organic soil (litter), filter paper, cotton, casein and flour. Each of these materials was equilibrated via the gas phase with unconfined water of known isotopic composition to quantify the isotopic difference between adsorbed water and unconfined water. Across all materials, isotopic fractionation was significant (p<0.05) and negative (on average -0.91 ± 0.22 ‰ for 18/16O and -20.6 ± 2.4 ‰ for 2/1H at an average solid : water ratio of 0.9). The observed isotopic fractionation was not caused by solutes, volatiles or old water because the fractionation did not disappear for washed or oven-dried silage, the isotopic fractionation was also found in filter paper and cotton, and the fractionation was independent of the isotopic composition of the unconfined water. Isotopic fractionation became linearly more negative with increasing volumetric solid : water ratio and even exceeded -4 ‰ for 18/16O and -44 ‰ for 2/1H. This fractionation behaviour could be modelled by assuming two water layers: a thin layer that is in direct contact and influenced by the surface of the solid and a second layer of varying thickness depending on the total moisture content that is in equilibrium with the surrounding vapour. When we applied the model to soil water under grassland, the soil water extracted from 7 and 20 cm depth was significantly closer to local meteoric water than without correction for the surface effect. This study has major implications for the interpretation of the isotopic composition of water extracted from organic matter, especially when the volumetric solid : water ratio is larger than 0.5 or for processes occurring at the solid-water interface.

Voyager measurements of the isotopic composition of cosmic-ray aluminum and implications for the propagation of cosmic rays

NASA Technical Reports Server (NTRS)

Lukasiak, A.; Mcdonald, F. B.; Webber, W. R.

1994-01-01

We report a new measurement of the cosmic-ray isotopic composition of aluminum in the low-energy range form 75 to 206 MeV per nucleon.This measurement was made using the high-energy telescope of the CRS experiment on the Voyager 1 and 2 spacecraft during the time period from 1977 to 1993 with an average solar modulation level about 497 MV, roughly the same as at Earth near sunspot minimum. We obtain approximately 430 Al events of which approximately 35 are Al-26 and 395 are Al-27. The Al isotopes were separated with an average mass resolution sigma of 0.35 amu. Our interpretation of the isotopic composition of cosmic-ray aluminum is based on a standard Leaky-Box model for the interstellar propagation of cosmic-ray nuclei using the latest cross sections of the New Mexico-Saclay collaboration as well as a disk-halo diffusion model. From our observed ratio Al-26/Al-27 of 8.3 +/- 2.4 % we deduce an average interstellar density of about 0.52 (+0.26, -0.2) atoms per cu cm. This density is larger than the value of 0.28 (+0.14, -0.11) atoms per cu cm we found from an analysis of the observed abundance of the longer lived Be-10 made using data from the Voyager detectors over almost the same time interval and using essentially the same propagation program.

Sources of osmium to the modern oceans: New evidence from the 190Pt-186Os system

USGS Publications Warehouse

McDaniel, D.K.; Walker, R.J.; Hemming, S.R.; Horan, M.F.; Becker, H.; Grauch, R.I.

2004-01-01

High precision Os isotope analysis of young marine manganese nodules indicate that whereas the composition of modern seawater is radiogenic with respect to 187Os/188Os, it has 186Os/188Os that is within uncertainty of the chondritic value. Marine Mn nodule compositions thus indicate that the average continental source of Os to modern seawater had long-term high Re/Os compared to Pt/Os. Analyses of loess and freshwater Mn nodules support existing evidence that average upper continental crust (UCC) has resolvably suprachondritic 186Os/188Os, as well as radiogenic 187Os/188Os. Modeling the composition of seawater as a two-component mixture of oceanic/cosmic Os with chondritic Os compositions and continentally-derived Os demonstrates that, insofar as estimates for the composition of average UCC are accurate, congruently weathered average UCC cannot be the sole continental source of Os to seawater. Our analysis of four Cambrian black shales confirm that organic-rich sediments can have 187Os/188Os ratios that are much higher than average UCC, but 186Os/188Os compositions that are generally between those of chondrites and average-UCC. Preferential weathering of black shales can result in dissolved Os discharged to the ocean basins that has a much lower 186Os/188Os than does average upper crust. Modeling the available data demonstrates that augmentation of estimated average UCC compositions with less than 0.1% additional black shale and 1.4% additional ultramafic rock can produce a continental end-member Os isotopic composition that satisfies the requirements imposed by the marine Mn nodule data. The interplay of these two sources provides a mechanism by which the 187Os/188Os of seawater can change as sources and weathering conditions change, yet seawater 186Os/188Os varies only minimally. ?? 2004 Elsevier Ltd.

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.

The 238U/235U isotope ratio of the Earth and the solar system: Constrains from a gravimetrically calibrated U double spike and implications for absolute Pb-Pb ages

NASA Astrophysics Data System (ADS)

Weyer, Stefan; Noordmann, Janine; Brennecka, Greg; Richter, Stephan

2010-05-01

The ratio of 238U and 235U, the two primordial U isotopes, has been assumed to be constant on Earth and in the solar system. The commonly accepted value for the 238U/235U ratio, which has been used in Pb-Pb dating for the last ~ 30 years, was 137.88. Within the last few years, it has been shown that 1) there are considerable U isotope variations (~1.3‰) within terrestrial material produced by isotope fractionation during chemical reactions [1-3] and 2) there are even larger isotope variations (at least 3.5‰) in calcium-aluminum-rich inclusions (CAIs) in meoteorites that define the currently accepted age of the solar system [4]. These findings are dramatic for geochronology, as a known 238U/235U is a requirement for Pb-Pb dating, the most precise dating technique for absolute ages. As 238U/235U variations can greatly affect the reported absolute Pb-Pb age, understanding and accurately measuring variation of the 238U/235U ratio in various materials is critical, With these new findings, the questions also arises of "How well do we know the average U isotope composition of the Earth and the solar system?" and "How accurate can absolute Pb-Pb ages be?" Our results using a gravimetrically calibrated 233U/236U double spike IRMM 3636 [5] indicate that the U standard NBL 950a, which was commonly used to define the excepted "natural" 238U/235U isotope ratio, has a slightly lower 238U/235U of 137.836 ± 0.024. This value is indistinguishable from the U isotope compositions for NBL 960 and NBL112A, which have been determined by several laboratories, also using the newly calibrated U double spike IRMM 3636 [6]. These findings provide new implications about the average U isotope composition of the Earth and the solar system. Basalts display a very tight range of U isotope variations (~0.25-0.32‰ relative to SRM 950a). Their U isotope composition is also very similar to that of chondrites [4], which however appear to show a slightly larger spread. Accepting terrestrial basalts to be the best representation of the U isotope composition of the Earth and the solar system, and the new 238U/235U for SRM 950a of 137.836, this would result in an average 238U/235U for the Earth and the solar system of ~ 137.80. The effect of a revised 238U/235U ratio on Pb-Pb ages is age dependent. It results in an age overestimation of ~0.8 Ma for the age of the solar system and up to 1.5 Ma for very young material (with bulk Earth U isotope composition). [1] Stirling, C.H., Andersen, M.B., Potter, E.-K., et al. (2007) EPSL 264, 208-225; [2] Weyer, S., Anbar, A. D., Gerdes, A., et al. (2008) GCA 72, 345-359. [3] Bopp, C.H., Lundstrom, C.C., Johnsons, T.M., Glessner, J.G. (2009) Geology 37, 611-614. [4] Brennecka, G.A., Weyer, S., Wadhwa, et al. (2010) Science, 327, p. 449. [5] Richter, S., Alonzo-Munoz, A., Eykens, R., et al. (2008) IJMS 269, 145-148. [6] Richter, S., et al. EGU meeting 2010.

Neutron activation analysis of nuclides from stellar and man-induced nuclear reactions

NASA Astrophysics Data System (ADS)

Oliver, L. L.

Neutron activation and gamma counting were used to determine the relative abundances of six stable tellurium isotopes in the acid-etched residues of the Allende meteorite. The results were correlated with the isotopic compositions of xenon and the elemental abundances of helium and neon in similarly prepared residues. Nucleosynthesis appears to be the only viable explanation or the anomalous isotopic and elemental compositions observed in these residues. Results suggest that the solar system condensed from an isotopically and chemically zoned nebula that was produced by the explosion of a supernova, concentric with the present Sun. A combination of neutron activation and mass spectrometry was used to determine the concentrations of fissiogenic iodine 129 and stable iodine 127 in rain, milk and the thyroids of man, cow and deer from Missouri. Rain and deer thyroids show the highest average values of the iodine 129/iodine 127 ratio. Milk and the thyroids of cattle and humans show successively lower values of the iodine 129/iodine 127 ratio due to dietary additives of mineral iodine and to biological averaging.

Xenon isotopic composition of the Mid Ocean Ridge Basalt (MORB) source

NASA Astrophysics Data System (ADS)

Peto, M. K.; Mukhopadhyay, S.

2012-12-01

Although convection models do not preclude preservation of smaller mantle regions with more pristine composition throughout Earth's history, it has been widely assumed that the moon forming giant impact likely homogenizes the whole mantle following a magma ocean that extended all the way to the bottom of the mantle. Recent findings of tungsten and xenon heterogeneities in the mantle [1,2,3,4], however, imply that i) the moon forming giant impact may not have homogenized the whole mantle and ii) plate tectonics was inefficient in erasing early formed compositional differences, particularly for the xenon isotopes. Therefore, the xenon isotope composition in the present day mantle still preserves a memory of early Earth processes. However, determination of the xenon isotopic composition of the mantle source is still scarce, since the mantle composition is overprinted by post-eruptive atmospheric contamination in basalts erupted at ocean islands and mid ocean ridges. The xenon composition of the depleted upper mantle has been defined by the gas rich sample, 2πD43 (also known as "popping rock"), from the North Atlantic (13° 469`N). However, the composition of a single sample is not likely to define the composition of the upper mantle, especially since popping rock has an "enriched" trace element composition. We will present Ne, Ar and Xe isotope data on MORB glass samples with "normal" helium isotope composition (8±1 Ra) from the Southeast Indian Ridge, the South Atlantic Ridge, the Sojourn Ridge, the Juan de Fuca, the East Pacific Rise, and the Gakkel Ridge. Following the approach of [1], we correct for syn- and post-eruptive atmosphere contamination, and determine the variation of Ar and Xe isotope composition of the "normal" MORB source. We investigate the effect of atmospheric recycling in the variation of MORB mantle 40Ar/36Ar and 129Xe/130Xe ratios, and attempt to constrain the average upper mantle argon and xenon isotopic compositions. [1] Mukhopadhyay, Nature 2012; [2] Tucker et al., EPSL (in review); [3] Moreira et al., Nature 1998 [4] Touboul et al., Science 2012.

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.

The Boron Isotopic Composition of Elephant Dung: Inputs to the Global Boron Budget

NASA Astrophysics Data System (ADS)

Williams, L. B.; Hervig, R. L.

2011-12-01

A survey of boron in kerogen showed isotopically light δ11B values (0 to -50%) that are distinctly different from most mineral and natural water B reservoirs. Diagenesis releases this isotopically light B into pore fluids when hydrocarbons are generated, thus enriching oilfield brines in 10B. This observation suggests that borated biomolecules (BM) are primarily tetrahedral favoring 10B, whereas 11B is preferred in trigonal coordination. Plants, with optimal concentrations up to 100ppm, contribute more B than animal remains to sediment. Elephants are one of the largest herbivores on earth, consuming 200 - 250 kg of plant material/day and producing 50 kg of manure/day. They are inefficient at digestion, thus the manure contains >50% undigested plant material. Dung samples are therefore ideal for studying the δ11B of both the food input and digested output of a significant B supply to sedimentary systems. Horse and rabbit manure were studied for comparison to evaluate B isotope variations in the food supply and potential vital effects on the output. B-content and isotopic composition of dung plant material and digested fractions were measured in the solid state by secondary ion mass spectrometry. The digests were rinsed in 1.8% mannitol, a B-complexing agent, to remove surface adsorbed-B, then air dried and Au-coated for charge compensation. Results showed that the elephant diet contains 3-13 ppm B, with an average δ11B of -20 ± 0.8% (1σ), while rabbit food had 88 ppm B with a δ11B of -50 ± 1.3 %. The digested fraction of the elephant dung contains 4-10ppm B with average δ11B values of -12 ± 1.2%. In comparison, horse manure with 11-21 ppm B has a δ11B of -10.7 ± 0.5% and rabbit manure contains 2-3 ppm B with a δ11B of -8.8 ± 1%. Boron isotope compositions of these manures are indistinguishable (within error). Clearly plant material is a major contributor of isotopically light B to sediments. The herbivores studied fractionate their total B intake in favor of 11B, thus increasing the δ11B of the (solid) digested material relative to the food source. This would not affect the overall BM input to the sediment because the dung contains the undigested plants. If we assume that the average B isotopic composition of dung, ~10ppm B at -20%, represents an average BM in sediment, and that the mass of sediments (1E24 g) is comparable to the mass of seawater with an average 5ppm B at +40%, then it is clear that BM plays a major role in balancing the global B budget. Note: This research was NOT funded by taxpayer dollars. The Phoenix Zoo kindly approved the proposal to sample elephant dung for this study and their support is greatly appreciated.

Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia

NASA Astrophysics Data System (ADS)

Brookman, Tom H.; Ambrose, Stanley H.

2012-09-01

Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C3 and C4 vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ13C and δ18O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north-south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.

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.

Past leaded gasoline emissions as a nonpoint source tracer in riparian systems: A study of river inputs to San Francisco Bay

USGS Publications Warehouse

Dunlap, C.E.; Bouse, R.; Flegal, A.R.

2000-01-01

Variations in the isotopic composition of lead in 1995-1998 river waters flowing into San Francisco Bay trace the washout of lead deposited in the drainage basin from leaded gasoline combustion. At the confluence of the Sacramento and San Joaquin rivers where they enter the Bay, the isotopic compositions of lead in the waters define a linear trend away from the measured historical compositions of leaded gas in California. The river waters are shifted away from leaded gasoline values and toward an isotopic composition similar to Sierra Nevadan inputs which became the predominant source of sedimentation in San Francisco Bay following the onset of hydraulic gold mining in 1853. Using lead isotopic compositions of hydraulic mine sediments and average leaded gasoline as mixing end members, we calculate that more than 50% of the lead in the present river water originated from leaded gasoline combustion. The strong adsorption of lead (log K(d) > 7.4) to particulates appears to limit the flushing of gasoline lead from the drainage basin, and the removal of that lead from the system may have reached an asymptotic limit. Consequently, gasoline lead isotopes should prove to be a useful nonpoint source tracer of the environmental distribution of particle- reactive anthropogenic metals in freshwater systems.

Boron contents and isotopic compositions of hog manure, selected fertilizers, and water in Minnesota

USGS Publications Warehouse

Komor, S.C.

1997-01-01

Boron-isotope (δ11B) values may be useful as surrogate tracers of contaminants and indicators of water mixing in agricultural settings. This paper characterizes the B contents and isotopic compositions of hog manure and selected fertilizers, and presents δ11B data for ground and surface water from two agricultural areas. Boron concentrations in dry hog manure averaged 61 mg/kg and in commercial fertilizers ranged from below detection limits in some brands of ammonium nitrate and urea to 382 mg/kg in magnesium sulfate. Values of δ11B of untreated hog manure ranged from 7.2 to 11.2o/oo and of N fertilizers were −2.0 to 0.7o/oo. In 22 groundwater samples from a sand-plain aquifer in east-central Minnesota, B concentrations averaged 0.04 mg/L and δ11B values ranged from 2.3 to 41.5o/oo. Groundwater beneath a hog feedlot and a cultivated field where hog manure was applied had B-isotope compositions consistent with the water containing hog-manure leachate. In a 775-km2 watershed with silty-loam soils in southcentral Minnesota: 18 samples of subsurface drainage from corn (Zea mays L.) and soybean (Glycine max L. Merr.) fields had average B concentrations of 0.06 mg/L and δ11B values of 5.3 to 15.1o/oo; 27 stream samples had average B concentrations of 0.05 mg/L and δ11B values of 1.0 to 19.0o/oo; and eight groundwater samples had average B concentrations of 0.09 mg/L and δ11B values of −0.3 to 23.0o/oo. Values of δ11B and B concentrations, when plotted against one another, define a curved mixing trend that suggests subsurface drainage and stream water contain mixtures of B from shallow and deep groundwater.

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.

Determination of the components of stormflow using water chemistry and environmental isotopes, Mattole River basin, California

USGS Publications Warehouse

Kennedy, V.C.; Kendall, C.; Zellweger, G.W.; Wyerman, T.A.; Avanzino, R.J.

1986-01-01

The chemical and isotopic composition of rainfall and stream water was monitored during a storm in the Mattole River basin of northwestern California. About 250 mm of rain fell during 6 days (???80% within a 42 h period) in late January, 1972, following 24 days of little or no precipitation. River discharge near Petrolia increased from 22 m3 s-1 to a maximum of 1300 m3 s-1 while chloride and silica concentrations decreased only from 3.2 to 2.1 and 11.5 to 8.6 mgl-1, respectively. Meanwhile, the isotopic composition of the river changed from ??D = - 42???, ??180 = - 6.8??? and 40 tritium units (T.U.) to extreme values at highest flow of ??D = - 35???, ??180 = - 5.9??? and 25 T.U. in response to volume-weighted rainfall averaging ??D = - 19.5???, ??180 = - 3.1??? and 18 T.U. Despite much rainfall of a composition quite different from that of the prestorm river water, "buffering" processes in the watershed greatly restricted changes in the chemical and isotopic content of the river during storm runoff. Because of the physical and hydrologic characteristics of the watershed, major contributions of groundwater to stormflow are very unlikely. The large increase in dissolved chemical load observed at maximum river discharge required that extensive interaction with, and presumably penetration of, soils occurred within a few hours time. Such a large increase in chemical load also required subsurface stormflow throughout a high proportion of the watershed. Chemical and isotopic stabilization of stormflow is believed to be due mainly to displacement of prestorm soil water, with some effects on river chemistry due to rapid rain-soil interactions. The isotopic and chemical composition of prestorm soil moisture cannot readily be predicted a priori because of possible variability in rainfall composition, evaporation, and exchange with atmospheric moisture, nor can it be assumed that baseflow has a predictable relation to the chemical or isotopic composition of water displaced from soils during storms. Therefore, it seems inappropriate to draw conclusions as to the relative proportions of groundwater and rainfall in runoff from a particular storm based only on the average compositions of rainfall, stormflow, and prestorm river water, as has been done in most previous isotope hydrograph studies. Given the great variation in hydrology, topography, soil characteristics, rainfall intensity and quantity, etc. from place to place, the relative amount of overland flow, subsurface flow from the unsaturated zone and of groundwater in stormflow can vary greatly in time and space. ?? 1986.

Implications of 187Os isotopic heterogeneities in a mantle plume: evidence from Gorgona Island and Curaçao

NASA Astrophysics Data System (ADS)

Walker, Richard J.; Storey, Michael; Kerr, Andrew C.; Tarney, John; Arndt, Nicholas T.

1999-03-01

Recent work has suggested that the mafic-ultramafic volcanism in evidence throughout portions of the Caribbean, Central America, and northern South America, including the islands of Gorgona and Curaçao, was generated as part of a middle-Cretaceous, large igneous province. New Re-Os isochron results for tholeiitic basalts from Gorgona and Curaçao indicate crystallization ages of 89.2 ± 5.2 and 85.6 ± 8.1 Ma, respectively, consistent with reported Ar ages. The Gorgona ultramafic suite shows a large range in initial Os isotopic composition, with γ Os values ranging from -0.5 to +12.4. This large range reflects isotopic heterogeneities in the mantle source similar to those observed for modern ocean island basalts. In contrast to ocean island basalts, however, Os isotopic compositions do not correlate with variations in Nd, Sr, or Pb isotopic compositions, which are within the range of depleted mid-ocean ridge basalts. The processes that produced these rocks evidently resulted in the decoupling of Os isotopes from the Nd, Sr, and Pb isotopic systems. Picrites from Curaçao have very uniform, chondritic initial Os isotopic compositions, with initial γ Os values ranging only from -0.4 to ±1.4. Basalts from Curaçao, however, define an isochron with a 187Os-enriched initial isotopic composition (γ Os = +9.5). In contrast to the 187Os-enriched ultramafic rocks from Gorgona, the enrichment in these basalts could have resulted from lithospheric contamination. If the Gorgona and Curaçao rocks were derived from the same plume, Os results, combined with Sr, Nd, and Pb data indicate a heterogeneous plume, with multiple compositionally and isotopically distinct domains. The Os isotopic results require derivation of Os from a minimum of two distinct reservoirs, one with a composition very similar to the chondritic average and one with long-term enriched Re/Os. Oceanic crustal recycling has been invoked to explain most of the 187Os enrichments that have been observed in ocean island basalt sources and could potentially apply to the Gorgona suite. Crustal recycling, however, requires large proportions of very ancient recycled basaltic crust in the sources of the 187Os-enriched ultramafic rocks to explain the magnitude of 187Os enrichments observed. For example, addition of 20% oceanic crust to fertile mantle, and nearly 3 billion years are necessary to generate a reservoir with the Os isotopic composition of the most radiogenic komatiites. If the recycled oceanic crust was added to basalt-depleted mantle, as may be indicated by ɛ Nd values for the komatiites averaging about +10, even larger proportions of older crust are required. Large proportions of oceanic mafic crust in the sources of the 187Os-enriched komatiites, although petrologically conceivable under certain melting conditions, is unlikely here given the limited trace element and lithophile isotope system variations. These results raise questions about the efficacy of using Os isotopes to constrain the proportion of recycled oceanic crust in other plumes. Other possible mechanisms for generating 187Os-enriched mantle include invoking the existence of a 187Os-enriched lower mantle, and minor outer core-lower mantle interactions.

Isotopic constraints on ice age fluids in active geothermal systems: Reykjanes, Iceland

NASA Astrophysics Data System (ADS)

Pope, Emily C.; Bird, Dennis K.; Arnórsson, Stefán; Fridriksson, Thráinn; Elders, Wilfred A.; Fridleifsson, Gudmundur Ó.

2009-08-01

The Reykjanes geothermal system is located on the landward extension of the Mid-Atlantic Ridge in southwest Iceland, and provides an on-land proxy to high-temperature hydrothermal systems of oceanic spreading centers. Previous studies of elemental composition and salinity have shown that Reykjanes geothermal fluids are likely hydrothermally modified seawater. However, δD values of these fluids are as low as -23‰, which is indicative of a meteoric water component. Here we constrain the origin of Reykjanes hydrothermal solutions by analysis of hydrogen and oxygen isotope compositions of hydrothermal epidote from geothermal drillholes at depths between 1 and 3 km. δDEPIDOTE values from wells RN-8, -9, -10 and -17 collectively range from -60 to -78‰, and δ18OEPIDOTE in these wells are between -3.0 and 2.3‰. The δD values of epidote generally increase along a NE trend through the geothermal field, whereas δ18O values generally decrease, suggesting a southwest to northeast migration of the geothermal upflow zone with time that is consistent with present-day temperatures and observed hydrothermal mineral zones. For comparative analysis, the meteoric-water dominated Nesjavellir and Krafla geothermal systems, which have a δDFLUID of ˜ -79‰ and -89‰, respectively, show δDEPIDOTE values of -115‰ and -125‰. In contrast, δDEPIDOTE from the mixed meteoric-seawater Svartsengi geothermal system is -68‰; comparable to δDEPIDOTE from well RN-10 at Reykjanes. Stable isotope compositions of geothermal fluids in isotopic equilibrium with the epidotes at Reykjanes are computed using published temperature dependent hydrogen and oxygen isotope fractionation curves for epidote-water, measured isotope composition of the epidotes and temperatures approximated from the boiling point curve with depth. Calculated δD and δ18O of geothermal fluids are less than 0‰, suggesting that fluids of meteoric or glacial origin are a significant component of the geothermal solutions. Additionally, δDFLUID values in equilibrium with geothermal epidote are lower than those of modern-day fluids, whereas calculated δ18OFLUID values are within range of the observed fluid isotope composition. We propose that modern δDEPIDOTE and δDFLUID values are the result of diffusional exchange between hydrous alteration minerals that precipitated from glacially-derived fluids early in the evolution of the Reykjanes system and modern seawater-derived geothermal fluids. A simplified model of isotope exchange in the Reykjanes geothermal system, in which the average starting δDROCK value is -125‰ and the water to rock mass ratio is 0.25, predicts a δDFLUID composition within 1‰ of average measured values. This model resolves the discrepancy between fluid salinity and isotope composition of Reykjanes geothermal fluids, explains the observed disequilibrium between modern fluids and hydrothermal epidote, and suggests that rock-fluid interaction is the dominant control over the evolution of fluid isotope composition in the hydrothermal system.

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.

Sedimentary input into the source of Martinique lavas: a Li perspective

NASA Astrophysics Data System (ADS)

Tang, M.; Chauvel, C.; Rudnick, R. L.

2013-12-01

The Lesser Antilles arc is known for the prominent continental crustal signatures in its lavas. It thus provides an ideal target for studying crustal recycling in subduction zones. Martinique Island, located in the middle of the Lesser Antilles arc, has been well characterized for its elemental and radiogenic isotope geochemistry (Labanieh et al., 2012). We measured Li isotopes in the Martinique lavas as well as sediments cored at the southern (Site 144) and northern part (Site 543) of the subducting slab. The sediments show a large isotopic variation (δ7Li ~ -4.2‰ to +3.2‰) but the average δ7Li of -1.1 × 2.4‰ (1 σ, n = 15) is significantly lower than that of N-MORB (δ7Li = + 3.4 × 0.7‰, 1 σ, Tomascak et al., 2008), reflecting the influence of chemical weathering in the continental provenance. Although the subducting sediments display marked mineralogical and chemical shifts from south to north due to different deposition distances to the continental platform (Carpentier et al., 2009), their average Li isotopic compositions are indiscernible from each other. With a few exceptions, the Li isotopic compositions of the Martinique lavas are systematically lighter than MORB, giving an average δ7Li of 1.6 × 1.4‰ (1 σ, n = 25, 4 exceptions excluded). The δ7Li values show no correlation with any radiogenic isotope ratios (206Pb/204Pb, 87Sr/86Sr, 143Nd/144Nd and 176Hf/177Hf), Li/Y ratio, La/Sm ratio and SiO2 content. Therefore, the light Li isotopic composition likely reflects the source characteristics rather than contamination within the arc crust. Incorporation of the isotopically light sediments from Site 144 and 543 in the source may explain the depletion of 7Li in the Martinique lavas. A two-end-member mixing model requires 2-5% addition of the sediments into the depleted mantle source, compared with 1-10% sediments constrained by radiogenic isotopes (Carpentier et al., 2008). References Carpentier, M., Chauvel, C., & Mattielli, N., 2008. Pb-Nd isotopic constraints on sedimentary input into the Lesser Antilles arc system. Earth and Planetary Science Letters, 272(1), 199-211. Carpentier, M., Chauvel, C., Maury, R. C., & Mattielli, N., 2009. The 'zircon effect' as recorded by the chemical and Hf isotopic compositions of Lesser Antilles forearc sediments. Earth and Planetary Science Letters, 287(1), 86-99. Labanieh, S., Chauvel, C., Germa, A., & Quidelleur, X., 2012. Martinique: a Clear Case for Sediment Melting and Slab Dehydration as a Function of Distance to the Trench. Journal of Petrology, 53(12), 2441-2464. Tomascak, P. B., Langmuir, C. H., le Roux, P. J., & Shirey, S. B. (2008). Lithium isotopes in global mid-ocean ridge basalts. Geochimica et Cosmochimica Acta, 72(6), 1626-1637.

Tracing mantle processes with Fe isotopes

NASA Astrophysics Data System (ADS)

Weyer, S.; Ionov, D.

2006-12-01

High precision Fe isotope measurements have been performed on various mantle peridotites (fertile lherzolites, harzburgites, metasomatised Fe-enriched rocks) and volcanic rocks (mainly oceanic basalts) from different localities and tectonic settings. Pimitive peridotites (Mg# = 0.894) yield delta56Fe = 0.02 and are significantly lighter than the basalts (average delta56Fe = 0.11). Furthermore, the peridotites display a negative correlation of iron isotopes with Mg#. Taken together, these findings imply that Fe isotopes fractionate during partial melting, with heavy isotopes preferentially entering the melt [1, 2]. A particularly good correlation of the Fe isotope composition and Mg# shown by poorly metasomatised spinel lherzolites of three localities (Horoman, Kamchatka and Lherz) was used to model Fe isotope fractionation during partial melting, resulting in alphamantle-melt = 1.0003. This value implies higher Fe isotope fractionation between residual mantle and mantle-derived melts (i.e. Delta56Femantle-melt = 0.2-0.3) than the observed difference between the peridotites and the basalts in this study. Our data on plagioclase lherzolites from Horoman and spinel lherzolites from other localities indicate that the difference in Fe isotope composition between mantle and basalts may be reduced by partial re-equilibration between the isotopically heavy basalts and the isotopically light depleted lithospheric mantle during melt ascent. Besides partial melting, the Fe isotope composition of mantle peridotites can also be significantly modified by metasomatic events. At two localities (Tok, Siberia and Tariat, Mongolia) Fe isotopes correlates with the Fe concentration of the peridotites, which was increased up to 14.5% FeO by melt percolation. Such processes can be accompanied by chromatographic effects and produce a range of Fe isotope compositions in the percolation columns, from extremely light to heavy (delta56Fe = -0.42 to +0.17). We propose that Fe isotopes can be used as a sensitive tracer to identify such metasomatic processes in the mantle. [1] Weyer et al. (2005) EPSL 240: 251-264 [2] Williams et al. (2005) EPSL 235 : 435-452

Light Stable Isotopic Compositions of Enriched Mantle Sources: Resolving the Dehydration Paradox

NASA Astrophysics Data System (ADS)

Dixon, J. E.; Bindeman, I. N.; Kingsley, R. H.

2017-12-01

An outstanding puzzle in mantle geochemistry has been the origin and evolution of Earth's volatile components. The "dehydration paradox" refers to the following conundrum. Mantle compositions for some enriched mid-ocean ridge (MORB) and ocean island (OIB) basalts basalts require involvement of a mostly dehydrated slab component to explain the trace element ratios and radiogenic isotopic compositions, but a fully hydrated slab component to explain the stable isotopic compositions. Volatile and stable isotopic data on enriched MORB show a diversity of enriched components. Pacific PREMA-type basalts (H2O/Ce = 215 ± 30, δDSMOW = -45 ± 5 ‰) are similar to those in the north Atlantic (H2O/Ce = 220 ± 30; δDSMOW = -30 to -40 ‰). Basalts with EM-type signatures have regionally variable volatile compositions. North Atlantic EM-type basalts are wetter (H2O/Ce = 330 ± 30) and have isotopically heavier hydrogen (δDSMOW = -57 ± 5 ‰) than north Atlantic MORB. South Atlantic EM-type basalts are damp (H2O/Ce = 120 ± 10) with intermediate δDSMOW (-68 ± 2 ‰), similar to dDSMOW for Pacific MORB. North EPR EM-type basalts are dry (H2O/Ce = 110 ± 20) and isotopically light (δDSMOW = -94 ± 3 ‰). Boron and lithium isotopic ratios parallel the trends observed for dDSMOW. A multi-stage metasomatic and melting model accounts for the origin of the enriched components by extending the subduction factory concept down through the mantle transition zone, with slab temperature a key variable. The dehydration paradox is resolved by decoupling of volatiles from lithophile elements, reflecting primary dehydration of the slab followed by secondary rehydration and re-equilibration by fluids derived from subcrustal hydrous phases (e.g., antigorite) in cooler, deeper parts of the slab. The "expanded subduction factory" model includes melting at several key depths, including 1) 180 to 280 km, where EM-type mantle compositions are generated above slabs with average to hot thermal profiles by addition of <1% carbonated sediment-derived supercritical fluids/melts to depleted asthenospheric or subcontinental lithospheric mantle, and 2) 410 to 660 km, where PREMA-type mantle sources are generated, above slabs with average to cool thermal profiles, by addition of <1% carbonated eclogite ± sediment-derived supercritical fluids to depleted mantle.

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.

Silicon and Zinc Isotopes in Ocean Island Basalts

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.; Moynier, F.

2013-12-01

Analyses of Ocean Island Basalts (OIB) have shown that the Earth's mantle contains isotopically distinct components, but current debate about the degree and scale of compositional variability persists. Isotopic heterogeneities in OIB for both radiogenic (e.g. Sr, Nd, Pb) and stable (e.g. Li, O, Ca) isotope systems have been attributed to the presence of recycled materials in different mantle reservoirs [1]. The study of both silicon and zinc isotopes in OIB form a complimentary approach to investigate potential heterogeneities in the mantle. Both isotope systems show limited fractionation during igneous process [2,3]. However, both Si and Zn exhibit larger (>1‰) variability in low-temperature environments (e.g. as a result of chemical weathering and biological utilization). Therefore, Si and Zn isotopes may be useful as tracers for the presence of crustal material (derived from low-T surface processes) in OIB source regions. Furthermore, characterizing the isotopic composition of the mantle is of central importance to the use of these isotopic systems as a basis for interplanetary comparisons. Here we present high-precision Si and Zn isotopic data obtained by MC-ICPMS for a diverse suite of OIB representing the EM-1, EM-2, and HIMU mantle components. Samples represent locations in the Pacific, Atlantic, and Indian Oceans. Data are reported as the permil deviation (×2 sd) from NBS28 for Si (δ30Si) and JMC-Lyon for Zn (δ66Zn). Average δ30Si values for OIB from EM-1 (-0.32×0.09‰), EM-2 (-0.30×0.03‰), and HIMU (-0.34×0.12‰) are all in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth (BSE) [4]. Similarly, the δ66Zn average values for OIB from the EM-1, EM-2, and HIMU components (0.31×0.06‰, 0.31×0.04‰, 0.31×0.05‰, respectively) agree well with previously published data for the δ66Zn value of BSE [3]. At the current levels of precision, both Si and Zn isotopes exhibit little variation in OIB, confirming the large-scale homogeneity of the mantle for these isotopic systems. Furthermore, when averaged according to surface location, neither Si nor Zn shows any variation in isotopic composition according to oceanic basin. However, some small variations in the data may be present; many HIMU samples (Mangaia, Cape Verde) are enriched in the lighter isotopes of Si (δ30Si tending toward chondritic values), which might reflect preservation of isotopic heterogeneity within the mantle, an incorporation of an isotopically light component in the source of these lavas, or isotopic fractionation during magmatic differentiation. References: [1] Hofmann, RiMG 2007 [2] Savage et al., GCA 2011 [3] Chen et al., EPSL 2013 [4] Savage et al., EPSL 2010

Delta13C values of grasses as a novel indicator of pollution by fossil-fuel-derived greenhouse gas CO2 in urban areas.

PubMed

Lichtfouse, Eric; Lichtfouse, Michel; Jaffrézic, Anne

2003-01-01

A novel fossil fuel pollution indicator based on the 13C/12C isotopic composition of plants has been designed. This bioindicator is a promising tool for future mapping of the sequestration of fossil fuel CO2 into urban vegetation. Theoretically, plants growing in fossil-fuel-CO2-contaminated areas, such as major cities, industrial centers, and highway borders, should assimilate a mixture of global atmospheric CO2 of delta13C value of -8.02 per thousand and of fossil fuel CO2 of average delta13C value of -27.28 per thousand. This isotopic difference should, thus, be recorded in plant carbon. Indeed, this study reveals that grasses growing near a major highway in Paris, France, have strikingly depleted delta13C values, averaging at -35.08 per thousand, versus rural grasses that show an average delta13C value of -30.59 per thousand. A simple mixing model was used to calculate the contributions of fossil-fuel-derived CO2 to the plant tissue. Calculation based on contaminated and noncontaminated isotopic end members shows that urban grasses assimilate up to 29.1% of fossil-fuel-CO2-derived carbon in their tissues. The 13C isotopic composition of grasses thus represents a promising new tool for the study of the impact of fossil fuel CO2 in major cities.

Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al Foil Impacts

NASA Technical Reports Server (NTRS)

Stadermann, Frank J.; Hoppe, Peter; Floss, Christine; Heck, Philipp R.; Hoerz, Friedrich; Huth, Joachim; Kearsley, Anton T.; Leitner, Jan; Marhas, Kuljeet K.; McKeegan, Kevin D.;

Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al foil Impacts

NASA Technical Reports Server (NTRS)

Stadermann, Frank J.; Hoppe, Peter; Floss, Christine; Hoerz, Friedrich; Huth, Joachim; Kearsley, Anton T.; Leitner, Jan; Marhas, Kuljeet K.; McKeegan, Kevin D.; Stephan, Thomas;

Zirconium isotope constraints on the composition of Theia and current Moon-forming theories

NASA Astrophysics Data System (ADS)

Akram, W.; Schönbächler, M.

2016-09-01

The giant impact theory is the most widely recognized formation scenario of the Earth's Moon. Giant impact models based on dynamical simulations predict that the Moon acquired a significant amount of impactor (Theia) material, which is challenging to reconcile with geochemical data for O, Si, Cr, Ti and W isotopes in the Earth and Moon. Three new giant impact scenarios have been proposed to account for this discrepancy - hit-and-run impact, impact with a fast-spinning protoEarth and massive impactors - each one reducing the proportion of the impactor in the Moon compared to the original canonical giant impact model. The validity of each theory and their different dynamical varieties are evaluated here using an integrated approach that considers new high-precision Zr isotope measurements of lunar rocks, and quantitative geochemical modelling of the isotopic composition of the impactor Theia. All analysed lunar samples (whole-rock, ilmenite and pyroxene separates) display identical Zr isotope compositions to that of the Earth within the uncertainty of 13 ppm for 96Zr/90Zr (2σ weighted average). This 13 ppm upper limit is used to infer the most extreme isotopic composition that Theia could have possessed, relative to the Earth, for each of the proposed giant impact theories. The calculated Theian composition is compared with the Zr isotope compositions of different solar system materials in order to constrain the source region of the impactor. As a first order approximation, we show that all considered models (including the canonical) are plausible, alleviating the initial requirement for the new giant impact models. Albeit, the canonical and hit-and-run models are the most restrictive, suggesting that the impactor originated from a region close to the Earth. The fast-spinning protoEarth and massive impactor models are more relaxed and increase the allowed impactor distance from the Earth. Similar calculations carried out for O, Cr, Ti and Si isotope data support these conclusions but exclude a CI- and enstatite chondrite-like composition for Theia. Thus, the impactor Theia most likely had a Zr isotope composition close to that of the Earth, and this suggests that a large part of the inner solar system (or accretion region of the Earth, Theia and enstatite chondrites) had a uniform Zr isotope composition.

Behaviour of Structural Carbonate Stable Carbon and Oxygen Isotope Compositions in Bioapatite During Burning of Bone

NASA Astrophysics Data System (ADS)

Munro, L. E.; Longstaffe, F. J.; White, C. D.

2003-12-01

Bioapatite, the principal inorganic phase comprising bone, commonly contains a small fraction of carbonate, which has been substituted into the phosphate structure during bone formation. The isotopic compositions of both the phosphate oxygen and the structural carbonate oxygen are now commonly used in palaeoclimatological and bioarchaeological investigations. The potential for post-mortem alteration of these isotopic compositions, therefore, is of interest, with the behaviour of structural carbonate being of most concern. In bioarchaeological studies, alteration of bone isotopic compositions has the potential to occur not only during low-temperature processes associated with burial but also during food preparation involving heating (burning, boiling). Here, we examine the stable isotopic behaviour of structural carbonate oxygen and carbon, and coexisting phosphate oxygen during the burning of bone. Freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned and incrementally heated from 25 to 900° C, in 25° intervals. The samples were then ground to a standardized grain-size (45<63μ m), and changes in bioapatite crystallinity (CI) were determined using powder X-ray diffraction (pXRD), and Fourier transform infra-red spectroscopy (FTIR). Combined differential thermal and thermogravimetric analyses (DTA/TG) were used to evaluate weight loss and associated reactions during heating. Stable carbon isotope compositions of the bioapatite remain relatively constant (+/-1‰ ) during heating to 650° C. A 4‰ increase in stable carbon isotopic composition then occurs between 650-750° C, accompanied by an increase in CI, followed by a 10‰ decline at temperatures above 800° C, as carbonate carbon is lost. Carbonate and phosphate oxygen isotopic compositions are correlated over the entire heating range, with carbonate being enriched relative to phosphate by about 8-10‰ below 500° C, 5-6‰ between 500-700° C, and 8-10‰ above 700° C. CI and oxygen isotopic compositions of carbonate and phosphate are not well correlated. Only modest CI changes are recorded from 25-675° C, compared with much larger changes in oxygen isotopic composition, especially above 300° C. On average, original isotopic compositions are largely preserved for both phosphate (+/-1‰ ) and carbonate (+/-2‰ ) oxygen at <300° C. At higher temperatures, however, both phosphate and carbonate oxygen in the bioapatite are systematically depleted of oxygen-18 relative to original values.

Long-term enrichment of the stable isotopic composition of stream water due to the release of groundwater recharge from extreme precipitation events

NASA Astrophysics Data System (ADS)

Boutt, D. F.

2017-12-01

The isotopic composition of surface and groundwater is impacted by a multitude of hydrologic processes. The long-term response of these systems to hydrologic change is critical for appropriately interpreting isotopic information for streamflow generation, stream-aquifer-coupling, sources of water to wells, and understanding recharge processes. To evaluate the response time of stream-aquifer systems to extreme precipitation events we use a long-term isotope dataset from Western Massachusetts with drainage areas ranging from 0.1 to > 800 km2. The year of 2011 was the wettest calendar year on record and the months of August and September of 2011 were the wettest consecutive two-month period in the 123 year record. Stable isotopic composition of surface waters of catchments ranging from 1 - 1000 km2 show an enrichment due to summertime and Tropical Storm precipitation. Enrichment in potential recharge water is shown to have a significant long-term impact (> 3 hydrologic years) on the isotopic composition of both surface and groundwater. This highlights the importance of groundwater sources of baseflow to streams and the transient storage and release mechanisms of shallow groundwater storage. The length of isotopic recession of stream water are also a strong function of watershed area. It is concluded that the stream water isotopes are consistent with a large pulse of water being stored and released from enriched groundwater emplaced during this period of above-average precipitation. Ultimately the results point to the importance of considering hydrological processes of streamflow generation and their role in hydrologic processes beyond traditional catchment response analysis.

Can Lightning Produce Significant Levels of Mass-Independent Oxygen Isotopic Fractionation in Nebular Dust?

NASA Technical Reports Server (NTRS)

Nuth, Joseph A.; Paquette, John A.; Farquhar, Adam

2012-01-01

Based on recent evidence that oxide grains condensed from a plasma will contain oxygen that is mass independently fractionated compared to the initial composition of the vapor, we present a first attempt to evaluate the potential magnitude of this effect on dust in the primitive solar nebula. This assessment relies on previous studies of nebular lightning to provide reasonable ranges of physical parameters to form a very simple model to evaluate the plausibility that lightning could affect a significant fraction of nebular dust and that such effects could cause a significant change in the oxygen isotopic composition of solids in the solar nebula over time. If only a small fraction of the accretion energy is dissipated as lightning over the volume of the inner solar nebula, then a large fraction of nebular dust will be exposed to lightning. If the temperature of such bolts is a few percent of the temperatures measured in terrestrial discharges, then dust will vaporize and recondense in an ionized environment. Finally, if only a small average decrease is assumed in the O-16 content of freshly condensed dust, then over the last 5 million years of nebular accretion the average delta O-17 of the dust could increase by more than 30 per mil. We conclude that it is possible that the measured " slope 1" oxygen isotope line measured in meteorites and their components represents a time-evolution sequence of nebular dust over the last several million years of nebular evolution O-16-rich materials formed first, then escaped further processing as the average isotopic composition of the dust graduaUy became increasingly depleted in O-16 .

U, Th, and Pb isotopes in hot springs on the Juan de Fuca Ridge

NASA Technical Reports Server (NTRS)

Chen, J. H.

1987-01-01

Concentrations and isotopic compositions of U, Th, and Pb in three hydrothermal fluids from the Juan de Fuca Ridge were determined from samples obtained by the Alvin submersible. The samples were enriched in Pb and Th relative to deep-sea water, and were deficient in U. No clear relationship with Mg was found, suggesting nonideal mixing between the hot hydrothermal fluids and the cold ambient seawater. Values for U-234/U-238 have a seawater signature, and show a U-234 enrichment relative to the equilibrium value. The Pb isotopic composition has a uniform midocean ridge basalt signature, and it is suggested that Pb in these fluids may represent the best average value of the local oceanic crust.

Zn isotopic heterogeneity in the mantle: A melting control?

NASA Astrophysics Data System (ADS)

Doucet, Luc S.; Mattielli, Nadine; Ionov, Dmitri A.; Debouge, Wendy; Golovin, Alexander V.

2016-10-01

We present new Zn elemental and isotope data on seventeen fertile and refractory mantle peridotite xenoliths. Eleven fertile peridotites are garnet and spinel lherzolites from Vitim and Tariat (Siberia and Mongolia) and represent some of the most pristine fertile peridotites available. Six refractory peridotites are spinel harzburgites from the Udachnaya kimberlite (Siberian craton) that are nearly pristine residues of high-degree polybaric melting at high pressure (7-4 GPa). Geochemical data suggest that Zn isotopic compositions in the peridotites have not been affected by post-melting processes such as metasomatism, contamination by the host-magmas or alteration. The fertile peridotites have uniform Zn concentrations (59 ± 2 ppm) and Zn isotopic compositions with δ66Zn (relative to JMC-Lyon-03-0749l) = +0.30 ± 0.03‰ consistent with the Bulk Silicate Earth estimates of δ66Zn = +0.28 ± 0.05‰ (Chen et al., 2013). The refractory peridotites have Zn concentrations ranging from 30 to 48 ppm and δ66Zn from + 0.10 ± 0.01 ‰ to + 0.18 ± 0.01 ‰ with an average of + 0.14 ± 0.03 ‰. Our data suggest that the lithospheric mantle has a heterogeneous Zn isotopic composition. Modeling of Zn isotope partitioning during partial melting of fertile mantle suggests that high degrees of melt extraction (>30%) may significantly fractionate Zn isotopes (up to 0.16‰) and that during mantle melting, Zn concentrations and isotopic compositions are mainly controlled by the stability of clinopyroxene and garnet within the melting residue. Because the stability of clinopyroxene and garnet is mainly pressure dependent we suggest that both the depth and the degrees of melt extraction may control Zn isotope fractionation during mantle melting.

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.

Zinc Isotopic Signatures of the Upper Continental Crust

NASA Astrophysics Data System (ADS)

Xia, Y.; Zhang, X.; Zhang, H.; Huang, F.

2016-12-01

To examine the Zn isotope systematics within the Upper Continental Crust (UCC), and isotope fractionation during chemical weathering in large spatial and temporal scales, we analyzed Zn isotopic compositions of loess, glacial diamictites, river sediments, and igneous rocks (samples in total 77). The Zn isotopic compositions (δ66Zn relative to JMC-Lyon) of loess display a limited variation (0.17‰ to 0.29‰), which is negatively correlated with Zn content and proxies for chemical weathering (e.g. CIA values), reflect the impact of chemical weathering. Glacial diamictites have more variable δ66Zn (0.09‰ to 0.48‰), but the average δ66Zn (0.29±0.03‰, 2SD) is similar to loess. δ66Zn of glacial diamictites correlate roughly negatively with CIA values, but have no correlation with Zn content, implying source heterogeneity and effect from chemical weathering. δ66Zn of A-type (0.39‰ to 0.45‰) and S-type (0.28‰ to 0.35‰) granites are both homogeneous, but the latter have systematically lighter δ66Zn. This may reflect no Zn isotopic fractionation during magmatic processes and involvement of isotopically light meta-sedimentary into the sources of S-type granites. Furthermore, δ66Zn in riverine sediments display a small variation from 0.23‰ to 0.37‰, while δ66Zn of the the shales vary from 0.14‰ to 0.53‰, which could result from a combination of processes, such as biological cycling and chemical weathering. Overall, our data suggest that incipient chemical weathering can fractionate Zn isotopes significantly, meanwhile, during this process, heavy Zn are released preferentially. The UCC is estimated to have an average δ66Zn of 0.30 ±0.03‰ (2SD) with data collected in this study, which is similar to the estimated value of Bulk Silicate Earth (0.28±0.05‰)[1] and mean dissolved riverine flux (0.33‰)[2], but distinctly lighter than the bulk composition of dissolved Zn in the ocean (0.51‰)[2]. [1] Chen et al., Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth. Earth and Planetary Science Letters 369, 34-42 (2013). [2] Little et al., The oceanic mass balance of copper and zinc isotopes, investigated by analysis of their inputs, and outputs to ferromanganese oxide sediments. Geochimica et Cosmochimica Acta 125, 673-693 (2014).

Stable C, O and clumped isotope systematics and 14C geochronology of carbonates from the Quaternary Chewaucan closed-basin lake system, Great Basin, USA: Implications for paleoenvironmental reconstructions using carbonates

NASA Astrophysics Data System (ADS)

Hudson, Adam M.; Quade, Jay; Ali, Guleed; Boyle, Douglas; Bassett, Scott; Huntington, Katharine W.; De los Santos, Marie G.; Cohen, Andrew S.; Lin, Ke; Wang, Xiangfeng

2017-09-01

Isotopic compositions of lacustrine carbonates are commonly used for dating and paleoenvironmental reconstructions. Here we use carbonate δ13C and δ18O, clumped (Δ47), and 14C compositions to better understand the carbonate isotope system in closed-basin lakes and trace the paleohydrologic and temperature evolution in the Chewaucan closed-basin lake system, northern Great Basin, USA, over the Last Glacial/Holocene transition. We focus on shorezone tufas to establish that they form in isotopic equilibrium with lake water and DIC, they can be dated reliably using 14C, and their clumped isotope composition can be used to reconstruct past lake temperature. Calculations of the DIC budget and reservoir age for the lake indicate residence time is short, and dominated by exchange with atmospheric CO2 at all past lake levels. Modern lake DIC and shorezone tufas yield δ13C and 14C values consistent with isotopic equilibrium with recent fossil fuel and bomb-influenced atmospheric CO2, supporting these calculations. δ13C values of fossil tufas are also consistent with isotopic equilibrium with pre-industrial atmospheric CO2 at all shoreline elevations. This indicates that the 14C reservoir effect for this material is negligible. Clumped isotope (Δ47) results indicate shorezone tufas record mean annual lake temperature. Modern (average 13 ± 2 °C) and 18 ka BP-age tufas (average 6 ± 2 °C) have significantly different temperatures consistent with mean annual temperature lowering of 7 ± 3 °C (1 SE) under full glacial conditions. For shorezone tufas and other lake carbonates, including spring mounds, mollusk shells, and ostracod tests, overall δ13C and δ18O values co-vary according to the relative contribution of spring and lacustrine end member DIC and water compositions in the drainage system, but specific isotope values depend strongly upon sample context and are not well correlated with past lake depth. This contrasts with the interpretation that carbonate isotopes in closed-basin lake systems reflect changes in DIC and water budgets connected to higher or lower lake volumes. Instead, a small overlapping range of isotope compositions characterize multiple lake levels, so that none can be identified uniquely by isotope composition alone. Relative to other lake carbonates, δ13C and δ18O values for ostracods in Ana River Canyon deposits are very strongly influenced by Ana River water, suggesting low lake level and volume characterized Summer Lake for most of the past 100,000 years. Coupled with sedimentologic observations, the Ana River deposits thus suggest dry conditions like today are close to the mean climate state in the northern Great Basin. By contrast, basin-integrating highstands such as that dating to ∼14 ka BP, during the last glacial termination, are hydrologically unique and short-lived. Overall, our results indicate carbonate isotope records must account for the specific geochemical and hydrologic characteristics of lake system in order to provide robust paleoenvironmental reconstructions.

Stable C, O and clumped isotope systematics and 14C geochronology of carbonates from the Quaternary Chewaucan closed-basin lake system, Great Basin, USA: Implications for paleoenvironmental reconstructions using carbonates

USGS Publications Warehouse

Hudson, Adam; Quade, Jay; Ali, Guleed; Boyle, Douglas P.; Bassett, Scott; Huntington, Katharine W.; De los Santos, Marie G.; Cohen, Andrew S.; Lin, Ke; Wang, Xiangfeng

2017-01-01

Isotopic compositions of lacustrine carbonates are commonly used for dating and paleoenvironmental reconstructions. Here we use carbonate δ13C and δ18O, clumped (Δ47), and 14C compositions to better understand the carbonate isotope system in closed-basin lakes and trace the paleohydrologic and temperature evolution in the Chewaucan closed-basin lake system, northern Great Basin, USA, over the Last Glacial/Holocene transition. We focus on shorezone tufas to establish that they form in isotopic equilibrium with lake water and DIC, they can be dated reliably using 14C, and their clumped isotope composition can be used to reconstruct past lake temperature. Calculations of the DIC budget and reservoir age for the lake indicate residence time is short, and dominated by exchange with atmospheric CO2 at all past lake levels. Modern lake DIC and shorezone tufas yield δ13C and 14C values consistent with isotopic equilibrium with recent fossil fuel and bomb-influenced atmospheric CO2, supporting these calculations. δ13C values of fossil tufas are also consistent with isotopic equilibrium with pre-industrial atmospheric CO2 at all shoreline elevations. This indicates that the 14C reservoir effect for this material is negligible. Clumped isotope (Δ47) results indicate shorezone tufas record mean annual lake temperature. Modern (average 13 ± 2 °C) and 18 ka BP-age tufas (average 6 ± 2 °C) have significantly different temperatures consistent with mean annual temperature lowering of 7 ± 3 °C (1 SE) under full glacial conditions. For shorezone tufas and other lake carbonates, including spring mounds, mollusk shells, and ostracod tests, overall δ13C and δ18O values co-vary according to the relative contribution of spring and lacustrine end member DIC and water compositions in the drainage system, but specific isotope values depend strongly upon sample context and are not well correlated with past lake depth. This contrasts with the interpretation that carbonate isotopes in closed-basin lake systems reflect changes in DIC and water budgets connected to higher or lower lake volumes. Instead, a small overlapping range of isotope compositions characterize multiple lake levels, so that none can be identified uniquely by isotope composition alone. Relative to other lake carbonates, δ13C and δ18O values for ostracods in Ana River Canyon deposits are very strongly influenced by Ana River water, suggesting low lake level and volume characterized Summer Lake for most of the past 100,000 years. Coupled with sedimentologic observations, the Ana River deposits thus suggest dry conditions like today are close to the mean climate state in the northern Great Basin. By contrast, basin-integrating highstands such as that dating to ∼14 ka BP, during the last glacial termination, are hydrologically unique and short-lived. Overall, our results indicate carbonate isotope records must account for the specific geochemical and hydrologic characteristics of lake system in order to provide robust paleoenvironmental reconstructions.

Microscale Variations in the 13C Content of the Murchison Meteorite

NASA Astrophysics Data System (ADS)

Romanek, C.; Gibson, E.; Socki, R.; Burkett, P. J.

1993-07-01

Heretofore unresolved micrometer-scale carbon isotopic zonation in the Murchison meteorite (CM3) is documented using a laser microprobe mass spectrometer. High-resolution isotopic gradients and heterogeneities between high- and low-temperature textural components help to constrain the processes that have shaped the physiochemical character of this carbonaceous chondrite. Previous bulk samples of Murchison yield an average delta ^13C value of - 5.7 +/- 4.3 per mil [1] while individual components such as micrometer-sized mineral separates (e.g., C(sub)graphite , C(sub)diamond, and SiC), acid- soluble extracts (e.g., CaCO3 and polar hydrocarbons), and insoluble residues (e.g., polycyclic aromatic hydrocarbons) are isotopically diverse (delta ^13C of -1000 to 29,000 per mil). While these studies shed light on the origin and occurrence of C-bearing phases, they fail to constrain intrinsic spatial isotopic heterogeneities. The power of the laser microprobe lies in the fact that in situ chemical and isotopic compositions are measured simultaneously for volatiles extracted from extremely small sample volumes (i.e., 0.025 mm^3 for 5 wt% C). Nd-YAG laser irradiation (1.06 micrometers) is directed onto texturally defined targets (>=50 micrometers wide) from which solid material is volatilized. Condensible gaseous phases are collected in a variable-temperature cold trap while the more volatile species (CH4 and CO) are quantified using an ion trap mass spectrometer. All gases are then converted to CO2 in a CuO furnace (containing Pt) held at 600 degrees C and analyzed for carbon and oxygen isotope ratios. The concentration and isotopic composition of condensed species are determined by stepped sublimation of unstable components and conversion to CO2. Preliminary isotopic analyses of the total volatile C content (i.e., bulk microanalysis) from distinct textural components at least 0.05 mm^3 in volume are described below. The most ^13C-depleted components within Murchison reside within the cores of chondrules and/or aggregates. Three typical cores were analyzed, with an average bulk composition of -21.0 +/- 0.5 per mil (n = 7). The bulk ^13C content of C-bearing phases increases monotonically outward in all directions within 100 to 200 micrometers of each core (i.e., within dust mantles) to a constant matrix value of -12.5 +/- 0.5 per mil (n = 40). The most isotopically enriched textural component found in Murchison is a regolith breccia clast without chondrules that has an average bulk delta ^13C value of -10 +/-0.5 per mil (n = 5). The clast was originally detectable only under cathodoluminescence, but with the aid of the laser microprobe it is now characterized by an unusually low volatile content and enriched ^13C composition. In general, the most isotopically enriched components also produce the lowest yield of gas (normalized to sampling volume). This trend of isotopic enrichment from chondrule to matrix has been documented previously for oxygen isotopes in carbonaceous chondrites [2]. Carbon isotopic gradients and heterogeneities within Murchison reflect fundamental changes in the chemical speciation and/or isotopic content of the main C-bearing components (i.e., acid-soluble and insoluble hydrocarbon fractions) within the meteorite. Perhaps core interiors and dust mantles are responding to environmental changes reflected in the speciation of C-bearing species distributed within the solar nebula or the parent body. Inverse correlations between hydrocarbon atomic mass number and ^13C abundance in the acid-soluble [3] and insoluble residues [4] of Murchison have been documented. Alternatively, micrometer-scale isotopic gradients may reflect fundamental changes in the isotopic composition of individual C-bearing species through time. Enrichments may represent kinetically controlled processes related to hydrocarbon formation. In contrast, assuming an equilibrium fractionation mechanism, isotopic enrichments may record a temperature-dependent component to hydrocarbon delta ^13C values. These opposing alternatives will be discussed in light of the isotopic composition of individual C-bearing components volatilized from tightly constrained sample volumes within Murchison. References: [1] Kerridge J. F. (1985) GCA, 49, 1707-1714. [2] Clayton R. N. and Mayeda T. K. (1984) EPSL, 67, 151-161. [3] Yuen G. et al. (1984) Nature, 307, 254. [4] Gilmour I. et al. (1991) Meteoritics, 26, 337-338.

A subduction wedge origin for Paleoarchean peridotitic diamonds and harzburgites from the Panda kimberlite, Slave craton: evidence from Re-Os isotope systematics

NASA Astrophysics Data System (ADS)

Westerlund, K. J.; Shirey, S. B.; Richardson, S. H.; Carlson, R. W.; Gurney, J. J.; Harris, J. W.

2006-09-01

An extensive study of peridotitic sulfide inclusion bearing diamonds and their prospective harzburgitic host rocks from the 53 Ma Panda kimberlite pipe, Ekati Mine, NWT Canada, has been undertaken with the Re-Os system to establish their age and petrogenesis. Diamonds with peridotitic sulfide inclusions have poorly aggregated nitrogen (<30% N as B centers) at N contents of 200-800 ppm which differs from that of chromite and silicate bearing diamonds and indicates residence in the cooler portion of the Slave craton lithospheric mantle. For most of the sulfide inclusions, relatively low Re contents (average 0.457 ppm) and high Os contents (average 339 ppm) lead to extremely low 187Re/188Os, typically << 0.05. An age of 3.52 ± 0.17 Ga (MSWD = 0.46) and a precise initial 187Os/188Os of 0.1093 ± 0.0001 are given by a single regression of 11 inclusions from five diamonds that individually provide coincident internal isochrons. This initial Os isotopic composition is 6% enriched in 187Os over 3.5 Ga chondritic or primitive mantle. Sulfide inclusions with less radiogenic initial Os isotopic compositions reflect isotopic heterogeneity in diamond forming fluids. The harzburgites have even lower initial 187Os/188Os than the sulfide inclusions, some approaching the isotopic composition of 3.5 Ga chondritic mantle. In several cases isotopically distinct sulfides occur in different growth zones of the same diamond. This supports a model where C-O-H-S fluids carrying a radiogenic Os signature were introduced into depleted harzburgite and produced diamonds containing sulfides conforming to the 3.5 Ga isochron. Reaction of this fluid with harzburgite led to diamonds with less radiogenic inclusions while elevating the Os isotope ratios of some harzburgites. Subduction is a viable way of introducing such fluids. This implies a role for subduction in creating early continental nuclei at 3.5 Ga and generating peridotitic diamonds.

Investigation of magnesium isotope fractionation during basalt differentiation: Implications for a chondritic composition of the terrestrial mantle

USGS Publications Warehouse

Teng, F.-Z.; Wadhwa, M.; Helz, R.T.

2007-01-01

To investigate whether magnesium isotopes are fractionated during basalt differentiation, we have performed high-precision Mg isotopic analyses by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) on a set of well-characterized samples from Kilauea Iki lava lake, Hawaii, USA. Samples from the Kilauea Iki lava lake, produced by closed-system crystal-melt fractionation, range from olivine-rich cumulates to highly differentiated basalts with MgO content ranging from 2.37 to 26.87??wt.%. Our results demonstrate that although these basalts have diverse chemical compositions, mineralogies, crystallization temperatures and degrees of differentiation, their Mg isotopic compositions display no measurable variation within the limits of our external precision (average ??26Mg = - 0.36 ?? 0.10 and ??25Mg = - 0.20 ?? 0.07; uncertainties are 2SD). This indicates that Mg isotopic fractionation during crystal-melt fractionation at temperatures of ??? 1055????C is undetectable at the level of precision of the current investigation. Calculations based on our data suggest that at near-magmatic temperatures the maximum fractionation in the 26Mg/24Mg ratio between olivine and melt is 0.07???. Two additional oceanic basalts, two continental basalts (BCR-1 and BCR-2), and two primitive carbonaceous chondrites (Allende and Murchison) analyzed in this study have Mg isotopic compositions similar to the Kilauea Iki lava lake samples. In contrast to a recent report [U. Wiechert, A.N. Halliday, Non-chondritic magnesium and the origins of the inner terrestrial planets, Earth and Planetary Science Letters 256 (2007) 360-371], the results presented here suggest that the Bulk Silicate Earth has a chondritic Mg isotopic composition. ?? 2007.

Oxygen isotope constraints on the alteration temperatures of CM chondrites

NASA Astrophysics Data System (ADS)

Verdier-Paoletti, Maximilien J.; Marrocchi, Yves; Avice, Guillaume; Roskosz, Mathieu; Gurenko, Andrey; Gounelle, Matthieu

2017-01-01

We report a systematic oxygen isotopic survey of Ca-carbonates in nine different CM chondrites characterized by different degrees of alteration, from the least altered known to date (Paris, 2.7-2.8) to the most altered (ALH 88045, CM1). Our data define a continuous trend that crosses the Terrestrial Fractionation Line (TFL), with a general relationship that is indistinguishable within errors from the trend defined by both matrix phyllosilicates and bulk O-isotopic compositions of CM chondrites. This bulk-matrix-carbonate (BMC) trend does not correspond to a mass-dependent fractionation (i.e., slope 0.52) as it would be expected during fluid circulation along a temperature gradient. It is instead a direct proxy of the degree of O-isotopic equilibration between 17,18O-rich fluids and 16O-rich anhydrous minerals. Our O-isotopic survey revealed that, for a given CM, no carbonate is in O-isotopic equilibrium with its respective surrounding matrix. This precludes direct calculation of the temperature of carbonate precipitation. However, the O-isotopic compositions of alteration water in different CMs (inferred from isotopic mass-balance calculation and direct measurements) define another trend (CMW for CM Water), parallel to BMC but with a different intercept. The distance between the BMC and CMW trends is directly related to the temperature of CM alteration and corresponds to average carbonates and serpentine formation temperatures of 110 °C and 75 °C, respectively. However, carbonate O-isotopic variations around the BMC trend indicate that they formed at various temperatures ranging between 50 and 300 °C, with 50% of the carbonates studied here showing precipitation temperature higher than 100 °C. The average Δ17O and the average carbonate precipitation temperature per chondrite are correlated, revealing that all CMs underwent similar maximum temperature peaks, but that altered CMs experienced protracted carbonate precipitation event(s) at lower temperatures than the least altered CMs. Our data suggest that the Δ17O value of Ca-carbonates could be a reliable proxy of the degree of alteration experienced by CM chondrites.

Silicon Isotope Geochemistry of Ocean Island Basalts: Search for Deep Mantle Heterogeneities and Evidence for Recycled Altered Oceanic Crust

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.; Moynier, F.

2014-12-01

Analyses of Ocean Island Basalts (OIB) have shown that the Earth's mantle contains isotopically distinct components, but debate about the degree and cause of variability persists. The study of silicon (Si) isotopes in OIBs has the potential to elucidate mantle heterogeneities. Relatively large (~several per mil) Si isotopic fractionation occurs in low-temperature environments during precipitation from dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes [1], but only a limited range (~tenths of a per mil) of Si isotope fractionation has been observed due to high-temperature igneous processes [2]. Therefore, Si isotopes may be useful as tracers for the presence of crustal material in OIB source regions in a manner similar to more conventional stable isotope systems, such as oxygen. Here we present the first comprehensive suite of high-precision Si isotopic data obtained by MC-ICP-MS for a diverse set of OIBs representing the EM-1, EM-2, and HIMU mantle components. In general, the Si isotopic compositions of OIBs analyzed here are agreement with previous estimates for Bulk Silicate Earth (BSE). However, small systematic variations are present; the HIMU end-member Mangaia and HIMU-type Cape Verde island São Nicolau are enriched in the light isotopes of Si (δ30Si = -0.37 ± 0.06‰ and δ30Si = -0.39 ± 0.04‰, respectively; errors are 2sd), with compositions intermediary between Mid Ocean Ridge Basalts and chondritic values. Additionally, Iceland samples from volcanic complexes in the Northern Rift Zone show similar Si isotope compositions (on average, δ30Si = -0.40 ± 0.06‰). In contrast, the δ30Si averages of the EM-1 end-member Pitcairn (-0.28 ± 0.07‰), the EM-2 end-member Samoa (-0.31 ± 0.07‰) and other OIB localities do not show any significant difference from previous estimates for the δ30Si value of BSE [3]. The Si isotopic variability in some HIMU-type and Icelandic OIBs most likely reflects the incorporation of recycled altered oceanic crust in the plume source. However, the sampling of a primitive reservoir enriched in the light isotopes of Si, as suggested by [4], cannot be ruled out as a potential source of Si isotope variations in OIBs. References: [1] Ziegler et al., GCA 2005 [2] Savage et al., GCA 2011 [3] Savage et al., EPSL 2010 [4] Huang et al., GCA 2014

Secular variations of iron isotopes in ferromanganese crusts: evidences for deeply sourced iron in the Pacific Ocean?

NASA Astrophysics Data System (ADS)

Rouxel, O. J.; Gueguen, B.

2016-12-01

Ferromanganese (Fe-Mn) crusts are potential archive of the Fe isotope composition of deep seawater through time. Here, we report Fe isotope composition of two pairs of Fe-Mn crusts collected on two volcanic seamounts from the Northern Pacific Ocean (Apuupuu Seamount, Hawaii) and the Southern Pacific Ocean (near Rurutu Island, Austral archipelago of French Polynesia). This approach allows (a) a direct comparison of the Fe isotope record in Fe-Mn crusts from the same seamount in order to address local effects, and (b) a comparison of geochemical composition of crusts between North and South Pacific in order to address the effect of more global geochemical processes. The results show that, despite different growth rates, diagenetic history, textures and geochemical patterns, Fe-Mn crusts from both North and South Pacific Oceans have fairly homogenous Fe isotope compositions over the last 17 Ma, yielding average δ56Fe values of -0.22 ± 0.20‰ (1sd, n = 54). The results also show striking correlations between Fe and Pb isotope ratios, indicating that local mixing between water masses is the main factor controlling Fe isotope composition in FeMn crusts. Recently, Horner et al. (2015) reported a range of δ56Fe values from -1.12‰ to 1.54‰ along a 76 Ma-old FeMn crust from the central pacific. However, secular variations of Fe isotopes inferred from other FeMn crusts in the Central North Pacific and Western Pacific (Yang and Rouxel, unpublished) show different patterns over the last 40 Ma, with δ56Fe ranging from -0.07 to -0.61‰ (n=81). Hence, the application of Fe isotopes as paleoceanographic proxies to trace deeply sourced iron at the scale of oceanic basins should be used with caution, prompting for an integrative approach combining diverse yet complimentary geochemical proxies.

Geochemistry of CI chondrites: Major and trace elements, and Cu and Zn Isotopes

NASA Astrophysics Data System (ADS)

Barrat, J. A.; Zanda, B.; Moynier, F.; Bollinger, C.; Liorzou, C.; Bayon, G.

2012-04-01

In order to check the heterogeneity of the CI chondrites and determine the average composition of this group of meteorites, we analyzed a series of six large chips (weighing between 0.6 and 1.2 g) of Orgueil prepared from five different stones. In addition, one sample from each of Ivuna and Alais was analyzed. Although the sizes of the chips used in this study were “large”, our results show evidence for minor chemical heterogeneity in Orgueil, particularly for alkali elements and U. After removal of one outlier sample, the spread of the results is considerably reduced. For most of the 46 elements analyzed in this study, the average composition calculated for Orgueil is in very good agreement with previous CI estimates. This average, obtained with a “large” mass of samples, is analytically homogeneous and is suitable for normalization purposes. Finally, the Cu and Zn isotopic ratios are homogeneously distributed within the CI parent body with a spread of less than 100 ppm per atomic mass unit (amu).

Mechanisms for Magnesium Isotopic Variation in Low-grade Metamorphosed Mudrocks from the British Caledonides

NASA Astrophysics Data System (ADS)

Wang, S.; Teng, F.; Rudnick, R. L.; Li, S.

2013-12-01

We report Mg isotope ratios for low-grade metamorphosed mudrocks from three lower Paleozoic basins (northern Lake District, southern Lake District and Southern Uplands) in the British Caledonides, previously analyzed for Li, Sr and Nd isotopes (Qiu et al., 2009, GCA), with the aim of understanding the behavior of Mg isotopes during subgreenschist-facies metamorphism, and the processes responsible for Mg isotopic variations in mudrocks. The δ26Mg of mudrocks varies greatly from -0.754 to 0.251, and displays no correlation with metamorphic grade, which ranges from diagenesis to subgreenschist-facies. Thus, low-grade metamorphism has no apparent influence on Mg isotopes. The variations instead likely reflect their provenance and mineralogical components. Samples from the northern Lake District, previously interpreted to derive from ancient, heavily weathered crust have δ26Mg (-0.06 × 0.11 on average) significantly heavier than that of average upper continental crust (~ -0.22), which is consistent with this interpretation. By contrast, mudrocks from the southern Lake District are characterized by low δ26Mg values (from -0.754 to -0.093) that require the presences of an unusually light component. The previously inferred provenance for these rocks of upper continental crust and arc volcanic detritus cannot explain such light isotopic compositions. Rather, such values may reflect the presence of carbonate in these samples and uptake of sea water Mg. Samples from the Southern Uplands, which contain the heaviest Li isotopes and ɛNd, and contain volcanic arc detritus, display Mg isotopic compositions divergent from a 'normal' mantle value (-0.25) towards both high and low δ26Mg values (from -0.742 to -0.079). Therefore, these mudrocks must contain a minimum of three end-members: mature felsic upper continental crust, arc lavas and carbonate. Given that limited Mg isotope fractionation occurs during low-grade metamorphism, Mg isotopes could be a potential tracer of provenance as well as carbonate involvement for fine-grained terrigenous sediments.

Isotopic measurements of the cosmic ray nuclei at 1.7 GeV/n and 0.5 GeV/n

NASA Technical Reports Server (NTRS)

Juliusson, E.

1975-01-01

Results are presented on the mean isotopic composition of cosmic ray nuclei, or the average neutron excess for the elements Be to Si. At 1.7 GeV/nucleon they have been obtained by comparing the abundances measured above a rigidity threshold at Palestine, Texas, with abundances measured above an equivalent velocity threshold at Cape Girardeau Missouri. At 0.5 GeV/nucleon the results are obtained by analysing the variation in the chemical composition with energy in the energy region around the geomagnetic cut-off.

Effects of mother lode-type gold mineralization on 187Os/188Os and platinum group element concentrations in peridotite: Alleghany District, California

USGS Publications Warehouse

Walker, R.J.; Böhlke, J.K.; McDonough, W.F.; Li, Ji

2007-01-01

Osmium isotope compositions and concentrations of Re, platinum group elements (PGE), and Au were determined for host peridotites (serpentinites and barzburgites) and hydrothermally altered ultramafic wall rocks associated with Mother Lode-type hydrothermal gold-quartz vein mineralization in the Alleghany district, California. The host peridotites have Os isotope compositions and Re, PGE, and Au abundances typical of the upper mantle at their presumed formation age during the late Proterozoic or early Paleozoic. The hydrothermally altered rocks have highly variable initial Os isotope compositions with ??os, values (% deviation of 187OS/188OS from the chondritic average calculated for the approx. 120 Ma time of mineralization) ranging from -1.4 to -8.3. The lowest Os isotope compositions are consistent with Re depletion of a chondritic source (e.g., the upper mantle) at ca. 1.6 Ga. Most of the altered samples are enriched in Au and have depleted and fractionated abundances of Re and PGE relative to their precursor peridotites. Geoehemical characteristics of the altered samples suggest that Re and some PGE were variably removed from the ultramafic rocks during the mineralization event. In addition to Re, the Pt and Pd abundances of the most intensely altered rocks appear to have been most affected by mineralization. The 187Os-depleted isotopic compositions of some altered rocks are interpreted to be a result of preferential 187Os loss via destruction of Re-rich phases during the event. For these rocks, Os evidently is not a useful tracer of the mineralizing fluids. The results do, however, provide evidence for differential mobility of these elements, and mobility of 187Os relative to the initial bulk Os isotope composition during hydrothermal metasomatic alteration of ultramafic rocks. ?? 2007 Society of Economic Geologists, Inc.

Disentangling Seasonality and Mean Annual Precipitation in the Indo-Pacific Warm Pool: Insights from Coupled Plant Wax C and H Isotope Measurements

NASA Astrophysics Data System (ADS)

Galy, V.; Oppo, D.; Dubois, N.; Arbuszewski, J. A.; Mohtadi, M.; Schefuss, E.; Rosenthal, Y.; Linsley, B. K.

2016-12-01

There is ample evidence suggesting that rainfall distribution across the Indo-Pacific Warm Pool (IPWP) - a key component of the global climate system - has substantially varied over the last deglaciation. Yet, the precise nature of these hydroclimate changes remains to be elucidated. In particular, the relative importance of variations in precipitation seasonality versus annual precipitation amount is essentially unknown. Here we use a set of surface sediments from the IPWP covering a wide range of modern hydroclimate conditions to evaluate how plant wax stable isotope composition records rainfall distribution in the area. We focus on long chain fatty acids, which are exclusively produced by vascular plants living on nearby land and delivered to the ocean by rivers. We relate the C (δ13C) and H (δD) isotope composition of long chain fatty acids preserved in surface sediments to modern precipitation distribution and stable isotope composition in their respective source area. We show that: 1) δ13C values reflect vegetation distribution (in particular the relative abundance of C3 and C4 plants) and are primarily recording precipitation seasonality (Dubois et al., 2014) and, 2) once corrected for plant fractionation effects, δD values reflect the amount-weighted average stable isotope composition of precipitation and are primarily recording annual precipitation amounts. We propose that combining the C and H isotope composition of long chain fatty acids thus allows independent reconstructions of precipitation seasonality and annual amounts in the IPWP. The practical implications for reconstructing past hydroclimate in the IPWP will be discussed.

Spring response to precipitation events using δ(18)O and δ(2)H in the Tanour catchment, NW Jordan.

PubMed

Hamdan, Ibraheem; Wiegand, Bettina; Toll, Mathias; Sauter, Martin

2016-12-01

The Tanour spring is one of the several karst springs located in the northern part of Jordan. Water samples from the Tanour spring and precipitation were collected in the area of Ajloun in NW Jordan for the analysis of stable oxygen and hydrogen isotopes to evaluate the spring response to precipitation events. Rainwater and snow samples were collected from different elevations during winters of 2013-2014 and 2014-2015. In addition, spring samples were collected between December 2014 and March 2015. δ(18)O values in rainwater vary from -3.26 to -17.34 ‰ (average: -7.84 ± 3.23 ‰), while δ(2)H values range between -4.4 and -110.4 ‰ (average: -35.7 ± 25.0 ‰). Deuterium excess ranges from 17.8 to 34.1 ‰ (average: 27.1 ± 4.0 ‰). The Local Meteoric Water Line for the study area was calculated to be δ(2)H = 7.66*δ(18)O + 24.43 (R(2) = 0.98). Pre-event spring discharge showed variation in δ(18)O (range -6.29 to -7.17 ‰; average -6.58 ± 0.19 ‰) and δ(2)H values (range -28.8 to -32.7 ‰; average: -30.5 ± 1.0 ‰). In contrast, δ(18)O and δ(2)H rapidly changed to more negative values during rainfall and snowmelt events and persisted for several days before returning to background values. Spring water temperature, spring discharge, and turbidity followed the trend in isotopic composition during and after the precipitation events. The rapid change in the isotopic composition, spring discharge, water temperature, and turbidity in response to recharge events is related to fast water travel times and low storage capacity in the conduit system of the karst aquifer. Based on the changes in the isotopic composition of spring water after the precipitation events, the water travel time in the aquifer is in the order of 5-11 days.

The isotopic composition of cosmic-ray beryllium and its implication for the cosmic ray's age

NASA Technical Reports Server (NTRS)

Lukasiak, A.; Ferrando, P.; Mcdonald, F. B.; Webber, W. R.

1994-01-01

We report a new measurement of the cosmic-ray isotopic composition of beryllium in the low-energy range from 35 to 113 MeV per nucleon. This measurement was made using the High Energy Telescope of the CRS experiment on the Voyager 1 and 2 spacecraft during the time period from 1977 to 1991. In this overall time period of 14 years the average solar modulation level was about 500 MV. The cosmic-ray beryllium isotopes were completely separated with an average mass resolution sigma of 0.185 amu. The isotope fractions of Be-7, Be-9, and Be-10 obtained are 52.4 +/- 2.9%, 43.3 +/- 3.7%, and 4.3 +/- 1.5%, respectively. The measured cosmic-ray abundances of Be-7 and Be-9 are found to be in agreement with calculations based on standard Leaky-Box model for the interstellar propagation of cosmic-ray nuclei using the recent cross sections of the New Mexico-Saclay collaboration. From our observed ratio Be-10/Be = 4.3 +/- 1.5% we deduce an average interstellar density of about 0.28 (+0.14, -0.11) atoms/cu cm, and acosmic-ray lifetime for escape of 27 (+19, -9) x 10(exp 6) years. The surviving fraction of Be-10 is found to be 0.19 +/- 0.07. Modifications to the conclusions of the Leaky-Box model when a diffusion + convection halo model for propagation is used are also considered.

The isotopic composition of cosmic-ray beryllium and its implication for the cosmic ray's age

NASA Astrophysics Data System (ADS)

Lukasiak, A.; Ferrando, P.; McDonald, F. B.; Webber, W. R.

1994-03-01

We report a new measurement of the cosmic-ray isotopic composition of beryllium in the low-energy range from 35 to 113 MeV per nucleon. This measurement was made using the High Energy Telescope of the CRS experiment on the Voyager 1 and 2 spacecraft during the time period from 1977 to 1991. In this overall time period of 14 years the average solar modulation level was about 500 MV. The cosmic-ray beryllium isotopes were completely separated with an average mass resolution sigma of 0.185 amu. The isotope fractions of Be-7, Be-9, and Be-10 obtained are 52.4 +/- 2.9%, 43.3 +/- 3.7%, and 4.3 +/- 1.5%, respectively. The measured cosmic-ray abundances of Be-7 and Be-9 are found to be in agreement with calculations based on standard Leaky-Box model for the interstellar propagation of cosmic-ray nuclei using the recent cross sections of the New Mexico-Saclay collaboration. From our observed ratio Be-10/Be = 4.3 +/- 1.5% we deduce an average interstellar density of about 0.28 (+0.14, -0.11) atoms/cu cm, and a cosmic-ray lifetime for escape of 27 (+19, -9) x 106 years. The surviving fraction of Be-10 is found to be 0.19 +/- 0.07. Modifications to the conclusions of the Leaky-Box model when a diffusion + convection halo model for propagation is used are also considered.

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.

Mixing ratio and carbon isotopic composition investigation of atmospheric CO2 in Beijing, China.

PubMed

Pang, Jiaping; Wen, Xuefa; Sun, Xiaomin

2016-01-01

The stable isotope composition of atmospheric CO2 can be used as a tracer in the study of urban carbon cycles, which are affected by anthropogenic and biogenic CO2 components. Continuous measurements of the mixing ratio and δ(13)C of atmospheric CO2 were conducted in Beijing from Nov. 15, 2012 to Mar. 8, 2014 including two heating seasons and a vegetative season. Both δ(13)C and the isotopic composition of source CO2 (δ(13)CS) were depleted in the heating seasons and enriched in the vegetative season. The diurnal variations in the CO2 mixing ratio and δ(13)C contained two peaks in the heating season, which are due to the effects of morning rush hour traffic. Seasonal and diurnal patterns of the CO2 mixing ratio and δ(13)C were affected by anthropogenic emissions and biogenic activity. Assuming that the primary CO2 sources at night (22:00-04:00) were coal and natural gas combustion during heating seasons I and II, an isotopic mass balance analysis indicated that coal combustion had average contributions of 83.83±14.11% and 86.84±12.27% and that natural gas had average contributions of 16.17±14.11% and 13.16±12.27%, respectively. The δ(13)C of background CO2 in air was the main error source in the isotopic mass balance model. Both the mixing ratio and δ(13)C of atmospheric CO2 had significant linear relationships with the air quality index (AQI) and can be used to indicate local air pollution conditions. Energy structure optimization, for example, reducing coal consumption, will improve the local air conditions in Beijing. Copyright © 2015 Elsevier B.V. All rights reserved.

Mixing ratio and carbon isotopic composition investigation of atmospheric CO2 in Beijing, China

NASA Astrophysics Data System (ADS)

Pang, J.; Wen, X.; Sun, X.

2016-12-01

The stable isotope composition of atmospheric CO2 can be used as a tracer in the study of urban carbon cycles, which are affected by anthropogenic and biogenic CO2 components. Continuous measurements of the mixing ratio and δ13C of atmospheric CO2 were conducted in Beijing from Nov. 15, 2012 to Mar. 8, 2014 including two heating seasons and a vegetative season. Both δ13C and the isotopic composition of source CO2 (δ13CS) were depleted in the heating seasons and enriched in the vegetative season. The diurnal variations in the CO2 mixing ratio and δ13C contained two peaks in the heating season, which are due to the effects of morning rush hour traffic. Seasonal and diurnal patterns of the CO2 mixing ratio and δ13C were affected by anthropogenic emissions and biogenic activity. Assuming that the primary CO2 sources at night (22:00-04:00) were coal and natural gas combustion during heating seasons I and II, an isotopic mass balance analysis indicated that coal combustion had average contributions of 83.83 ± 14.11% and 86.84 ± 12.27% and that natural gas had average contributions of 16.17 ± 14.11% and 13.16 ± 12.27%, respectively. The δ13C of background CO2 in air was the main error source in the isotopic mass balance model. Both the mixing ratio and δ13C of atmospheric CO2 had significant linear relationships with the air quality index (AQI) and can be used to indicate local air pollution conditions. Energy structure optimization, for example, reducing coal consumption, will improve the local air conditions in Beijing.

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.

Boron Isotopic Composition of Metasomatized Mantle Xenoliths from the Western Rift, East Africa

NASA Astrophysics Data System (ADS)

Hudgins, T.; Nelson, W. R.

2017-12-01

The Western Branch of the East African Rift System is known to have a thick lithosphere and sparse, alkaline volcanism associated with a metasomatized mantle source. Recent work investigating the relationship between Western Branch metasomatized mantle xenoliths and associated lavas has suggested that these metasomes are a significant factor in the evolution of the rift. Hydrous/carbonated fluids or silicate melts are potent metasomatic agents, however gaining insight into the source of a metasomatic agent proves challenging. Here we investigate the potential metasomatic fluid sources using B isotope analysis of mineral separates from Western Branch xenoliths. Preliminary SIMS analyses of phlogopite from Katwe Kikorongo and Bufumbira have and average B isotopic composition of -28.2‰ ± 5.1 and -16.4‰ ± 3.6, respectively. These values are are dissimilar to MORB (-7.5‰ ± 0.7; Marschall and Monteleone, 2015), primitive mantle (-10‰ ± 2; Chaussidon and Marty, 1995), and bulk continental crust (-9.1‰ ± 2.4; Marschall et al., 2017) and display significant heterogeneity across a relatively short ( 150km) portion of the Western Branch. Though displaying large variability, these B isotopic compositions are indicative of a metasomatic agent with a more negative B isotopic composition than MORB, PM, or BCC. These results are consistent with fluids that released from a subducting slab and may be related to 700 Ma Pan-African subduction.

Tracing ground-water movement by using the stable isotopes of oxygen and hydrogen, upper Penitencia Creek alluvial fan, Santa Clara Valley, California

USGS Publications Warehouse

Muir, K.S.; Coplen, Tyler B.

1981-01-01

Starting in 1965 the Santa Clara Valley Water District began importing about i00,000 acre-feet per year of northern California water. About one-half of this water was used to artificially recharge the Upper Penitencia Creek alluvial fan in Santa Clara Valley. In order to determine the relative amounts of local ground water and recharged imported water being pumped from the wells, stable isotopes of oxygen and hydrogen were used to trace the movement of the imported water in the alluvial fan. To trace the movement of imported water in the Upper Penitencia Creek alluvial fan, well samples were selected to give areal and depth coverage for the whole fan. The stable isotopes of oxygen-16, oxygen-18, and deuterium were measured in the water samples of imported water and from the wells and streams in the Santa Clara Valley. The d18oand dD compositions of the local runoff were about -6.00 o/oo (parts per thousand) and -40 o/oo, respectively; the average compositions for the local native ground-water samples were about -6.1 o/oo and -41 o/oo, respectively; and the average compositions of the imported water samples were -10.2 o/oo and -74 o/oo, respectively. (The oxygen isotopic composition of water samples is reported relative to Standard Mean Ocean Water, in parts per thousand.) The difference between local ground water and recharged imported water was about 4.1 o/oo in d18o and 33 o/oo in dL. The isotopic data indicate dilution of northern California water with local ground water in a downgradient direction. Two wells contain approximately 74 percent northern California water, six wells more than 50 percent. Data indicate that there may be a correlation between the percentage of northern California water and the depth or length of perforated intervals in wells.

Molybdenum Isotopic Composition of the Archean Mantle As Inferred from Studies of Komatiites

NASA Astrophysics Data System (ADS)

Greber, N. D.; Puchtel, I. S.; Nagler, T. F.; Mezger, K.

2014-12-01

Molybdenum isotopic composition has been shown to be a powerful tool in studies of planetary processes, e.g. estimating core formation temperatures [1,2]. However, Mo isotope compositions of terrestrial reservoirs are not well constrained. In order to better constrain the Mo isotopic composition of the early Earth's mantle, komatiites from four locations were analyzed for their Mo concentrations and isotopic compositions. Komatiites are particularly appropriate for this type of study because they formed by high degrees of partial melting of the mantle leading to a complete base metal sulfide removal from the residual mantle and the production of sulfur-undersaturated melts and thus a quantitative removal of Mo from the source into the melt. All samples, except for two strongly altered specimens specifically chosen to study the effects of secondary alteration, are very fresh having preserved most of their primary mineralogy. The Mo concentrations in komatiites range from 10 to 120 ng/g. Fresh komatiites have lighter δ98Mo (NIST SRM 3134 = 0.25‰, [3]) than altered samples. The estimated primary Mo isotope compositions of the studied komatiite melts range from 0.02 ± 0.16‰ to 0.19 ± 0.14‰ and are therefore indistinguishable within analytical uncertainty (2SD) from published values for chondritic meteorites (0.09 ± 0.04 ‰; 2SD; [2]) and lighter than the proposed average for Earth's continental crust (0.3 to 0.4‰ [4]). All data combined, although overlapping in errors, show a consistent trend of lighter δ98Mo and lower Mo concentrations in more melt-depleted mantle sources, indicating incompatible behaviour of Mo and preferential mobilization of heavy Mo isotopes during mantle melting. [1] Hin et al. (2013) EPSL, 379 [2] Burkhardt et al. (2014) EPSL, 391 [3] Nägler, et al. (2014) GGR, 38. [4] Voegelin et al. (2014) Lithos, 190-191.

Mass Dependent Fractionation of Hg Isotopes in Source Rocks, Mineral Deposits and Spring Waters of the California Coast Ranges, USA

NASA Astrophysics Data System (ADS)

Smith, C. N.; Kesler, S. E.; Blum, J. D.; Rytuba, J. J.

2007-12-01

We present here the first study of the isotopic composition of Hg in rocks, ore deposits, and active hydrothermal systems from the California Coast Ranges, one of Earth's largest Hg-depositing systems. The Franciscan Complex and Great Valley Sequence, which form the bedrock in the California Coast Ranges, are intruded and overlain by Tertiary volcanic rocks including the Clear Lake Volcanic Sequence. These rocks contain two types of Hg deposits, hot-spring deposits that form at shallow depths (<300 m) and silica-carbonate deposits that extend to greater depths (200 to 1000 m), as well as active springs and geothermal systems that release Hg to the present surface. The Franciscan Complex and Great Valley Sequence contain clastic sedimentary rocks with higher concentrations of Hg than volcanic rocks of the Clear Lake Volcanic Field. Mean Hg isotope compositions for all three rock units are similar, although the range of values in Franciscan Complex rocks is greater than in either Great Valley or Clear Lake rocks. Hot spring and silica-carbonate Hg deposits have similar average isotopic compositions that are indistinguishable from averages for the three rock units, although δ202Hg values for the Hg deposits have a greater variance than the country rocks. Precipitates from dilute spring and saline thermal waters in the area have similarly large variance and a mean δ202Hg value that is significantly lower than the ore deposits and rocks. These observations indicate there is little or no isotopic fractionation during release of Hg from its source rocks into hydrothermal solutions. Isotopic fractionation does appear to take place during transport and concentration of Hg in deposits, especially in their uppermost parts. Boiling of hydrothermal fluids is likely the most important process causing of the observed Hg isotope fractionation. This should result in the release of Hg with low δ202Hg values into the atmosphere from the top of these hydrothermal systems and a consequent enrichment in heavy Hg isotopes in the upper crust through time.

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.

Osmium Stable Isotope Composition of Chondrites and Iron Meteorites: Implications for Planetary Core Formation

NASA Astrophysics Data System (ADS)

Nanne, J. A. M.; Millet, M. A.; Burton, K. W.; Dale, C. W.; Nowell, G. M.; Williams, H. M.

2016-12-01

Mass-dependent Os stable isotope fractionation is expected to occur during metal-silicate segregation as well as during crystallization of metal alloys due to the different bonding environment between silicate and metals. As such, Os stable isotopes have the potential to resolve questions pertaining to planetary accretion and differentiation. Here, we present stable Os isotope data for a set of chondrites and iron meteorites to examine the processes associated with core solidification. Carbonaceous, ordinary, and enstatite chondrites show no detectable stable isotope variation with a δ190Os weighted average of +0.12±0.04 (n=37). The uniform composition observed for chondrites implies Os stable isotope homogeneity of the bulk solar nebula. Contrary to chondrites, iron meteorites display a large range in Os stable isotope compositions from δ190Os of +0.05 up to +0.49‰. Variation is only observed in the IIAB and IIIAB irons. Type IVB irons display values similar to chondrites (+0.107±0.047 [n=3]) and IVA compositions are slightly different +0.187±0.004 (n=2). The type IIAB and IIIAB groups show values both within the chondritic range and up to heavier values extending up to +0.49‰. Since core formation in small planetary bodies is expected to quantitatively sequester Os in metal phases, bulk planetary cores are expected to display chondritic δ190Os values. Conversely, samples of the IIAB and IIIAB group display significant variation, possibly indicating that stable isotope fractionation occurred during solidification of the parent-body core. However, no covariation is observed between δ190Os and either Os abundance or radiogenic Os isotope ratios. Instead, liquid immiscibility during core crystallization, where the liquid metal splits into separate S- and P-rich liquids, may be a source of Os stable isotope fractionation.

Re-Os systematics of komatiites and komatiitic basalts at Dundonald Beach, Ontario, Canada: Evidence for a complex alteration history and implications of a late-Archean chondritic mantle source

NASA Astrophysics Data System (ADS)

Gangopadhyay, A.; Sproule, R. A.; Walker, R. J.; Lesher, C.

2004-12-01

Re-Os concentrations and isotopic compositions have been examined in one komatiite unit and one komatiitic basalt unit at Dundonald Beach, which is part of the spatially-extensive 2.7 Ga Kidd-Munro volcanic assemblage in the Abitibi greenstone belt, Ontario, Canada. The komatiitic rocks in this locality record at least three episodes of alteration of Re-Os elemental and isotope systematics. First, an average of 40% and as much as 75% Re was lost due to shallow degassing during eruption and/or hydrothermal leaching during or immediately after the lava emplacement. Second, the Re-Os isotope systematics of the rocks with 187Re/188Os ratios >1 were reset at ˜2.5 Ga, most likely due to a regional metamorphic event. Finally, there is evidence for relatively recent gain and loss of Re. The variations in Os concentrations in the Dundonald komatiites yield a relative bulk distribution coefficient for Os (DOs solid/liquid) of 2-4, consistent with those obtained for stratigraphically-equivalent komatiites in the nearby Alexo area and in Munro Township. This suggests that Os was moderately compatible during crystal-liquid fractionation of the magma parental to the Kidd-Munro komatiitic rocks. Furthermore, whole-rock samples and chromite separates with low 187Re/188Os ratios (<1) yield a precise chondritic average initial 187Os/188Os ratio of 0.1083 ± 0.0006 (\\gammaOs = 0.0 ± 0.6). The chondritic initial Os isotopic composition of the mantle source for the Dundonald rocks is consistent with that determined for komatiites in the Alexo area and in Munro Township. Our Os isotope results for the Dundonald komatiitic rocks, combined with those in the Alexo and Pyke Hill areas suggest that the mantle source region for the Kidd- Munro volcanic assemblage had evolved along a long-term chondritic Os isotopic trajectory until their eruption at ˜2.7 Ga. The chondritic initial Os isotopic composition of the Kidd-Munro komatiites is indistinguishable from that of the projected contemporaneous convective upper mantle. The uniform chondritic Os isotopic composition of the ˜2.7 Ga mantle source for the Kidd-Munro komatiites contrasts with the typical large-scale Os isotopic heterogeneity in the mantle sources for komatiites from the Gorgona Island, present-day ocean island basalts or arc-related lavas. This suggests a significantly more homogeneous mantle source in the Archean compared to the presentday mantle.

Fluid heterogeneity during granulite facies metamorphism in the Adirondacks: stable isotope evidence

USGS Publications Warehouse

Valley, J.W.; O'Neil, J.R.

1984-01-01

The preservation of premetamorphic, whole-rock oxygen isotope ratios in Adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived, hot CO2-H2O fluids during granulite facies metamorphism. This conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations. The data suggest that these rocks were not an open system during metamorphism; that fluid/rock ratios were in many instances between 0.0 and 0.1; that externally derived fluids, as well as fluids derived by metamorphic volatilization, rose along localized channels and were not pervasive; and thus that no single generalization can be applied to metamorphic fluid conditions in the Adirondacks. Analyses of 3 to 4 coexisting minerals from Adirondack marbles show that isotopic equilibrium was attained at the peak of granulite and upper amphibolite facies metamorphism. Thus the isotopic compositions of metamorphic fluids can be inferred from analyses of carbonates and fluid budgets can be constructed. Carbonates from the granulite facies are on average, isotopically similar to those from lower grade or unmetamorphosed limestones of the same age showing that no large isotopic shifts accompanied high grade metamorphism. Equilibrium calculations indicate that small decreases in ??18O, averaging 1 permil, result from volatilization reactions for Adirondack rock compositions. Additional small differences between amphibolite and granulite facies marbles are due to systematic lithologie differences. The range of Adirondack carbonate ??18O values (12.3 to 27.2) can be explained by the highly variable isotopic compositions of unmetamorphosed limestones in conjunction with minor 18O and 13C depletions caused by metamorphic volatilization suggesting that many (and possibly most) marbles have closely preserved their premetamorphic isotopic compositions. Such preservation is particularly evident in instances of high ??18O calcites (25.0 to 27.2), low ??18O wollastonites (-1.3 to 3.5), and sharp gradients in ??18O (18 permil/15m between marble and anorthosite, 8 permil/25 m in metasediments, and 6 permil/1 m in skarn). Isotopic exchange is seen across marble-anorthosite and marble-granite contacts only at the scale of a few meters. Small (<5 m) marble xenoliths are in approximate exchange equilibrium with their hosts, but for larger xenoliths and layers of marble there is no evidence of exchange at distances greater than 10 m from meta-igneous contacts. ?? 1984 Springer-Verlag.

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

ISOTOPIC COMPOSITION OF THE COMMON LEAD OF JAPAN

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

Sakai, H.; Sato, K.

1958-11-01

Lead tetramethyl was synthesized from lead iodide isolated from 14 galenas, 2 anglesites, and 6 pyromorphites of Japan. The mass spectrometric analysis was carried out for the peaks of lead and lead hydride ions. The isotopic compositions of leads from these minerais lie wiyhn a narrow range. The average values for gnlanas are 18.51 O 0.05 for Pb/sup 238//Pb/sup 204/ 15.60 plus or minus 0.05 for Pb/sup 207//Pb/sup 204/8.76 plus or minus 0.15 forPb/ sup 208//Pb/sup 204/ For lead of secondary minerals they are 18.52 plus or minus 0.05, 15.62 plus or minus 0.05, and 38.78 plus or minus 0.15,more » respectively. No detectabla difference was observed between the isotopic compositions of primary and secondary lead ores. The ratios, U/sub 238/Pb/sup 204, and Th/sup 232/ U/sup 238/, in the source magma are estimated from the lead abundances. They are« less

Source area and seasonal variation of dissolved Sr isotope composition in rivers of the Amazon basin

NASA Astrophysics Data System (ADS)

Santos, Roberto V.; Sondag, Francis; Cochonneau, Gerard; Lagane, Christelle; Brunet, Pierre; Hattingh, Karina; Chaves, Jeane G. S.

2014-05-01

We present dissolved Sr isotope data collected over 8 years from three main river systems from the Amazon Basin: Beni-Madeira, Solimões, Amazon, and Negro. The data show large 87Sr/86Sr ratio variations that were correlated with the water discharge and geology of the source areas of the suspended sediments. The Beni-Madeira system displays a high average 87Sr/86Sr ratio and large 87Sr/86Sr fluctuations during the hydrological cycle. This large average value and fluctuations were related to the presence of Precambrian rocks and Ordovician sediments in the source area of the suspended sediment of the river. In contrast, the Solimões system displays a narrow range of Sr isotope ratio variations and an average value close to 0.709. This river drains mostly Phanerozoic rocks of northern Peru and Ecuador that are characterized by low Sr isotope ratios. Despite draining areas underlain by Precambrian rocks and having high 87Sr/86Sr ratios, such rivers as the Negro and Tapajós play a minor role in the total Sr budget of the Amazon Basin. The isotopic fluctuations in the Beni-Madeira River were observed to propagate downstream at least as far as Óbidos, in the Amazon River. This signal is characterized by an inverse relationship between the concentration of elemental Sr and its isotopic ratios. During the raining season there is an increase in Sr isotopic ratio accompanied by a decrease in elemental Sr concentration. During the dry season, the Sr isotopic ration decreases and the elemental Sr concentration increases.

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.

Vertical variation in the amplitude of the seasonal isotopic content of rainfall as a tool to jointly estimate the groundwater recharge zone and transit times in the Ordesa and Monte Perdido National Park aquifer system, north-eastern Spain.

PubMed

Jódar, Jorge; Custodio, Emilio; Lambán, Luis Javier; Martos-Rosillo, Sergio; Herrera-Lameli, Christian; Sapriza-Azuri, Gonzalo

2016-12-15

The time series of stable water isotope composition relative to meteorological stations and springs located in the high mountainous zone of the Ordesa and Monte Perdido National Park are analyzed in order to study how the seasonal isotopic content of precipitation propagates through the hydrogeological system in terms of the aquifer recharge zone elevation and transit time. The amplitude of the seasonal isotopic composition of precipitation and the mean isotopic content in rainfall vary along a vertical transect, with altitudinal slopes for δ 18 O of 0.9‰/km for seasonal amplitude and -2.2‰/km for isotopic content. The main recharge zone elevation for the sampled springs is between 1950 and 2600m·a.s.l. The water transit time for the sampled springs ranges from 1.1 to 4.5yr, with an average value of 1.85yr and a standard deviation of 0.8yr. The hydrological system tends to behave as a mixing reservoir. Copyright © 2016 Elsevier B.V. All rights reserved.

Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

PubMed Central

Balci, Nurgul; Brunner, Benjamin; Turchyn, Alexandra V.

2017-01-01

Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62−) and elemental sulfur (S°) to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6) by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4) from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2). During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O) of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4), acid production, and mixed valence state sulfur species generated by the oxidation of the two different substrates suggests a metabolic flexibility in response to sulfur substrate availability. Our results demonstrate that microbial processing of mixed-valence-state sulfur species generates a significant sulfur isotope fractionation in acidic environments and oxidation of mixed-valence state sulfur species may produce sulfate with characteristic sulfur and oxygen isotope signatures. Elemental sulfur and tetrathionate are not only intermediate-valence state sulfur compounds that play a central role in sulfur oxidation pathways, but also key factors in shaping these isotope patterns. PMID:28861071

Evapotranspiration Partitioning Using Rapid Measurements of Isotopic Composition of Water Vapor in a Semi Arid Evergreen Forest

NASA Astrophysics Data System (ADS)

Meuth, J. A.; Dominguez, F.

2011-12-01

Evapotranspiration partitioning into transpiration and evaporation is an important step in understanding the relative contribution of the vegetated land surface to total atmospheric moisture in an area. This type of study has rarely been done over long time periods focusing on small time scales of variation. The relative contributions of whole canopy transpiration and soil evaporation to total evapotranspiration were determined in a mid-latitude semi arid evergreen forest using stable isotope measurements of atmospheric water vapor. We used a cavity ringdown spectrometer to collect continuous 5-second average isotopic and water vapor measurements throughout the ecosystem boundary layer. In addition, we analyzed the isotopic composition of liquid water extracted from soil, leaf and stem samples to obtain relative contributions of transpiration and evaporation to whole canopy evapotranspriation. The results from this method provided many time periods throughout the day with statistically significant data. This method can be used to follow daily, monthly, or yearly cycles of evapotranspiration partitioning with relative ease and accuracy.

Carbon isotope compositions of terrestrial C3 plants as indicators of (paleo)ecology and (paleo)climate.

PubMed

Kohn, Matthew J

2010-11-16

A broad compilation of modern carbon isotope compositions in all C3 plant types shows a monotonic increase in δ(13)C with decreasing mean annual precipitation (MAP) that differs from previous models. Corrections for temperature, altitude, or latitude are smaller than previously estimated. As corrected for altitude, latitude, and the δ(13)C of atmospheric CO(2), these data permit refined interpretation of MAP, paleodiet, and paleoecology of ecosystems dominated by C3 plants, either prior to 7-8 million years ago (Ma), or more recently at mid- to high latitudes. Twenty-nine published paleontological studies suggest preservational or scientific bias toward dry ecosystems, although wet ecosystems are also represented. Unambiguous isotopic evidence for C4 plants is lacking prior to 7-8 Ma, and hominid ecosystems at 4.4 Ma show no isotopic evidence for dense forests. Consideration of global plant biomass indicates that average δ(13)C of C3 plants is commonly overestimated by approximately 2‰.

Osmium isotopic tracing of atmospheric emissions from an aluminum smelter

NASA Astrophysics Data System (ADS)

Gogot, Julien; Poirier, André; Boullemant, Amiel

2015-09-01

We present for the first time the use of osmium isotopic composition as a tracer of atmospheric emissions from an aluminum smelter, where alumina (extracted from bauxite) is reduced through electrolysis into metallic aluminum using carbonaceous anodes. These anodes are consumed in the process; they are made of petroleum coke and pitch and have high Re/Os elementary ratio. Due to the relatively large geological age of their source material, their osmium shows a high content of radiogenic 187Os produced from in situ187Re radioactive decay. The radiogenic isotopic composition (187Os/188Os ∼ 2.5) of atmospheric particulate emissions from this smelter is different from that of other typical anthropogenic osmium sources (that come from ultramafic geological contexts with unradiogenic Os isotopes, e.g., 187Os/188Os < 0.2) and also different from average eroding continental crust 187Os/188Os ratios (ca. 1.2). This study demonstrates the capacity of osmium measurements to monitor particulate matter emissions from the Al-producing industry.

Thallium-isotopic compositions of euxinic sediments as a proxy for global manganese-oxide burial

NASA Astrophysics Data System (ADS)

Owens, Jeremy D.; Nielsen, Sune G.; Horner, Tristan J.; Ostrander, Chadlin M.; Peterson, Larry C.

2017-09-01

Thallium (Tl) isotopes are a new and potentially powerful paleoredox proxy that may track bottom water oxygen conditions based on the global burial flux of manganese oxides. Thallium has a residence time of ∼20 thousand years, which is longer than the ocean mixing time, and it has been inferred that modern oxic seawater is conservative with respect to both concentration and isotopes. Marine sources of Tl have nearly identical isotopic values. Therefore, the Tl sinks, adsorption onto manganese oxides and low temperature oceanic crust alteration (the dominant seawater output), are the primary controls of the seawater isotopic composition. For relatively short-term, ∼million years, redox events it is reasonable to assume that the dominant mechanism that alters the Tl isotopic composition of seawater is associated with manganese oxide burial because large variability in low temperature ocean crust alteration is controlled by long-term, multi-million years, average ocean crust production rates. This study presents new Tl isotope data for an open ocean transect in the South Atlantic, and depth transects for two euxinic basins (anoxic and free sulfide in the water column), the Cariaco Basin and Black Sea. The Tl isotopic signature of open ocean seawater in the South Atlantic was found to be homogeneous with ε205Tl = -6.0 ± 0.3 (±2 SD, n = 41) while oxic waters from Cariaco and the Black Sea are -5.6 and -2.2, respectively. Combined with existing data from the Pacific and Arctic Oceans, our Atlantic data establish the conservatism of Tl isotopes in the global ocean. In contrast, partially- and predominantly-restricted basins reveal Tl isotope differences that vary between open-ocean (-6) and continental material (-2) ε205Tl, scaling with the degree of restriction. Regardless of the differences between basins, Tl is quantitatively removed from their euxinic waters below the chemocline. The burial of Tl in euxinic sediments is estimated to be an order of magnitude less than each of the modern ocean outputs and imparts no isotopic fractionation. Thallium removal into pyrite appears to be associated with a small negative fractionation between -1 and -3 ε205Tl, which renders Tl-depleted waters below the chemocline enriched in isotopically-heavy Tl. Due to the quantitative removal of Tl from euxinic seawater, Tl isotope analyses of the authigenic fraction of underlying euxinic sediments from both the Black Sea and Cariaco Basin capture the Tl isotope value of the oxic portion of their respective water column with no net isotope fractionation. Since the Tl isotope composition of seawater is largely dictated by the relative fraction of Mn-oxide burial versus oceanic crust alteration, we contend that the Tl isotope composition of authigenic Tl in black shales, deposited under euxinic conditions but well-connected to the open ocean, can be utilized to reconstruct the Tl isotope composition of seawater, and thus to reconstruct the global history of Mn-oxide burial.

The silicon isotopic composition of fine-grained river sediments and its relation to climate and lithology

NASA Astrophysics Data System (ADS)

Bayon, G.; Delvigne, C.; Ponzevera, E.; Borges, A. V.; Darchambeau, F.; De Deckker, P.; Lambert, T.; Monin, L.; Toucanne, S.; André, L.

2018-05-01

The δ30Si stable isotopic composition of silicon in soils and fine-grained sediments can provide insights into weathering processes on continents, with important implications on the Si budget of modern and past oceans. To further constrain the factors controlling the distribution of Si isotopes in sediments, we have analysed a large number (n = 50) of separate size-fractions of sediments and suspended particulate materials collected near the mouth of rivers worldwide. This includes some of the world's largest rivers (e.g. Amazon, Congo, Mackenzie, Mississippi, Murray-Darling, Nile, Yangtze) and rivers from the case study areas of the Congo River Basin and Northern Ireland. Silt-size fractions exhibit a mean Si isotopic composition (δ30Si = -0.21 ± 0.19‰; 2 s.d.) similar to that previously inferred for the upper continental crust. In contrast, clay-size fractions display a much larger range of δ30Si values from -0.11‰ to -2.16‰, which yield a global δ30Siclay of -0.57 ± 0.60‰ (2 s.d.) representative of the mean composition of the average weathered continental crust. Overall, these new data show that the Si isotopic signature transported by river clays is controlled by the degree of chemical weathering, as inferred from strong relationships with Al/Si ratios. At a global scale, the clay-bound Si isotopic composition of the world's largest river systems demonstrates a link with climate, defining a general correlation with mean annual temperature (MAT) in corresponding drainage basins. While the distribution of Si isotopes in river sediments also appears to be influenced by the tectonic setting, lithological effects and sediment recycling from former sedimentary cycles, our results pave the way for their use as paleo-weathering and paleo-climate proxies in the sedimentary record.

Determination of the isotopic composition of evapotranspiration in a mature oil palm plantation in Jambi province, Indonesia.

NASA Astrophysics Data System (ADS)

Bonazza, Mattia; Meijide, Ana; Knohl, Alexander

2017-04-01

Evapotranspiration (ET) is defined as the sum of the water vapor fluxes from evaporation (E) and transpiration (T). The relative proportion between these two quantities depends on the species, on their age and on the structure of the stand and canopy. Evaporation represents the fraction of water that doesn't contribute to plants growth hence it often considered as "unused" water by the plants root system. For this reason, in a fast changing environment like Indonesia where, since almost 30 years, tropical rainforests are gradually converted into extensive oil palm plantation, it is important to quantify the amount of evaporated water to improve agricultural practices and water quality. As powerful tracers of the hydrological cycle, water stable isotopes represent an important tool to estimate the isotopic composition of the evapotranspiration flux and they can be used as a starting point for the determination of the T/ET ratio, which can be considered as a plant water uptake efficiency indicator. The isotopic composition (δDvand δ18Ov) and the mixing ratio (qv) of water vapor measured in a stand is the result of the isotopic mixing between two members; ecosystem evapotranspiration (δET) and background air (δa). With the implementation of laser-based isotopic analysers we are now able to improve the measurement frequency of δDvand δ18Ov that leads us to an improved estimation of δET. Here we present the results of a measurement campaign, performed with a Picarro L-2120i and conducted in a mature oil palm plantation in the province of Jambi, Indonesia. We measured the atmospheric water vapor mixing ratio and isotopic composition at 5 sampling heights (21 m, 16 m, 9 m, 3.5 and 0.3 m) along a flux tower throughout the oil palm canopy (average height 10 m). The range of the water vapor isotopic composition was between -19 and -11 and -134 and -82 ‰ for δ18Ov and δDvrespectively. A fairly open canopy structure resulted in small mixing ratio gradients along the vertical profile. We collected and analysed all rain event and estimated the variability of the water vapor isotopic composition. Micrometeorological measurements, provided by the tower's sensors, were used to calculate ET using the Bowen ratio energy balance. To determine the isotopic composition of the evapotranspiration flux we used and compared two different methods: Keeling plot and flux gradient approach.

Compositional changes in the UCC through time revealed by tungsten isotopes

NASA Astrophysics Data System (ADS)

Mundl, A.; Walker, R. J.; Reimink, J. R.; Rudnick, R. L.; Gaschnig, R. M.

2017-12-01

During periods of glaciation, ice scrapes off large areas of Earth's surface. The resulting sediments, termed glacial diamictites, are typically little affected by chemical alteration during their accumulation and lithification. The fine-grained matrix of a diamictite can therefore provide important information about the average composition of a portion of the upper continental crust (UCC) preceding the time of its deposition. Major and trace element studies of diamictites have reported compositional changes in the UCC through Earth's history, documenting changes in its average lithology. Short-lived radiogenic isotope systems are useful tools to further study crustal evolution via diamictites, as small-scale 182W (182Hf → 182W, t½ = 8.9 Ma) and 142Nd (146Nd → 142Nd, t½= 103 Ma) anomalies may reflect mantle or crustal processes that occurred very early in Earth history. We have investigated 182W/184W ratios in thirteen glacial diamictite composites from four different continents. These rocks were deposited during the Archean (3.0 Ga), Proterozoic (2.4, 2.3, 2.2, 0.6 Ga) and Paleozoic (0.3 Ga) in South Africa, as well as during the Proterozoic (2.4, 0.7, 0.6 Ga) in North America, and the Paleozoic (0.3 Ga) in South America. Individual glacial diamictites sample multiple crustal sources, so the isotopic compositions of the diamictites are more representative of the UCC at the time of deposition, than the komatiites and early Archean supracrustal rocks, which have been the focus of most prior studies. Tungsten isotope compositions reveal well-resolved deficits in 182W/184W of as much as 14 ppm in three of the four Archean samples from South Africa. By contrast, there are no clearly resolved deficits in Paleoproterozoic diamictites from the same area, although results for multiple analyses of the same samples suggest that a small deficit of 6 ppm may be present. No anomalies are present in younger diamictites. The Archean diamictites provide additional evidence for considerable heterogeneity in 182W in Archean crustal rocks, consistent with prior studies of individual rock units. The lack of anomalies in younger diamictites suggests that the isotopically heterogeneous nature of 182W in the Archean crust had disappeared by the beginning of the Proterozoic, as with 142Nd. Reasons for the transition remain unclear.

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

2013-01-01

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleo-environmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analysis. More experiments are planned to discern these two or other possible scenarios.

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.

Annual cycles of mass flux and isotopic composition of pteropod shells settling into the deep Sargasso sea

NASA Astrophysics Data System (ADS)

Jasper, John P.; Deuser, Werner G.

1993-04-01

Mass fluxes and stable isotopic compositions ( δ18O and δ13C) pteropod shells collected during a 6-year series of 2-month sediment-trap deployments in the deep (3.2 km) Sargasso Sea provide information on annual population changes, habitat depths and life spans of thecosome pteropods (Euthecosomata). The flux of pteropod shells responds to the annual cycle of primary production in the upper ocean. Flux maxima of the shells (> 1 mm) of eight species occur from late winter through autumn. Seasonal changes in the hydrography of the upper water column are quite accurately recorded in the δ18O variations of six perennial species, which generally confirm the distinction between non-migratory ( Creseis acicula, Creseis virgula conica, and Diacria quadridentata) and diurnally migratory taxa ( Styliola subula, Cuvierina columnella, and Clio pyramidata). Isotopic records of C. acicula and C. virgula conica are consistent with shell formation above 50 m. The records of the migratory species reflect what appear to be average calcification depths of 50-75 m. Average annual δ13C variations reveal the annual cycles of primary production and stratification of near-surface waters. Adult life spans of the species studied appear to be no more than a few months. The results of this study should be useful in paleoceanographic reconstructions based on isotopic measurements of sedimentary pteropod shells.

Identification of an Extremely 180-Rich Presolar Silicate Grain in Acfer 094

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Messenger, S.

2009-01-01

Presolar silicate grains have been abundantly identified since their first discovery less than a decade ago [1,2,3]. The O isotopic compositions of both silicate and oxide stardust indicate the vast majority (>90%) condensed around Orich asymptotic giant branch (AGB) stars. Though both presolar phases have average sizes of 300 nm, grains larger than 1 m are extremely uncommon for presolar silicates. Thus, while numerous isotopic systems have been measured in presolar oxide grains [4], very few isotopic analyses for presolar silicates exist outside of O and Si [2,5]. And still, these measurements suffer from isotopic dilution with surrounding matrix material [6]. We conduct a search for presolar silicates in the primitive carbonaceous chondrite Acfer 094 and in some cases obtain high spatial resolution, high precision isotopic ratios.

The distribution of lead concentrations and isotope compositions in the eastern Tropical Atlantic Ocean

NASA Astrophysics Data System (ADS)

Bridgestock, Luke; Rehkämper, Mark; van de Flierdt, Tina; Paul, Maxence; Milne, Angela; Lohan, Maeve C.; Achterberg, Eric P.

2018-03-01

Anthropogenic emissions have dominated marine Pb sources during the past century. Here we present Pb concentrations and isotope compositions for ocean depth profiles collected in the eastern Tropical Atlantic Ocean (GEOTRACES section GA06), to trace the transfer of anthropogenic Pb into the ocean interior. Variations in Pb concentration and isotope composition were associated with changes in hydrography. Water masses ventilated in the southern hemisphere generally featured lower 206Pb/207Pb and 208Pb/207Pb ratios than those ventilated in the northern hemisphere, in accordance with Pb isotope data of historic anthropogenic Pb emissions. The distributions of Pb concentrations and isotope compositions in northern sourced waters were consistent with differences in their ventilation timescales. For example, a Pb concentration maximum at intermediate depth (600-900 m, 35 pmol kg-1) in waters sourced from the Irminger/Labrador Seas, is associated with Pb isotope compositions (206Pb/207Pb = 1.1818-1.1824, 208Pb/207Pb = 2.4472-2.4483) indicative of northern hemispheric emissions during the 1950s and 1960s close to peak leaded petrol usage, and a transit time of ∼50-60 years. In contrast, North Atlantic Deep Water (2000-4000 m water depth) featured lower Pb concentrations and isotope compositions (206Pb/207Pb = 1.1762-1.184, 208Pb/207Pb = 2.4482-2.4545) indicative of northern hemispheric emissions during the 1910s and 1930s and a transit time of ∼80-100 years. This supports the notion that transient anthropogenic Pb inputs are predominantly transferred into the ocean interior by water mass transport. However, the interpretation of Pb concentration and isotope composition distributions in terms of ventilation timescales and pathways is complicated by (1) the chemical reactivity of Pb in the ocean, and (2) mixing of waters ventilated during different time periods. The complex effects of water mass mixing on Pb distributions is particularly apparent in seawater in the Tropical Atlantic Ocean which is ventilated from the southern hemisphere. In particular, South Atlantic Central Water and Antarctic Intermediate Water were dominated by anthropogenic Pb emitted during the last 50-100 years, despite estimates of much older average ventilation ages in this region.

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.

Constraints on post-depositional isotope modifications in East Antarctic firn from analysing temporal changes of isotope profiles

NASA Astrophysics Data System (ADS)

Münch, Thomas; Kipfstuhl, Sepp; Freitag, Johannes; Meyer, Hanno; Laepple, Thomas

2017-09-01

The isotopic composition of water in ice sheets is extensively used to infer past climate changes. In low-accumulation regions their interpretation is, however, challenged by poorly constrained effects that may influence the initial isotope signal during and after deposition of the snow. This is reflected in snow-pit isotope data from Kohnen Station, Antarctica, which exhibit a seasonal cycle but also strong interannual variations that contradict local temperature observations. These inconsistencies persist even after averaging many profiles and are thus not explained by local stratigraphic noise. Previous studies have suggested that post-depositional processes may significantly influence the isotopic composition of East Antarctic firn. Here, we investigate the importance of post-depositional processes within the open-porous firn (≳ 10 cm depth) at Kohnen Station by separating spatial from temporal variability. To this end, we analyse 22 isotope profiles obtained from two snow trenches and examine the temporal isotope modifications by comparing the new data with published trench data extracted 2 years earlier. The initial isotope profiles undergo changes over time due to downward advection, firn diffusion and densification in magnitudes consistent with independent estimates. Beyond that, we find further modifications of the original isotope record to be unlikely or small in magnitude (≪ 1 ‰ RMSD). These results show that the discrepancy between local temperatures and isotopes most likely originates from spatially coherent processes prior to or during deposition, such as precipitation intermittency or systematic isotope modifications acting on drifting or loose surface snow.

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.

Evidence for a nonmagmatic component in potassic hydrothermal fluids of porphyry cu-Au-Mo systems, Yukon, Canada

NASA Astrophysics Data System (ADS)

Selby, David; Nesbitt, Bruce E.; Creaser, Robert A.; Reynolds, Peter H.; Muehlenbachs, Karlis

2001-02-01

Isotopic (H, Sr, Pb, Ar) and fluid inclusion data for hydrothermal fluids associated with potassic alteration from three Late Cretaceous porphyry Cu occurrences, west central Yukon, suggest a nonmagmatic fluid component was present in these hydrothermal fluids. Potassic stage quartz veins contain a dominant assemblage of saline and vapor-rich fluid inclusions that have δD values between -120 and -180‰. Phyllic stage quartz veins are dominated by vapor-rich fluid inclusions and have δD values that overlap with but are, on average, heavier (-117 to -132‰) than those in potassic stage quartz veins. These δD values are significantly lower than those from plutonic quartz phenocrysts (-91 to -113‰), and from values typically reported for primary fluids from porphyry-style mineralization (-40 to -100‰). The initial Sr ( 87Sr/ 86Sr i) isotopic values for the plutons are 0.7055 (Casino), 0.7048 (Mt. Nansen), and 0.7055 (Cash). The 87Sr/ 86Sr i compositions of hydrothermal K-feldspar ranges from magmatic Sr i values to more radiogenic compositions (Casino: 0.70551-0.70834, n = 8; Mt. Nansen: 0.7063-0.7070, n = 4; Cash: 0.7058, n = 1). The fluid inclusion waters from potassic quartz veins have 87Sr/ 86Sr i values that are similar to those of co-existing hydrothermal K-feldspar. The Pb isotopic compositions of hydrothermal K-feldspar show a weak positive correlation with Sr i for identical samples. Fluid inclusion waters of phyllic quartz veins also have Sr i compositions more radiogenic than the plutons. The Pb isotopic composition of pyrite and bornite from phyllic alteration veins are similar to, or more radiogenic than, hydrothermal K-feldspar Pb isotopic values. Hydrothermal K-feldspar samples yield 40Ar/ 39Ar ages (Casino = 71.9 ± 0.7 to 73.4 ± 0.8 Ma; Mt. Nansen = 68.2 ± 0.7 and 69.5 ± 0.6 Ma; Cash = 68.3 ± 0.8 Ma) similar to the U-Pb zircon, K-Ar biotite and Re-Os molybdenite ages of the Late Cretaceous plutons, with the age spectra indicating no excess 40Ar or disturbance. The 40Ar/ 36Ar values (285-292) of the K-feldspar samples are similar to the atmospheric compositions (295 ± 5) during Late Cretaceous time. The H, Sr, Pb, and Ar isotopic compositions of hydrothermal K-feldspar and quartz vein fluid inclusion waters that characterize the potassic hydrothermal fluids show evidence for an exotic component in addition to magmatic water (fluid). This component has a low δD, radiogenic Sr and Pb, and an atmospheric Ar composition. The inheritance of pre-existing isotope compositions from the host rocks, postpotassic alteration isotope exchange, or the replenishment of the magma chamber with magma of different isotopic composition cannot explain the isotope data. We suggest that to generate the observed H, Sr, Pb, and Ar isotope compositions, crustal fluids must be a component (15-94%) of potassic hydrothermal fluids in porphyry mineralization in the deposits studied.

Magnesium Isotopic Composition of Kamchatka Sub-Arc Mantle Peridotites

NASA Astrophysics Data System (ADS)

Hu, Y.; Teng, F. Z.; Ionov, D. A.

2016-12-01

Subduction of the oceanic slab may add a crustal isotopic signal to the mantle wedge. The highly variable Mg isotopic compositions (δ26Mg) of the subducted oceanic crust input[1] and arc lava output[2] imply a distinctive Mg isotopic signature of the mantle wedge. Magnesium isotopic data on samples from the sub-arc mantle are still limited, however. To characterize the Mg isotopic composition of typical sub-arc mantle, 17 large and fresh spinel harzburgite xenoliths from Avacha volcano were analyzed. The harzburgites were formed by 30% melt extraction at ≤ 1 2 GPa and fluid fluxing condition, and underwent possible fluid metasomatism as suggested by distinctively high orthopyroxene mode in some samples, the presence of accessory amphibole and highly variable Ba/La ratios[3]. However, their δ26Mg values display limited variation from -0.32 to -0.21, which are comparable to the mantle average at -0.25 ± 0.07[4]. The overall mantle-like and homogenous δ26Mg of Avacha sub-arc peridotites are consistent with their similar chemical compositions and high MgO contents (> 44 wt%) relative to likely crustal fluids. Furthermore, clinopyroxene (-0.24 ± 0.10, 2SD, n = 5), a late-stage mineral exsolved from high-temperature, Ca-rich residual orthopyroxene, is in broad Mg isotopic equilibrium with olivine (-0.27 ± 0.04, 2SD, n = 17) and orthopyroxene (-0.22 ± 0.06, 2SD, n = 17). Collectively, this study finds that the Kamchatka mantle wedge, as represented by the Avacha peridotites, has a mantle-like δ26Mg, and low-degree fluid-mantle interaction does not cause significant Mg isotope fractionation in sub-arc mantle peridotites. [1] Wang et al., EPSL, 2012 [2] Teng et al., PNAS, 2016 [3] Ionov, J. Petrol., 2010, [4] Teng et al., GCA, 2010.

Regional fluid migration in the Illinois basin: evidence from in situ oxygen isotope analysis of authigenic K-feldspar and quartz from the Mount Simon Sandstone

USGS Publications Warehouse

Chen, Zhensheng; Riciputi, Lee R.; Mora, Claudia I.; Fishman, Neil S.

2001-01-01

Oxygen isotope compositions of widespread, authigenic K-feldspar and quartz overgrowths and cements in the Upper Cambrian Mount Simon Sandstone were measured by ion microprobe in 11 samples distributed across the Illinois basin and its periphery. Average K-feldspar δ18O values increase systematically from +14‰ ± 1‰ in the southernmost and deepest samples in Illinois to +24‰ ± 2‰ in the northernmost outcrop sample in Wisconsin. A similar trend was observed for quartz overgrowths (22‰ ± 2‰ to 28‰ ± 2‰). Constant homogenization temperatures (100–130 °C) of fluid inclusions associated with quartz overgrowths throughout the basin suggest that the geographic trend in oxygen isotope compositions is a result of diagenetic modification of a south to north migrating basinal fluid.

Barium isotopes in cold-water corals

NASA Astrophysics Data System (ADS)

Hemsing, Freya; Hsieh, Yu-Te; Bridgestock, Luke; Spooner, Peter T.; Robinson, Laura F.; Frank, Norbert; Henderson, Gideon M.

2018-06-01

Recent studies have introduced stable Ba isotopes (δ 138 / 134Ba) as a novel tracer for ocean processes. Ba isotopes could potentially provide insight into the oceanic Ba cycle, the ocean's biological pump, water-mass provenance in the deep ocean, changes in activity of hydrothermal vents, and land-sea interactions including tracing riverine inputs. Here, we show that aragonite skeletons of various colonial and solitary cold-water coral (CWC) taxa record the seawater (SW) Ba isotope composition. Thirty-six corals of eight different taxa from three oceanic regions were analysed and compared to δ 138 / 134Ba measurements of co-located seawater samples. Sites were chosen to cover a wide range of temperature, salinity, Ba concentrations and Ba isotope compositions. Seawater samples at the three sites exhibit the well-established anti-correlation between Ba concentration and δ 138 / 134Ba. Furthermore, our data set suggests that Ba/Ca values in CWCs are linearly correlated with dissolved [Ba] in ambient seawater, with an average partition coefficient of DCWC/SW = 1.8 ± 0.4 (2SD). The mean isotope fractionation of Ba between seawater and CWCs Δ138/134BaCWC-SW is -0.21 ± 0.08‰ (2SD), indicating that CWC aragonite preferentially incorporates the lighter isotopes. This fractionation likely does not depend on temperature or other environmental variables, suggesting that aragonite CWCs could be used to trace the Ba isotope composition in ambient seawater. Coupled [Ba] and δ 138 / 134Ba analysis on fossil CWCs has the potential to provide new information about past changes in the local and global relationship between [Ba] and δ 138 / 134Ba and hence about the operation of the past global oceanic Ba cycle in different climate regimes.

Human drinking water compared with river waters throughout the United States with respect to their stable hydrogen and oxygen isotopic composition

NASA Astrophysics Data System (ADS)

Landwehr, J. M.; Coplen, T. B.; Qi, H.

2009-04-01

The composition of stable isotopes of hydrogen (^2H) and oxygen (^18O) in animal tissues, such as hair, nail, teeth and bone, has been used to trace migrations and geographic origin of individuals. Variations of these isotopic ratios in tissue are known to show significant correlations with the isotopic composition of ingested water, as well as with diet and other oxygen sources. Drinking water in natural ecosystems is defined by what is locally available for animal consumption, primarily surface waters such as streams, ponds, lakes, seeps, springs, etc. Tap water provides the drinking water in many human ecosystems. It may derive from local sources but can also draw on more diverse sources, such as large rivers with watersheds larger than those of local creeks, deep ground waters or even imported supplies, which may be isotopically distinct from local ecosystem supplies. Because of the potentially complex hydrologic pathways of water sources available in either animal or human ecosystems, the stable isotopic composition of these supplies may differ significantly from that of the (weighted average) local precipitation which is sometimes used to represent local water supplies. For example, water samples taken from three different taps in Washington, D.C., USA, on August 15, 2007, had measured ^2H and ^18O values of -41.7 per mill and -6.13 per mill, -41.7 per mill and -6.06 per mill, and -42.2 per mill and -6.22 per mill, respectively. A water sample taken on the same day from the Potomac River, which is the source of the D.C. water supply, had ^2H and ^18O values of -41.7 per mill and -6.06 per mill, respectively, consistent with that of the urban tap water. However, precipitation samples collected locally in Reston, Virginia, USA, had ^2H and ^18O values of -16.1 per mill and -3.13 per mill, respectively, for the week ending on August 15, 2007; -17.5 per mill and -3.40 per mill, respectively, for the month preceding August 15, 2007; and -13.6 per mill and -3.39 per mill, respectively, for the average values for the month of August over three years. The isotopic composition of local precipitation was significantly more positive than that for the concurrently available tap water and the river water from which it was drawn. Thus, in order to allow valid geographic inferences for forensic purposes, it is necessary to have available the measured isotopic composition of drinking waters or of their appropriate sources. We have now collected tap water samples concurrently at 345 sites throughout the United States and measured ^2H and ^18O during both summer (2007) and winter (2008) seasons. Since large rivers are frequently the source of urban water supplies, we compare this information with data published for rivers and streams throughout the United States (Coplen and Kendall, 2000). These data and analyses should inform the use of stable isotopes of water for forensic determinations.

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2010-01-01

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V-PDB) apparent isotopic fractionation accompanies the pyrolysis extractions. We postulate that this isotope offset could be the result of incomplete thermal desorption during pyrolysis. We are continuing to investigate the reliability of this pyrolysis technique for correcting carbon isotope measurements of mineral surface catalyzed organic compounds.

Genetic link between EMI and EMII: An adakite connection

NASA Astrophysics Data System (ADS)

Shimoda, Gen

2009-10-01

Geochemical modeling of the origin of enriched mantle I (EMI) and enriched mantle II (EMII) is conducted from the perspective of adakite production. For the model, the average composition of adakites is re-estimated from published data for eighteen trace elements. Although the concentrations determined for highly incompatible elements are very high (about 100 times of primitive mantle), these high concentrations can be explained by melting of oceanic crust without sediment contribution. The compiled data further suggest that the mantle-slab melt reaction would play a major role in the production of basic adakites. In addition, crystal fractionation in the magma chamber should produce additional chemical variations in adakites, in particular for acidic adakites. To examine the effect of chemical variations on the isotopic composition of recycled adakites, broad correlations between trace elements and SiO 2 concentrations, and the MELTS program are employed. The results suggest that recycling of a basic adakite (SiO 2 = 55%) can account for EMI isotopic signatures with storage times of about 2.0 Gyr. The isotopic compositions of less-basic adakites and their evolved magmas shift towards EMII values with increasing SiO 2 concentrations. In particular, evolved acidic adakite can yield EMII isotopic signatures. These lines of evidence suggest that the recycling of adakites at various stages of evolution can conceivably produce the entire isotopic range between EMI and EMII reservoirs. Consequently, adakite recycling via sediment subduction or subduction erosion can account for the origins of EMI and EMII reservoirs. In this context, residual garnet under high pressure and plagioclase fractionation at low pressure might play an essential role in producing the chemical variations among adakites that ultimately govern the isotopic compositions of these geochemical reservoirs.

Alteration of the Carbon and Nitrogen Isotopic Composition in the Martian Surface Rocks Due to Cosmic Ray Exposure

NASA Technical Reports Server (NTRS)

Pavlov, A. A.; Pavlov, A. K.; Ostryakov, V. M.; Vasilyev, G. I.; Mahaffy, P.; Steele, A.

2014-01-01

C-13/C-12 and N-15/N-14 isotopic ratios are pivotal for our understanding of the Martian carbon cycle, history of the Martian atmospheric escape, and origin of the organic compounds on Mars. Here we demonstrate that the carbon and nitrogen isotopic composition of the surface rocks on Mars can be significantly altered by the continuous exposure of Martian surface to cosmic rays. Cosmic rays can effectively produce C-13 and N-15 isotopes via spallation nuclear reactions on oxygen atoms in various Martian rocks. We calculate that in the top meter of the Martian rocks, the rates of production of both C-13 and N-15 due to galactic cosmic rays (GCRs) exposure can vary within 1.5-6 atoms/cm3/s depending on rocks' depth and chemical composition. We also find that the average solar cosmic rays can produce carbon and nitrogen isotopes at a rate comparable to GCRs in the top 5-10 cm of the Martian rocks. We demonstrate that if the total carbon content in a surface Martian rock is <10 ppm, then the "light," potentially "biological" C-13/C-12 ratio would be effectively erased by cosmic rays over 3.5 billion years of exposure. We found that for the rocks with relatively short exposure ages (e.g., 100 million years), cosmogenic changes in N-15/N-14 ratio are still very significant. We also show that a short exposure to cosmic rays of Allan Hills 84001 while on Mars can explain its high-temperature heavy nitrogen isotopic composition (N-15/N-14). Applications to Martian meteorites and the current Mars Science Laboratory mission are discussed.

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

2014-01-01

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas- and liquids-rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make qualitative and semi-quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II-S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = -215.2 per mille (V-SMOW), ranging from - 271.8 per mille for the Marcellus Shale to -51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of -89.7 per mille, ranging from -156.0 per mille for the Barnett Shale to -50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analyses. Understanding the role that these H-bearing compounds play in terrestrial shale paleo-environmental reconstruction may also prove useful as analogs for understanding the interactions of water and potential kerogen/organic compounds on the planet Mars.

Stable isotopes in water vapor and rainwater over Indian sector of Southern Ocean and estimation of fraction of recycled moisture.

PubMed

Rahul, P; Prasanna, K; Ghosh, Prosenjit; Anilkumar, N; Yoshimura, Kei

2018-05-15

Stable Hydrogen and Oxygen isotopic composition of water vapor, rainwater and surface seawater show a distinct trend across the latitude over the Southern Indian Ocean. Our observations on isotopic composition of surface seawater, water vapor and rainwater across a transect covering the tropical Indian Ocean to the regions of the Southern Ocean showed a strong latitudinal dependency; characterized by the zonal process of evaporation and precipitation. The sampling points were spread across diverse zones of SST, wind speed and rainfall regimes. The observed physical parameters such as sea surface temperature, wind speed and relative humidity over the oceanic regions were used in a box model calculation across the latitudes to predict the isotopic composition of water vapor under equilibrium and kinetic conditions, and compared with results from isotope enabled global spectral model. Further, we obtained the average fraction of recycled moisture across the oceanic transect latitudes as 13.4 ± 7.7%. The values of recycled fraction were maximum at the vicinity of the Inter Tropical Convergence Zone (ITCZ), while the minimum values were recorded over the region of subsidence and evaporation, at the Northern and Southern latitudes of the ITCZ. These estimates are consistent with the earlier reported recyling values.

Environmental control on eastern broadleaf forest species' leaf wax distributions and D/H ratios

NASA Astrophysics Data System (ADS)

Tipple, Brett J.; Pagani, Mark

2013-06-01

Local climate and environment broadly affect the deuterium/hydrogen (D/H) ratios of plant materials, however the degree to which an individual plant's leaf waxes D/H ratios are affected by these parameters remains in question. Understanding these issues is particularly important in order to reconstruct past floral transitions and changes in the paleohydrologic cycle. For this study, we sampled five co-occurring tree species, Acer rubrum, Platanus occidentalis, Juniperus virginiana, Pinus taeda, and Pinus strobus and soils at forty sites along the East Coast of the US, from Florida to Maine. Hydrogen isotopic compositions of leaf wax n-alkanes, stem and surface waters were analyzed and compared against high-resolution temperature, precipitation, relative humidity, and vapor pressure deficit data to determine environmental controls on isotopic composition. Our results demonstrate that each tree species produce a unique distribution of n-alkanes with distinct chain length pattern. Average n-alkane chain lengths recovered from soils, A. rubrum, and J. virginiana leaves show significant correlations with mean annual temperature. δD values of A. rubrum leaf n-alkanes were strongly correlated to modeled mean annual precipitation δD values and other climate parameters related to latitude (i.e. temperature, relative humidity, vapor pressure deficit), while the δD values of J. virginiana n-alkanes were not. Differences in correspondence may reflect the timing of leaf wax synthesis between the two species. Further, soil n-alkane D/H compositions were strongly correlated to modeled mean annual precipitation δD values, while the apparent hydrogen isotopic fractionation was not. These findings indicate that the isotope ratio of n-alkanes from soils in Eastern North American forests and similar ecosystems likely represents a time-averaged value that smooth out the environmental influence any one plant experiences.

Tracing chlorine sources of thermal and mineral springs along and across the Cascade Range using halogen and chlorine isotope compositions

USGS Publications Warehouse

Cullen, Jeffrey T.; Barnes, Jaime D.; Hurwitz, Shaul; Leeman, William P.

2015-01-01

In order to provide constraints on the sources of chlorine in spring waters associated with arc volcanism, the major/minor element concentrations and stable isotope compositions of chlorine, oxygen, and hydrogen were measured in 28 thermal and mineral springs along the Cascade Range in northwestern USA. Chloride concentrations in the springs range from 64 to 19,000 mg/L and View the MathML source values range from +0.2‰ to +1.9‰ (average=+1.0±0.4‰), with no systematic variation along or across the arc, nor correlations with their presumed underlying basement lithologies. Additionally, nine geochemically well-characterized lavas from across the Mt. St. Helens/Mt. Adams region of the Cascade Range (Leeman et al., 2004 and Leeman et al., 2005) were analyzed for their halogen concentrations and Cl isotope compositions. In the arc lavas, Cl and Br concentrations from the volcanic front are higher than in lavas from the forearc and backarc. F and I concentrations progressively decrease from forearc to backarc, similar to the trend documented for B in most arcs. View the MathML source values of the lavas range from −0.1 to +0.8‰ (average = +0.4±0.3‰). Our results suggest that the predominantly positive View the MathML source values observed in the springs are consistent with water interaction with underlying 37Cl-enriched basalt and/or altered oceanic crust, thereby making thermal spring waters a reasonable proxy for the Cl isotope compositions of associated volcanic rocks in the Cascades. However, waters with View the MathML source values >+1.0‰ also suggest additional contributions of chlorine degassed from cooling magmas due to subsurface vapor–liquid HCl fractionation in which Cl is lost to the aqueous fluid phase and 37Cl is concentrated in the ascending magmatic HCl vapor. Future work is necessary to better constrain Cl isotope behavior during volcanic degassing and fluid–rock interaction in order to improve volatile flux estimates through subduction zones.

Nitrogen and carbon isotopic dynamics of subarctic soils and plants in southern Yukon Territory and its implications for paleoecological and paleodietary studies.

PubMed

Tahmasebi, Farnoush; Longstaffe, Fred J; Zazula, Grant; Bennett, Bruce

2017-01-01

We examine here the carbon and nitrogen isotopic compositions of bulk soils (8 topsoil and 7 subsoils, including two soil profiles) and five different plant parts of 79 C3 plants from two main functional groups: herbs and shrubs/subshrubs, from 18 different locations in grasslands of southern Yukon Territory, Canada (eastern shoreline of Kluane Lake and Whitehorse area). The Kluane Lake region in particular has been identified previously as an analogue for Late Pleistocene eastern Beringia. All topsoils have higher average total nitrogen δ15N and organic carbon δ13C than plants from the same sites with a positive shift occurring with depth in two soil profiles analyzed. All plants analyzed have an average whole plant δ13C of -27.5 ± 1.2 ‰ and foliar δ13C of -28.0 ± 1.3 ‰, and average whole plant δ15N of -0.3 ± 2.2 ‰ and foliar δ15N of -0.6 ± 2.7 ‰. Plants analyzed here showed relatively smaller variability in δ13C than δ15N. Their average δ13C after suitable corrections for the Suess effect should be suitable as baseline for interpreting diets of Late Pleistocene herbivores that lived in eastern Beringia. Water availability, nitrogen availability, spacial differences and intra-plant variability are important controls on δ15N of herbaceous plants in the study area. The wider range of δ15N, the more numerous factors that affect nitrogen isotopic composition and their likely differences in the past, however, limit use of the modern N isotopic baseline for vegetation in paleodietary models for such ecosystems. That said, the positive correlation between foliar δ15N and N content shown for the modern plants could support use of plant δ15N as an index for plant N content and therefore forage quality. The modern N isotopic baseline cannot be applied directly to the past, but it is prerequisite to future efforts to detect shifts in N cycling and forage quality since the Late Pleistocene through comparison with fossil plants from the same region.

Hg isotopes reveal in-stream processing and legacy inputs in East Fork Poplar Creek, Oak Ridge, Tennessee, USA

DOE PAGES

Demers, Jason D.; Blum, Joel D.; Brooks, Scott C.; ...

2018-03-01

In this paper, natural abundance stable Hg isotope measurements were used to place new constraints on sources, transport, and transformations of Hg along the flow path of East Fork Poplar Creek (EFPC), a point-source contaminated headwater stream in Oak Ridge, Tennessee. Particulate-bound Hg in the water column of EFPC within the Y-12 National Security Complex, was isotopically similar to average metallic Hg(0) used in industry, having a mean δ 202Hg value of -0.42 ± 0.09‰ (1SD) and near-zero Δ 199Hg. On average, particulate fraction δ 202Hg values increased downstream by 0.53‰, while Δ 199Hg decreased by -0.10‰, converging with themore » Hg isotopic composition of the fine fraction of streambed sediment along the 26 km flow path. The dissolved fraction behaved differently. Although initial Δ 199Hg values of the dissolved fraction were also near-zero, these values increased transiently along the flow path. Initial δ 202Hg values of the dissolved fraction were more variable than in the particulate fraction, ranging from -0.44 to 0.18‰ among three seasonal sampling campaigns, but converged to an average δ 202Hg value of 0.01 ± 0.10‰ (1SD) downstream. Dissolved Hg in the hyporheic and riparian pore water had higher and lower δ 202Hg values, respectively, compared to dissolved Hg in stream water. Finally, variations in Hg isotopic composition of the dissolved and suspended fractions along the flow path suggest that: (1) physical processes such as dilution and sedimentation do not fully explain decreases in total mercury concentrations along the flow path; (2) in-stream processes include photochemical reduction, but microbial reduction is likely more dominant; and (3) additional sources of dissolved mercury inputs to EFPC at baseflow during this study predominantly arise from the hyporheic zone.« less

Hg isotopes reveal in-stream processing and legacy inputs in East Fork Poplar Creek, Oak Ridge, Tennessee, USA

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

Demers, Jason D.; Blum, Joel D.; Brooks, Scott C.

In this paper, natural abundance stable Hg isotope measurements were used to place new constraints on sources, transport, and transformations of Hg along the flow path of East Fork Poplar Creek (EFPC), a point-source contaminated headwater stream in Oak Ridge, Tennessee. Particulate-bound Hg in the water column of EFPC within the Y-12 National Security Complex, was isotopically similar to average metallic Hg(0) used in industry, having a mean δ 202Hg value of -0.42 ± 0.09‰ (1SD) and near-zero Δ 199Hg. On average, particulate fraction δ 202Hg values increased downstream by 0.53‰, while Δ 199Hg decreased by -0.10‰, converging with themore » Hg isotopic composition of the fine fraction of streambed sediment along the 26 km flow path. The dissolved fraction behaved differently. Although initial Δ 199Hg values of the dissolved fraction were also near-zero, these values increased transiently along the flow path. Initial δ 202Hg values of the dissolved fraction were more variable than in the particulate fraction, ranging from -0.44 to 0.18‰ among three seasonal sampling campaigns, but converged to an average δ 202Hg value of 0.01 ± 0.10‰ (1SD) downstream. Dissolved Hg in the hyporheic and riparian pore water had higher and lower δ 202Hg values, respectively, compared to dissolved Hg in stream water. Finally, variations in Hg isotopic composition of the dissolved and suspended fractions along the flow path suggest that: (1) physical processes such as dilution and sedimentation do not fully explain decreases in total mercury concentrations along the flow path; (2) in-stream processes include photochemical reduction, but microbial reduction is likely more dominant; and (3) additional sources of dissolved mercury inputs to EFPC at baseflow during this study predominantly arise from the hyporheic zone.« less

Tracking nitrate sources in the Chaohu Lake, China, using the nitrogen and oxygen isotopic approach.

PubMed

Yu, Qibiao; Wang, Fang; Li, Xinyan; Yan, Weijin; Li, Yanqiang; Lv, Shucong

2018-05-07

The Chaohu Lake is highly polluted and suffers from severe eutrophication. Nitrate is a key form of nitrogen that can cause water quality degradation. In this study, hydrochemical and dual isotopic approaches were utilized to identify the seasonal variation of nitrate sources in the Chaohu Lake and its inflowing rivers. The average nitrate concentrations ([NO 3 - ]) of the lake and its inflowing rivers were 89.9 and 140.8 μmol L -1 , respectively. The isotopic values of δ 15 N-NO 3 - and δ 18 O-NO 3 - in the lake ranged from - 1.01 to + 16.67‰ and from - 4.39 to + 22.20‰, respectively. The two major rivers had distinct isotopic compositions, with average δ 15 N-NO 3 - values of + 17.52 and + 3.51‰, and average δ 18 O-NO 3 - values of + 2.71 and + 7.47‰ for the Nanfei River and Hangbu River, respectively. The results show that soil organic ammonium and urban wastewater discharge were the main sources of nitrate in the Chaohu Lake, and nitrate assimilation was an important process affected [NO 3 - ] and isotopic compositions, especially in the western Chaohu Lake. The elevated [NO 3 - ] and δ 15 N-NO 3 - values in the western Chaohu Lake indicate the high influence of human activities. Urban wastewater discharge was the primary nitrate source in the Nanfei River and soil organic ammonium was the main source in the Hangbu River. Although nitrate from direct atmospheric deposition was low, its strong flushing effect can substantially improve riverine [NO 3 - ] and nitrate loading from terrestrial ecosystem. The relatively high nitrate fluxes from the Hangbu River indicate that nitrogen loading from agricultural watershed is unneglectable in watershed nitrogen sources reduction strategies.

Hafnium and neodymium isotopes and REY distribution in the truly dissolved, nanoparticulate/colloidal and suspended loads of rivers in the Amazon Basin, Brazil

NASA Astrophysics Data System (ADS)

Merschel, Gila; Bau, Michael; Schmidt, Katja; Münker, Carsten; Dantas, Elton L.

2017-09-01

Radiogenic isotopes in river sediments and river waters have been widely used in provenance studies, as these samples naturally integrate the geology/chemistry of the entire catchment. While the Hf and Nd isotope systems are coupled during igneous processes, they are decoupled during supergene processes at the Earth's surface, which is reflected by the isotope composition of riverine sediments. We present the first data for both Hf and Nd isotope compositions of the dissolved (0.2 μm-filtrates rich in nanoparticles and colloids, NPCs) and the truly dissolved (1 kDa-ultrafiltrates) load of rivers. Hafnium and Nd isotope compositions and concentrations of the Rare Earths and Yttrium (REY) and Hf were determined for suspended particles (>0.2 μm) as well as for the dissolved and the truly dissolved load of the Rio Solimões, the Amazon's largest tributary draining the Andes, and of the Rio Negro, an organic NPC- and particle-rich river draining the rainforest of northern Amazonia. We also analyzed the Nd isotope compositions of suspended sediments and 0.2 μm-filtered water samples from the Amazon River and its tributaries Rio Tapajos, Rio Xingu and Rio Jari. Our novel results clearly show that the decoupling of the Hf and Nd isotope systems is related to incongruent weathering processes on the continent, as this decoupling can already be observed in the different Hf and Nd pools, i.e. in the particulate, the NPC-dominated dissolved and the truly dissolved load of rivers. In the Rio Negro and Rio Solimões, a strong particle size-dependent difference in Hf isotope composition is observed. Values of εHf become more radiogenic as filter poresize decreases, which can be related to the density- and size-dependent distribution of Hf-rich minerals, e.g. zircons, and their absence from the truly dissolved pool. In contrast, the Nd isotope composition of Amazonian river waters reflects that of their catchment geology. Tributaries draining the Precambrian Brazilian and Guyana shields show very unradiogenic εNd values of -19 to -25 in their dissolved load, whereas the Rio Solimões draining the Andes yields a more radiogenic εNd signal of only -7. The dissolved Nd isotope composition of the Amazon is dominated by its Andean tributaries and averages at -8. Although Nd isotope compositions are thought to not being fractionated by Earth surface processes, significant differences of 1.3-1.9 ε-units can be observed between the dissolved and suspended loads in the Amazon River and its main tributary, the Rio Solimões. In these rivers, the dissolved load is more radiogenic than the suspended sediment, which is likely due to incongruent weathering and related mineral sorting in the Andean headwaters. In contrast, the organic-rich and mineral-poor shield rivers do not show a difference between the truly dissolved, dissolved and suspended load, as the Nd in all these pools is controlled by surface- and solution-complexation and hence isotopically homogenized by continuous exchange and re-equilibration.

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

Mid-to-Lower-level Plutonic Rocks From Crust of the Southern Mariana Forearc: Implications for Growth of Continental Crust

NASA Astrophysics Data System (ADS)

Fryer, P.; Reagan, M.

2006-12-01

Tonalitic plutonic rocks dredged from the southern Mariana forearc are similar in terms of major element composition to tonalitic plutonic rocks of the Tanzawa Mountains on the Izu Peninsula of Japan. The tonalites of the Tanzawa Mountains have been interpreted to represent mid-lower crustal plutonic rocks that make up the 6.0 to 6.3 km/s layer identified in seismic velocity profiles of the Izu arc at 32°N. The tonalities of the southern Mariana forearc may be analogous to the Tanzawa tonalities in terms of lithology and presumably seismic velocities, but have distinctive trace element and isotopic compositions. The exposure of these rocks on the southern Mariana forearc in a location where it is narrower by up to 80 km than elsewhere along its strike indicates a truncation of the arc lithosphere by tectonic erosion in the southern Mariana forearc. If tectonic processes in the forearc have exposed silicic plutonic rock of the arc lithosphere within 150 km of the volcanic front, then the structure of the Mariana arc and forearc is likely similar to that of the Izu arc, where seismic velocity structure suggests 25% of the arc/forearc lithosphere is comprised of a mid-crustal level tonalitic plutonic complex. The trace element and Sr isotopic compositions of the tonalities dredged from the Mariana forearc links them to a suprasubduction-zone environment. The Pb isotopic compositions, however, are consistent with crystallization ages that may be as old as Cretaceous. The compositions of these tonalites differ markedly from those of silicic volcanic rocks that have erupted throughout the history of the IBM arc and suggest that they represent a minor component of the arc. Nevertheless, the presence of Cretaceous tonalites in the Mariana forearc suggests that a portion of its crust may predate subduction initiation. The presence of silicic mid-to-lower crustal level plutonics beneath the Mariana arc as well as Eocene rhyolites on Saipan indicate that average major element composition of the arc crust may be comparable with average continental crust. This is consistent with estimates of the average composition of the Izu arc crust from seismic velocity studies and petrologic studies of exposures of the Izu arc crust in southern Japan's Izu peninsula. These data imply that the island arc that developed along the entire margin of the Philippine Sea plate may have had a generally similar structure and composition. Most components of the IBM arc crust, however, have relatively flat rare-earth patterns and low rare-earth concentrations compared with average continental crust. The averaged composition of the IBM crust, as a whole, differs markedly from that suggested by studies of the velocity structure of the central Aleutian arc. If the continental crust was generated in oceanic island arc settings throughout the history of the Earth, then its sources were significantly more enriched in LREE than the sources for the Cenozoic IBM arcs.

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).

Stable isotope composition of waters in the Great Basin, United States 1. Air-mass trajectories

USGS Publications Warehouse

Friedman, I.; Harris, J.M.; Smith, G.I.; Johnson, C.A.

2002-01-01

Isentropic trajectories, calculated using the NOAA/Climate Monitoring and Diagnostics Laboratory's isentropic transport model, were used to determine air-parcel origins and the influence of air mass trajectories on the isotopic composition of precipitation events that occurred between October 1991 and September 1993 at Cedar City, Utah, and Winnemucca, Nevada. Examination of trajectories that trace the position of air parcels backward in time for 10 days indicated five distinct regions of water vapor origin: (1) Gulf of Alaska and North Pacific, (2) central Pacific, (3) tropical Pacific, (4) Gulf of Mexico, and (5) continental land mass. Deuterium (??D) and oxygen-18 (??18O) analyses were made of precipitation representing 99% of all Cedar City events. Similar analyses were made on precipitation representing 66% of the precipitation falling at Winnemucca during the same period. The average isotopic composition of precipitation derived from each water vapor source was determined. More than half of the precipitation that fell at both sites during the study period originated in the tropical Pacific and traveled northeast to the Great Basin; only a small proportion traversed the Sierra Nevada. The isotopic composition of precipitation is determined by air-mass origin and its track to the collection station, mechanism of droplet formation, reequilibration within clouds, and evaporation during its passage from cloud to ground. The Rayleigh distillation model can explain the changes in isotopic composition of precipitation as an air mass is cooled pseudo-adiabatically during uplift. However, the complicated processes that take place in the rapidly convecting environment of cumulonimbus and other clouds that are common in the Great Basin, especially in summer, require modification of this model because raindrops that form in the lower portion of those clouds undergo isotopic change as they are elevated to upper levels of the clouds from where they eventually drop to the ground.

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.

In-Situ Oxygen Isotopic Composition of Tagish Lake: An Ungrouped Type 2 Carbonaceous Chondrite

NASA Technical Reports Server (NTRS)

Zolensky, Michael E.; Engrand, Cecile; Gounelle, Matthieu; Zolensky, Mike E.

2001-01-01

We have measured the oxygen isotopic composition of several components of Tagish Lake by ion microprobe. This meteorite constitutes the best preserved sample of C2 matter presently available for study. It presents two different lithologies (carbonate-poor and -rich) which have fairly comparable oxygen isotopic composition, with regard to both the primary or secondary minerals. For the olivine and pyroxene grains, their delta O-18 values range from - 10.5% to + 7.4% in the carbonate-poor lithology, with a mean Delta O-17 value of - 3.7 2.4%. In the carbonate-rich lithology, delta O-18 varies from - 7.9% to + 3.3%, and the mean Delta O-17 value is - 4.7 +/- 1.4%. Olivine inclusions (Fo(sub >99)) with extreme O-16-enrichment were found in both lithologies: delta O-18 = - 46.1 %, delta O-187= - 48.3% and delta O-18 = - 40.6%, delta O-17 = - 41.2% in the carbonate-rich lithology; delta O-18 = - 41.5%, delta O-17 = -43.4%0 in the carbonate-poor lithology. Anhydrous minerals in the carbonate-poor lithology are slightly more O-16-rich than in the carbonate-rich one. Four low-iron manganese-rich (LIME) olivine grains do not have an oxygen isotopic composition distinct from the other "normal" olivines. The phyllosilicate matrix presents the same range of oxygen isotopic compositions in both lithologies: delta O-18 from approximately 11 % to approximately 6%, with an average Delta. O-17 approximately 0%. Because the bulk Tagish Lake oxygen isotopic composition given by Brown et al. is on the high end of our matrix analyses, we assume that this "bulk Tagish Lake" composition probably only represents that of the carbonate-rich lithology. Calcium carbonates have delta O-18 values up to 35%, with Delta O-17 approximately 0.5%0. Magnetite grains present very high Delta O-17 values approximately + 3.4%0 +/- 1.2%. Given our analytical uncertainties and our limited carbonate data, the matrix and the carbonate seem to have formed in isotopic equilibrium. In that case, their large isotopic fractionation would argue for a low temperature (CM-like, T approximately 0 deg) formation. Magnetite probably formed during a separate event. Tagish Lake magnetite data is surprisingly compatible with that of R-chondrites and unequilibrated ordinary (LL3) chondrites. Our oxygen isotope data strongly supports the hypothesis of a single precursor for both lithologies. Drastic mineralogical changes between the two lithologies not being accompanied with isotopic fractionation seem compatible with the alteration model presented by Young et aI. Tagish Lake probably represents the first well preserved large sample of the C2 matter that dominates interplanetary matter since the formation of the solar system.

Fontinalis antipyretica as a bioindicator of environmental conditions in freshwater ecosystem from Sava River watershed and Cerknişko Lake, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Mechora, Špela; Stibilj, Vekoslava

2014-05-01

Polluted waters recharging from agriculture water systems into watersheds have influence on water quality and living habitat. Stable isotopes of carbon and nitrogen in combination with other minor and trace elements are often used to trace biogeochemical processes and contamination of water systems. The aim of the study was to assess state of environment with minor and trace elements and stable isotopes of C and N in selected Slovenian streams. Ten locations in Notranjska region, Slovenia, with different land use in the catchment (town, village, agricultural areas, farms, dairy farms), including reference point considered as non-polluted site, were sampled. Samples of water and aquatic moss F. antipyretica in Slovenian fresh waters were taken in all four seasons during years 2010 and 2012, but for stable isotope analyses of C and N only in three seasons during years 2010 and 2011. The water chemistry of investigated locations is dominated by hydrogen carbonate - calcium - magnesium, concentrations of nitrate seasonally range from 2.07 mg/l to 6.4 mg/l and at reference site does not exceed 1.3 mg/l. Total alkalinity of water at investigated locations ranges from 2.9 to 6.02 mM. The pH of investigated water range from 7.2 to 8.5, waters are saturated with oxygen (up to 134%) and conductivity ranges from 295 to 525 mikroS/cm, while at reference site conductivity is up to 180 mikroS/cm. The content of minor and trace elements in F. antipyretica ranged for Ni 4-38 mikrog/g, Zn 17-105 mikrog/g, Pb 2-28 mikrog/g, Cd 220-1953 ng/g, Cu 4-27 mikrog/g, Cr 4-49 mikrog/g, As 1-6 mikrog/g and Se 0.33-3.24 mikrog/g. The most polluted watershed was Pšata stream (agricultural areas, cattle farm) with highest values for Ni, Cr, Pb, Zn and As. The highest content of Se, was found in village (dairy farms) in Žerovniščica stream. The highest values were measured in February and October. Isotopic composition of dissolved inorganic carbon seasonally range from -13.3 to -8.1‰, and indicate waters dominated by degradation of organic matter and dissolution of carbonates. At the reference point average measured isotopic composition of dissolved inorganic carbon value is -2.7‰ which confirmed that this is a non-polluted site. Isotopic composition of carbon of F. antipyretica seasonally ranges from -45 to -32.9‰ and isotopic composition of nitrogen from -0.2‰ to 6.5‰, respectively. In comparison to C3 terrestrial plants F. antipyretica has more negative isotopic composition of carbon value, which is probably related with the difference in CO2 plant fixation and depends on isotopic composition of dissolved inorganic carbon in water, which is primarily controlled by geological composition and soil thickness in the watershed. Higher isotopic composition of nitrogen value found in F. antipyretica is related to agricultural activity in watershed, while at the reference site measured isotopic composition of nitrogen value is -4.1 ‰. From our study it is evident that isotopic composition of carbon and nitrogen is useful tracer of natural and anthropogenic inputs from terrestrial (fertilizing, sewage sludge) to water system.

Re-Os systematics of komatiites and komatiitic basalts at Dundonald Beach, Ontario, Canada: Evidence for a complex alteration history and implications of a late-Archean chondritic mantle source

NASA Astrophysics Data System (ADS)

Gangopadhyay, Amitava; Sproule, Rebecca A.; Walker, Richard J.; Lesher, C. Michael

2005-11-01

Osmium isotopic compositions, and Re and Os concentrations have been examined in one komatiite unit and two komatiitic basalt units at Dundonald Beach, part of the 2.7 Ga Kidd-Munro volcanic assemblage in the Abitibi greenstone belt, Ontario, Canada. The komatiitic rocks in this locality record at least three episodes of alteration of Re-Os elemental and isotope systematics. First, an average of 40% and as much as 75% Re may have been lost due to shallow degassing during eruption and/or hydrothermal leaching during or immediately after emplacement. Second, the Re-Os isotope systematics of whole rock samples with 187Re/ 188Os ratios >1 were reset at ˜2.5 Ga, possibly due to a regional metamorphic event. Third, there is evidence for relatively recent gain and loss of Re in some rocks. Despite the open-system behavior, some aspects of the Re-Os systematics of these rocks can be deciphered. The bulk distribution coefficient for Os (D Ossolid/liquid) for the Dundonald rocks is ˜3 ± 1 and is well within the estimated D values obtained for komatiites from the nearby Alexo area and stratigraphically-equivalent komatiites from Munro Township. This suggests that Os was moderately compatible during crystal-liquid fractionation of the magmas parental to the Kidd-Munro komatiitic rocks. Whole-rock samples and chromite separates with low 187Re/ 188Os ratios (<1) yield a precise chondritic average initial 187Os/ 188Os ratio of 0.1083 ± 0.0006 (γ Os = 0.0 ± 0.6) for their well-constrained ˜2715 Ma crystallization age. The chondritic initial Os isotopic composition of the mantle source for the Dundonald rocks is consistent with that determined for komatiites in the Alexo area and in Munro Township, suggesting that the mantle source region for the Kidd-Munro volcanic assemblage had evolved with a long-term chondritic Re/Os before eruption. The chondritic initial Os isotopic composition of the Kidd-Munro komatiites is indistinguishable from that of the projected contemporaneous convective upper mantle. The uniform chondritic Os isotopic composition of the Kidd-Munro komatiites contrasts with the typical large-scale Os isotopic heterogeneity in the mantle sources for ca. 89 Ma komatiites from the Gorgona Island, arc-related rocks and present-day ocean island basalts. This suggests that the Kidd-Munro komatiites sampled a late-Archean mantle source region that was significantly more homogeneous with respect to Re/Os relative to most modern mantle-derived rocks.

Evaluating the Historical Importance of Impact Induced Hydrothermal Systems on Mars Using the Stable Isotopic Composition of Martian Water

NASA Technical Reports Server (NTRS)

Niles, Paul B.

2010-01-01

The importance of impact events during the early history of Mars is obvious through a simple examination of the character of the martian surface. This ancient, heavily cratered terrain has been shown to be associated with extensive phyllosilicate deposits. This geologic link could suggest that the extensive phyllosilicate-forming alteration may have occurred during early martian history through impact-induced hydrothermal alteration. However, examination of the oxygen isotopic composition of water on Mars suggests that the extensive phyllosilicate deposits were formed primarily through low temperature (<30 C) interactions, and that high temperature weathering in impact-induced hydrothermal systems have not been a dominant process on Mars. The average oxygen isotopic composition of water on Earth is dictated by the nature of water-rock interactions. If these interactions occur at higher temperatures then the water will contain a higher proportion of 18O, while lower temperature interactions will result in water with a lower proportion of 18O. Water on Earth today contains a higher proportion of 18O because of plate tectonics and hydrothermal interaction at mid-ocean ridges. The oxygen isotopic composition of water on early earth, however, may have been quite different, containing a smaller proportion of 18O suggesting much less hydrothermal interaction. Because there are not yet any direct measurements of the oxygen isotopic composition of water on Mars, it needs to be inferred through examination of carbonates preserved in martian meteorites and the isotopic composition of atmospheric CO2. This can be done because the oxygen incorporated into carbonates and CO2 is easily exchanged with liquid water if it is present. Independently, both measurements provide an estimate for the (Sigma)18O of water on Mars to be near -16%. This composition is consistent with low temperature weathering of the silicate crust, and indicates that impact hydrothermal systems did not play an important role in the early alteration of the planet. However, our understanding of impact-induced hydrothermal systems remains unclear. If most of the water mobilized by an impact event remained at relatively low temperatures (<30deg), low-temperature interactions could predominate in these environments. These conditions would be consistent with the isotopic constraints suggested in this study.

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.

Carbon isotope compositions of terrestrial C3 plants as indicators of (paleo)ecology and (paleo)climate

PubMed Central

Kohn, Matthew J.

2010-01-01

A broad compilation of modern carbon isotope compositions in all C3 plant types shows a monotonic increase in δ13C with decreasing mean annual precipitation (MAP) that differs from previous models. Corrections for temperature, altitude, or latitude are smaller than previously estimated. As corrected for altitude, latitude, and the δ13C of atmospheric CO2, these data permit refined interpretation of MAP, paleodiet, and paleoecology of ecosystems dominated by C3 plants, either prior to 7–8 million years ago (Ma), or more recently at mid- to high latitudes. Twenty-nine published paleontological studies suggest preservational or scientific bias toward dry ecosystems, although wet ecosystems are also represented. Unambiguous isotopic evidence for C4 plants is lacking prior to 7–8 Ma, and hominid ecosystems at 4.4 Ma show no isotopic evidence for dense forests. Consideration of global plant biomass indicates that average δ13C of C3 plants is commonly overestimated by approximately 2‰. PMID:21041671

The mantle source of island arc magmatism during early subduction: Evidence from Hf isotopes in rutile from the Jijal Complex (Kohistan arc, Pakistan)

NASA Astrophysics Data System (ADS)

Ewing, Tanya A.; Müntener, Othmar

2018-05-01

The Cretaceous-Paleogene Kohistan arc complex, northern Pakistan, is renowned as one of the most complete sections through a preserved paleo-island arc. The Jijal Complex represents a fragment of the plutonic roots of the Kohistan arc, formed during its early intraoceanic history. We present the first Hf isotope determinations for the Jijal Complex, made on rutile from garnet gabbros. These lithologies are zircon-free, but contain rutile that formed as an early phase. Recent developments in analytical capabilities coupled with a careful analytical and data reduction protocol allow the accurate determination of Hf isotope composition for rutile with <30 ppm Hf for the first time. Rutile from the analysed samples contains 5-35 ppm Hf, with sample averages of 13-17 ppm. Rutile from five samples from the Jijal Complex mafic section, sampling 2 km of former crustal thickness, gave indistinguishable Hf isotope compositions with εHf(i) ranging from 11.4 ± 3.2 to 20.1 ± 5.7. These values are within error of or only slightly more enriched than modern depleted mantle. The analysed samples record variable degrees of interaction with late-stage melt segregations, which produced symplectitic overprints on the main mineral assemblage as well as pegmatitic segregations of hydrous minerals. The indistinguishable εHf(i) across this range of lithologies demonstrates the robust preservation of the Hf isotope composition of rutile. The Hf isotope data, combined with previously published Nd isotope data for the Jijal Complex garnet gabbros, favour derivation from an inherently enriched, Indian Ocean type mantle. This implies a smaller contribution from subducted sediments than if the source was a normal (Pacific-type) depleted mantle. The Jijal Complex thus had only a limited recycled continental crustal component in its source, and represents a largely juvenile addition of new continental crust during the early phases of intraoceanic magmatism. The ability to determine the Hf isotope composition of rutile with low Hf contents is an important development for zircon-free mafic lithologies. This study highlights the potential of Hf isotope analysis of rutile to characterise the most juvenile deep arc crust cumulates worldwide.

The Abundance and Isotopic Composition of Water in Howardite-Eucrite-Diogenite Meteorites

NASA Astrophysics Data System (ADS)

Barrett, T. J.; Tartèse, R.; Anand, M.; Franchi, I. A.; Grady, M. M.; Greenwood, R. C.; Charlier, B. L. A.

2014-09-01

Using SIMs techniques we measure OH abundances and D/H ratios in apatite grains from two Eucrites (DaG 945, DaG 844).The average δD values of these two samples are also similar to carbonaceous chondrites, the Earth and the Moon.

Chlorine Isotopes: As a Possible Tracer of Fluid/Bio-Activities on Mars and a Progress Report on Chlorine Isotope Analysis by TIMs

NASA Technical Reports Server (NTRS)

Nakamura, N.; Nyquist, L.E.; Reese, Y.; Shih, C-Y.; Numata, M.; Fujitani, T.; Okano, O.

2009-01-01

Significantly large mass fractionations between chlorine isotopes (Cl-35, Cl-37) have been reported for terrestrial materials including both geological samples and laboratory materials. Also, the chlorine isotopic composition can be used as a tracer for early solar system processes. Moreover, chlorine is ubiquitous on the Martian surface. Typical chlorine abundances in Gusev soils are approx.0.5 %. The global surface average chlorine abundance also is approx.0.5 %. Striking variations among outcrop rocks at Meridiani were reported with some chlorine abundances as high as approx.2%. Characterizing conditions under which chlorine isotopic fractionation may occur is clearly of interest to planetary science. Thus, we have initiated development of a chlorine isotopic analysis technique using TIMS at NASA-JSC. We present here a progress report on the current status of development at JSC and discuss the possible application of chlorine isotopic analysis to Martian meteorites in a search for fluid- and possibly biological activity on Mars.

Extreme isotopic variations in the upper mantle: evidence from Ronda

NASA Astrophysics Data System (ADS)

Reisberg, Laurie; Zindler, Alan

1986-12-01

The Ronda Ultramafic Complex in southern Spain represents a piece of the Earth's mantle which has been tectonically emplaced into the crust. Nd and Sr isotopic analyses are presented for leached, hand-picked Cr-diopside separates prepared from 15 rock and 18 river sediment samples from Ronda. These results demonstrate that within this small, contiguous body there exists the entire range of Nd isotopic compositions, and much of the range of Sr compositions, found in rocks derived from the sub-oceanic mantle. The sediment cpx samples show that the average isotopic composition of the massif becomes progressively less "depleted" moving from SW to NE along the long axis of the massif. The rock cpx samples document 143Nd/ 144Nd variations from 0.5129 to 0.5126 and 87Sr/ 86Sr variations from 0.7031 to 0.7039 within a uniform outcrop less than 10 m in extent. Thus, extreme isotopic fluctuations exist over a wide range of wavelengths. Sr and Nd isotopes are generally inversely correlated, forming a trend on a Nd-Sr diagram that sharply crosscuts that of the "mantle array". Many of the 143Nd/ 144Nd values, and all of the Sm/Nd values, from one section of the massif are lower than that SCV015SCV0 of the bulk earth, implying that this region existed, or was influenced by a component which existed, in a LREE-enriched environment for a significant period of time. Among the sediment cpxs there is a positive correlation between 143Nd/ 144Nd and 147Sm/ 144Nd. The rock cpx separates display considerably more scatter. A simple, single-stage differentiation event starting with a uniform mantle source cannot explain these results. At least one episode of mixing with a LREE-enriched component is required. If these results from Ronda are typical of the upper mantle, basalts with different isotopic compositions need not derive from spatially separated mantle sources.

The Relative Importance of Convective and Trade-wind Orographic Precipitation to Streamflow in the Luquillo Mountains, Eastern Puerto Rico

NASA Astrophysics Data System (ADS)

Scholl, M. A.; Shanley, J. B.; Occhi, M.; Scatena, F. N.

2012-12-01

Like many mountainous areas in the tropics, watersheds in the Luquillo Mountains of Puerto Rico (18.3° N) have abundant rainfall and stream discharge, but relatively little storage capacity. Therefore, the water supply is vulnerable to drought and water availability may be affected by projected changes in regional temperature and atmospheric dynamics due to global warming. To help determine the links between climate and water availability, precipitation patterns were analyzed, and stable-isotope signatures of precipitation from different seasonal weather systems were established to identify those that are most important in maintaining streamflow and groundwater recharge. Stable isotope data include cloud water, rainfall, throughfall, streamflow, and groundwater from the Rio Mameyes and Rio Icacos/ Rio Blanco watersheds. Precipitation inputs have a wide range of stable isotope values, from fog/cloud water with δ2H and δ18O averaging +3.2‰, -1.74‰ respectively, to tropical storm rain with values as low as -154‰, -20.4‰. Spatial and temporal patterns of water isotopic values on this Caribbean island are different than higher latitude, continental watersheds. The data exhibit a 'reverse seasonality', with higher isotopic values in winter and lower values in summer; and stable isotope values of stream water do not decrease as expected with increasing altitude, because of cloud water input. Rain isotopic values vary predictably with local and mesoscale weather patterns and correlate strongly with cloud altitude. This correlation allows us to assign isotopic signatures to different sources of precipitation, and to investigate which climate patterns contribute to streamflow and groundwater recharge. At a measurement site at 615 m in the Luquillo Mountains, the average length of time between rain events was 15 h, and 45% of the rain events were <2 mm, reflecting the frequent small rain events of the trade-wind orographic rainfall weather pattern. Long-term average streamflow isotopic composition indicates a disproportionately large contribution of this trade-wind precipitation to streamflow, highlighting the importance of this climate pattern to the hydrology of the watersheds. Isotopic composition of groundwater suggests a slightly higher proportion of convective precipitation, but still smaller than in total rainfall. Hydrograph separation experiments yielded information on stormflow characteristics, with quantification of contributing sources determined from water isotopes and solute chemistry. The evidence that intense convective rain events run off and light trade-wind showers appear to contribute much of the baseflow indicates that the area may undergo a change in water supply if the trade-wind orographic precipitation dynamics in the Caribbean are affected by future climate change.

Isotopic Discrimination During Leaf Litter Decomposition

NASA Astrophysics Data System (ADS)

Ngao, J.; Rubino, M.

2006-12-01

Methods involving stable isotopes have been successfully applied since decades in various research fields. Tracing 13C natural abundance in ecosystem compartments greatly enhanced the understanding of the C fluxes in the plant-soil-atmosphere C exchanges when compartments present different C isotopic signatures (i.e. atmospheric CO2 vs photosynthetic leaves, C3 vs C4; etc.). However, the assumption that no isotopic discrimination occurs during respiration is commonly made in numbers of C isotope-based ecological studies. Furthermore, verifications of such assumption are sparse and not enough reliable. The aim of our study is to assess the potential isotopic discrimination that may occur during litter decomposition. Leaf litter from an Arbutus unedo (L.) stand (Tolfa, Italy) was incubated in 1L jars, under constant laboratory conditions (i.e. 25 ° C and 135% WC). During the entire incubation period, gravimetric mass loss, litter respiration rates and the isotopic composition of respired CO2 are monitored at regular intervals. Data from 7 months of incubation will be presented and discussed. After two months, the litter mass loss averaged 16% of initial dry mass. During the same time-period, the respiration rate decreased significantly by 58% of the initial respiration rate. Isotopic compositions of respired CO2 ranged between -27.95‰ and - 25.69‰. Mean values did not differ significantly among the sampling days, in spite of an apparent enrichment in 13C of respired CO2 with time. The significance of these isotopic enrichment will be determined at a longer time scale. They may reveal both/either a direct microbial discrimination during respiration processes and/or a use of different litter compounds as C source along time. Further chemical and compound-specific isotopic analysis of dry matter will be performed in order to clarify these hypotheses. This work is part of the "ALICE" project, funded by the European Union's Marie Curie Fellowship Actions that aims to implement an advanced laser spectrometry technology to measure the isotopic composition in respired CO2. The laser spectrometer will be used to investigate the isotopic discrimination during soil respiration, in laboratory and field studies.

Nucleosynthetic osmium isotope anomalies in acid leachates of the Murchison meteorite

NASA Astrophysics Data System (ADS)

Reisberg, L.; Dauphas, N.; Luguet, A.; Pearson, D. G.; Gallino, R.; Zimmermann, C.

2009-01-01

We present osmium isotopic results obtained by sequential leaching of the Murchison meteorite, which reveal the existence of very large internal anomalies of nucleosynthetic origin (ɛ 184Os from - 108 to 460; ɛ 186Os from - 14.1 to 12.6; ɛ 188Os from - 2.6 to 1.6; ɛ 190Os from - 1.7 to 1.1). Despite these large variations, the isotopic composition of the total leachable osmium (weighted average of the leachates) is close to that of bulk chondrites. This is consistent with efficient large-scale mixing of Os isotopic anomalies in the protosolar nebula. The Os isotopic anomalies are correlated, and can be explained by the variable contributions of components derived from the s, r and p-processes of nucleosynthesis. Surprisingly, much of the s-process rich osmium is released by relatively mild leaching, suggesting the existence of an easily leachable s-process rich presolar phase, or alternatively, of a chemically resistant r-process rich phase. Taken together with previous evidence for a highly insoluble s-process rich carrier, such as SiC, these results argue for the presence of several presolar phases with anomalous nucleosynthetic compositions in the Murchison meteorite. The s-process composition of Os released by mild leaching diverges slightly from that released by aggressive digestion techniques, perhaps suggesting that the presolar phases attacked by these differing procedures condensed in different stellar environments. The correlation between ɛ 190Os and ɛ 188Os can be used to constrain the s-process 190Os/ 188Os ratio to be 1.275 ± 0.043. Such a ratio can be reproduced in a nuclear reaction network for a MACS value for 190Os of ~ 200 ± 22 mbarn at 30 keV. More generally, these results can help refine predictions of the s-process in the Os mass region, which can be used in turn to constrain the amount of cosmoradiogenic 187Os in the solar system and hence the age of the Galaxy. We also present evidence for extensive internal variation of 184Os abundances in the Murchison meteorite. A steep anti-correlation is observed between ɛ 184Os and ɛ 188Os. Since 184Os is formed uniquely by the p-process, this anti-correlation cannot be explained by variable addition or subtraction of s-process Os to average solar system material. Instead, this suggests that p-process rich presolar grains (e.g., supernova condensates) may be present in meteorites in sufficient quantities to influence the Os isotopic compositions of the leachates. Nevertheless, 184Os is a low abundance isotope and we cannot exclude the possibility that the measured anomalies for this isotope reflect unappreciated analytical artifacts.

Software for peak finding and elemental composition assignment for glycosaminoglycan tandem mass spectra.

PubMed

Hogan, John D; Klein, Joshua A; Wu, Jiandong; Chopra, Pradeep; Boons, Geert-Jan; Carvalho, Luis; Lin, Cheng; Zaia, Joseph

2018-04-03

Glycosaminoglycans (GAGs) covalently linked to proteoglycans (PGs) are characterized by repeating disaccharide units and variable sulfation patterns along the chain. GAG length and sulfation patterns impact disease etiology, cellular signaling, and structural support for cells. We and others have demonstrated the usefulness of tandem mass spectrometry (MS2) for assigning the structures of GAG saccharides; however, manual interpretation of tandem mass spectra is time-consuming, so computational methods must be employed. In the proteomics domain, the identification of monoisotopic peaks and charge states relies on algorithms that use averagine, or the average building block of the compound class being analyzed. While these methods perform well for protein and peptide spectra, they perform poorly on GAG tandem mass spectra, due to the fact that a single average building block does not characterize the variable sulfation of GAG disaccharide units. In addition, it is necessary to assign product ion isotope patterns in order to interpret the tandem mass spectra of GAG saccharides. To address these problems, we developed GAGfinder, the first tandem mass spectrum peak finding algorithm developed specifically for GAGs. We define peak finding as assigning experimental isotopic peaks directly to a given product ion composition, as opposed to deconvolution or peak picking, which are terms more accurately describing the existing methods previously mentioned. GAGfinder is a targeted, brute force approach to spectrum analysis that utilizes precursor composition information to generate all theoretical fragments. GAGfinder also performs peak isotope composition annotation, which is typically a subsequent step for averagine-based methods. Data are available via ProteomeXchange with identifier PXD009101. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

Holocene provenance shift of suspended particulate matter in the Amazon River basin

NASA Astrophysics Data System (ADS)

Höppner, Natalie; Lucassen, Friedrich; Chiessi, Cristiano M.; Sawakuchi, André O.; Kasemann, Simone A.

2018-06-01

The strontium (Sr), neodymium (Nd) and lead (Pb) isotope signatures of suspended particulate matter (SPM) in rivers reflect the radiogenic isotope signatures of the rivers' drainage basin. These signatures are not significantly affected by weathering, transport or depositional cycles, but document the sedimentary contributions of the respective sources. We report new Sr, Nd and Pb isotope ratios and element concentrations of modern SPM from the Brazilian Amazon River basin and document the past evolution of the basin by analyzing radiogenic isotopes of a marine sediment core from the slope off French Guiana archiving the last 40 kyr of Amazon River SPM, and the Holocene section of sediment cores raised between the Amazon River mouth and the slope off French Guiana. The composition of modern SPM confirms two main source areas, the Andes and the cratonic Shield. In the marine sediment core notable changes occurred during the second phase of Heinrich Stadial 1 (i.e. increased proportion of Shield rivers SPM) and during the last deglaciation (i.e. increased proportion of Madeira River SPM) together with elsewhere constant source contributions. Furthermore, we report a prominent offset in Sr and Nd isotopic composition between the average core value (εNd: -11.7 ± 0.9 (2SD), 87Sr/86Sr: 0.7229 ± 0.0016 (2SD)) and the average modern Amazon River SPM signal (εNd: -10.5 ± 0.5 (2SD), 87Sr/86Sr: 0.7213 ± 0.0036 (2SD)). We suggest that a permanent change in the Amazon River basin sediment supply during the late Holocene to a more Andean dominated SPM was responsible for the offset.

Bioconversion of Coal: Hydrologic indicators of the extent of coal biodegradation under different redox conditions and coal maturity, Velenje Basin case study, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Grassa, Fausto; Lazar, Jerneja; Jamnikar, Sergej; Zavšek, Simon; McIntosh, Jennifer

2014-05-01

Underground mining of coal and coal combustion for energy has significant environmental impacts. In order to reduce greenhouse gas emissions, other lower -carbon energy sources must be utilized. Coalbed methane (CBM) is an important source of relatively low-carbon energy. Approximately 20% of world's coalbed methane is microbial in origin (Bates et al., 2011). Interest in microbial CBM has increased recently due to the possibility of stimulating methanogenesis. Despite increasing interest, the hydrogeochemical conditions and mechanisms for biodegradation of coal and microbial methane production are poorly understood. This project aims to examine geochemical characteristics of coalbed groundwater and coalbed gases in order to constrain biogeochemical processes to better understand the entire process of coal biodegradation of coal to coalbed gases. A better understanding of geochemical processes in CBM areas may potentially lead to sustainable stimulation of microbial methanogenesis at economical rates. Natural analogue studies of carbon dioxide occurring in the subsurface have the potential to yield insights into mechanisms of carbon dioxide storage over geological time scales (Li et al., 2013). In order to explore redox processes related to methanogenesis and determine ideal conditions under which microbial degradation of coal is likely to occur, this study utilizes groundwater and coalbed gas samples from Velenje Basin. Determination of the concentrations of methane, carbondioxide, nitrogen, oxygen, argon was performed with homemade NIER mass spectrometer. Isotopic composition of carbon dioxide, isotopic composition of methane, isotopic composition of deuterium in methane was determined with Europa-Scientific IRMS with an ANCA-TG preparation module and Thermo Delta XP GC-TC/CF-IRMS coupled to a TRACE GC analyzer. Total alkalinity of groundwater was measured by Gran titration. Major cations were analyzed by ICP-OES and anions by IC method. Isotopic composition of dissolved inorganic carbon was determined by MultiflowBio preparation module. The stable isotope composition of sulphur was determined with a Europa Scientific 20-20 continuous flow IRMS ANCA-SL preparation module. Concentrations of tritium were determined with the electrolytic enrichment method. PHREEQC for Windows was used to perform thermodynamic modelling. The average coalbed gas composition in the coalbed seam is approximately carbon dioxide: methane > 2:1, where a high proportion of CO2 is adsorbed on the lignite structure, while methane is present free in coal fractures. It can be concluded that isotopic composition of carbon in methane from -70.4‰ to -50.0‰ is generated via acetate fermentation and via reduction of carbon dioxide, while isotopic composition of carbon in methane values range from -50.0‰ to -18.8‰, thermogenic methane can be explained by secondary processes, causing enrichment of residual methane with the heavier carbon isotope. Isotopic composition of deuterium in methane range from -343.9‰ to -223.1‰. Isotopic composition of carbon in carbon dioxide values at excavation fields range from -11.0‰ to +5‰ and are endogenic and microbial in origin. The major ion chemistry, redox conditions, stable isotopes and tritium measured in groundwater from the Velenje Basin, suggest that the Pliocene and Triassic aquifers contain distinct water bodies. Groundwater in the Triassic aquifer is dominated by hydrogen carbonate, calcium, magnesium and isotopic composition of dissolved inorganic carbon indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has isotopic composition of oxygen and isotopic composition of deuterium values which plot near surface waters on the local and global meteoric water lines and detectable tritium reflects recent recharge. In contrast, groundwater in the Pliocene aquifers is enriched in magnesium, sodium, calcium, potassium, and silica and has alkalinity and isotopic composition of dissolved inorganic carbon values with low sulphate and nitrate concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and magnesium-rich clay minerals. Pliocene aquifer waters are also depleted in heavier oxygen isotope and heavier deuterium isotope and have tritium concentrations near the detection limit, suggesting these waters are older. References Bates, B.L., McIntosh J.C., Lohse K.A., Brooks P.D. 2011: Influence of groundwater flowpaths, residence times, and nutrients on the extent of microbial methanogenesis in coal beds: Powder River Basin, USA, Chemical geology, 284, 45-61. Li, W., Cheng Y., Wang L., Zhou H., Wang H., Wang L. 2013: Evaluating the security of geological coalbed sequestration of supercritical CO2 reservoirs: The Haishiwan coalfield, China as a natural analogue, International Journal of Greenhouse Gas Control, 13, 102-111.

Molar tooth structures in calcareous nodules, early Neoproterozoic Burovaya Formation, Turukhansk region, Siberia

NASA Astrophysics Data System (ADS)

Pope, Michael C.; Bartley, Julie K.; Knoll, Andrew H.; Petrov, Peter Yu.

2003-05-01

Molar tooth structures are abundant in large (1-2 m diameter) carbonate nodules within fine-grained, subtidal carbonates of the early Neoproterozoic (lower Upper Riphean) Burovaya Formation along the Sukhaya Tunguska River, Turukhansk Uplift, northwestern Siberia. Although molar tooth structures are regionally abundant in this unit, here they occur only within the nodules. Stable isotopic compositions of molar-tooth-filling dolomicrospar cements and of thinly bedded dolomicrite within and surrounding the nodules are indistinguishable from one another. The carbon isotopic compositions (mean δ13C=+2.8‰ PDB±0.4) reflect mean average oceanic surface water composition during their formation; the light oxygen isotopic compositions (mean δ18O=-6.4‰ PDB±2.2) are generally similar to those of other little-altered Meso- to Neoproterozoic limestones and dolostones. These molar tooth structures have no features that would support a tectonic origin; they more likely formed through bacterial processes. Carbonate cement filling of these voids occurred soon after their formation, but the mechanism responsible for this carbonate precipitation is currently uncertain. Local restriction of molar tooth structures to early diagenetic nodules suggests that penecontemporaneous lithification was required for the formation, or at least preservation, of these widespread Mesoproterozoic to Neoproterozoic features.

The Mantle Isotopic Array: A Tale of Two FOZOs

NASA Astrophysics Data System (ADS)

Apen, F. E.; Mukhopadhyay, S.; Williams, C. D.

2017-12-01

Oceanic basalts display isotopic arrays that suggest mixing between a depleted component, several enriched components, and a primitive component. The topology of the arrays provides information on mantle mixing, the distribution of heterogeneities, and information on mantle structure. Here we use a global compilation of mid-ocean ridge basalt (MORB) and ocean island basalt (OIB) He-Sr-Nd-Pb isotopic data to further analyze the topology of these arrays. Previous work indicated that OIB isotopic arrays converge to a common component [1-3] referred to as the focus zone, or FOZO. Our analyses suggest that while all OIBs do point to a common component with unradiogenic 4He/3He ratios relative to MORBs, this component has to be quite variable in its He, Sr, Nd and Pb isotopic compositions. FOZO cannot be a pure component but must represent a heterogeneous mixture of primitive and recycled material. Our analyses of the MORB and OIB isotopic compositions also indicate that while MORBs and OIBs sample the same components, the topology of their mixing arrays are quite distinct. Different MOR segments show quasi-linear isotopic arrays that all converge to a common component. This component is distinctive from the OIB FOZO being more depleted and more restrictive in its He, Sr, Nd and Pb composition. We suggest two common but distinguishable components are present in the mantle arrays: one common to MORBs and the other to OIBs, and we refer to them as MORB-FOZO and OIB-FOZO, respectively. We interpret the two FOZOs to represent the average composition of small-scale heterogeneities that make up the background matrix in the sources of MORBs and OIBs. The depleted and enriched components that are sampled in MORBs and OIBs reflect relatively large-scale heterogeneities distributed within the matrix, material that have yet to be deformed into the smaller length scales of the matrix material. Differences between the two FOZO compositions reflects the inclusion of a component with primitive He in OIBs along with differences in mixing timescales and mantle processing rates for MORBs and OIBs. The two distinct FOZO compositions must also indicate limited direct mixing between the two over Earth's 4.5 Gyr history. References: [1] Hart et al., Science 1992; [2] Farley et al., EPSL 1992; [3] Hanan and Graham, Science 1996.

Ages and stable-isotope compositions of secondary calcite and opal in drill cores from Tertiary volcanic rocks of the Yucca Mountain area, Nevada

USGS Publications Warehouse

Szabo, B. J.; Kyser, T.K.

1990-01-01

Stable-isotope compositions of fracture- and cavity-filling calcite from the unsaturated zone of three drill cores at Yucca Mountain Tertiary volcanic complex indicate that the water from which the minerals precipitated was probably meteoric in origin. A decrease in 18O in the calcite with depth is interpreted as being due to the increase in temperature in drill holes corresponding to an estimated average geothermal gradient of 34?? per kilometer. A few of the calcite samples and all of the opal samples yielded uranium-series ages older than 400 000 yr, although most of the calcite samples yielded ages between 26 000 and 310 000 yr. The stable-isotope and uranium-series dates from precipitated calcite and opal of this reconnaissance study suggest a complex history of fluid movement through the volcanic pile, and episodes of fracture filling predominantly from meteoric water during at least the past 400 000 yr. -Authors

Isotopic composition of strontium in three basalt-andesite centers along the Lesser Antilles arc

USGS Publications Warehouse

Hedge, C.E.; Lewis, J.F.

1971-01-01

Si87/Sr86 ratios have been determined for lavas and py lastic rocks from three basalt-andesite centers along the Lesser Antilles arc-Mt. Misery on the island of St. Kitts, Soufriere on the island of St. Vincent, and Carriacou, an island of The Grenadines. The average Si87/Sr86 content of these rocks is 0.7038 for Mt. Misery, 0.7041 for Soufriere, and 0.7053 for Carriacou. All the Sr87/Sr86 values from each center are the same within analytical uncertainty (??0.0002). The constancy of strontium isotopic data within each center supports the hypothesis that basalts and andesites for each specific center investigated are generated from the same source - in agreement with petrographic and major- and minor-element data. Strontium isotopic compositions and elemental concentrations, particularly of strontium and nickel, indicate that this source was mantle peridotite and that the relationship between the respective basalts and andesites is probably fractional crystallization. ?? 1971 Springer-Verlag.

Generation and Reworking of Archaean and Hadean Crust

NASA Astrophysics Data System (ADS)

Hawkesworth, C.; Kemp, T.; Storey, C.; Dhuime, B.

2008-12-01

Combined Hf and O isotopes in well-dated zircons are increasingly used to investigate the age of the crustal source rocks of detrital and inherited zircons. O isotopes are used to screen out samples that may have a sediment contribution in the parental magma, since sediments yield hybrid model ages that are difficult to interpret. Mafic and granitic rocks also have different Lu/Hf ratios, and so in principle the Hf isotope ratios of zircons can be used to investigate the broad composition of the average crust. The unradiogenic Hf isotope compositions of the Jack Hills zircons from Western Australia indicate the existence of enriched (crustal) reservoirs by at least 4.3 Ga (Y. Amelin et al., 1998, Nature v. 399, p. 252- 255; T. M. Harrison et al., 2005, Science, v. 310, p. 1947-1950). We report in situ Hf isotope analyses of the Jack Hills zircons in which the Pb isotope age information is measured concurrently with the Hf isotope data. The simple data arrays provide clear evidence for Earth differentiation at 4.5 Ga, with the production of both continental crust-like material and a mafic crustal reservoir with higher Lu/Hf. The continued resampling of this reservoir over at least 1.5 Ga argues for a substantial stabilised volume of mafic crust, and, in tandem with oxygen isotope data, the existence of Hadean continents. Zircons remain poor windows into the upper mantle. We therefore investigate Nd isotopes in well-dated titanites; they have closure temperatures for Pb in the range 600-750oC and they can retain cores with distinct age and REE chemistry to subsequent rim overgrowths. Nd isotopes offer a complementary approach to Hf in zircon that can be used to construct the both depleted mantle evolution and crustal growth curves.

Titanium stable isotopic variations in chondrites, achondrites and lunar rocks

NASA Astrophysics Data System (ADS)

Greber, Nicolas D.; Dauphas, Nicolas; Puchtel, Igor S.; Hofmann, Beda A.; Arndt, Nicholas T.

2017-09-01

Titanium isotopes are potential tracers of processes of evaporation/condensation in the solar nebula and magmatic differentiation in planetary bodies. To gain new insights into the processes that control Ti isotopic variations in planetary materials, 25 komatiites, 15 chondrites, 11 HED-clan meteorites, 5 angrites, 6 aubrites, a martian shergottite, and a KREEP-rich impact melt breccia have been analyzed for their mass-dependent Ti isotopic compositions, presented using the δ49Ti notation (deviation in permil of the 49Ti/47Ti ratio relative to the OL-Ti standard). No significant variation in δ49Ti is found among ordinary, enstatite, and carbonaceous chondrites, and the average chondritic δ49Ti value of +0.004 ± 0.010‰ is in excellent agreement with the published estimate for the bulk silicate Earth, the Moon, Mars, and the HED and angrite parent-bodies. The average δ49Ti value of komatiites of -0.001 ± 0.019‰ is also identical to that of the bulk silicate Earth and chondrites. OL-Ti has a Ti isotopic composition that is indistinguishable from chondrites and is therefore a suitable material for reporting δ49Ti values. Previously published isotope data on another highly refractory element, Ca, show measurable variations among chondrites. The decoupling between Ca and Ti isotope systematics most likely occurred during condensation in the solar nebula. Aubrites exhibit significant variations in δ49Ti, from -0.07 to +0.24‰. This is likely due to the uniquely reducing conditions under which the aubrite parent-body differentiated, allowing chalcophile Ti3+ and lithophile Ti4+ to co-exist. Consequently, the observed negative correlation between δ49Ti values and MgO concentrations among aubrites is interpreted to be the result of isotope fractionation driven by the different oxidation states of Ti in this environment, such that isotopically heavy Ti4+ was concentrated in the residual liquid during magmatic differentiation. Finally, KREEPy impact melt breccia SaU 169 exhibits a heavy δ49Ti value of +0.330 ± 0.034‰ which is interpreted to result from Ti isotopic fractionation during ilmenite precipitation in the late stages of lunar magma ocean crystallization. A Rayleigh distillation calculation predicts that a δ49Ti value of +0.330‰ is achieved after removal of 94% of Ti in ilmenite.

Tracing subduction zone fluid-rock interactions using trace element and Mg-Sr-Nd isotopes

NASA Astrophysics Data System (ADS)

Wang, Shui-Jiong; Teng, Fang-Zhen; Li, Shu-Guang; Zhang, Li-Fei; Du, Jin-Xue; He, Yong-Sheng; Niu, Yaoling

2017-10-01

Slab-derived fluids play a key role in mass transfer and elemental/isotopic exchanges in subduction zones. The exhumation of deeply subducted crust is achieved via a subduction channel where fluids from various sources are abundant, and thus the chemical/isotopic compositions of these rocks could have been modified by subduction-zone fluid-rock interactions. Here, we investigate the Mg isotopic systematics of eclogites from southwestern Tianshan, in conjunction with major/trace element and Sr-Nd isotopes, to characterize the source and nature of fluids and to decipher how fluid-rock interactions in subduction channel might influence the Mg isotopic systematics of exhumed eclogites. The eclogites have high LILEs (especially Ba) and Pb, high initial 87Sr/86Sr (up to 0.7117; higher than that of coeval seawater), and varying Ni and Co (mostly lower than those of oceanic basalts), suggesting that these eclogites have interacted with metamorphic fluids mainly released from subducted sediments, with minor contributions from altered oceanic crust or altered abyssal peridotites. The positive correlation between 87Sr/86Sr and Pb* (an index of Pb enrichment; Pb* = 2*PbN/[CeN + PrN]), and the decoupling relationships and bidirectional patterns in 87Sr/86Sr-Rb/Sr, Pb*-Rb/Sr and Pb*-Ba/Pb spaces imply the presence of two compositionally different components for the fluids: one enriched in LILEs, and the other enriched in Pb and 87Sr/86Sr. The systematically heavier Mg isotopic compositions (δ26Mg = - 0.37 to + 0.26) relative to oceanic basalts (- 0.25 ± 0.07) and the roughly negative correlation of δ26Mg with MgO for the southwestern Tianshan eclogites, cannot be explained by inheritance of Mg isotopic signatures from ancient seafloor alteration or prograde metamorphism. Instead, the signatures are most likely produced by fluid-rock interactions during the exhumation of eclogites. The high Rb/Sr and Ba/Pb but low Pb* eclogites generally have high bulk-rock δ26Mg values, whereas high Pb* and 87Sr/86Sr eclogites have mantle-like δ26Mg values, suggesting that the two fluid components have diverse influences on the Mg isotopic systematics of these eclogites. The LILE-rich fluid component, possibly derived from mica-group minerals, contains a considerable amount of isotopically heavy Mg that has shifted the δ26Mg of the eclogites towards higher values. By contrast, the 87Sr/86Sr- and Pb-rich fluid component, most likely released from epidote-group minerals in metasediments, has little Mg so as not to modify the Mg isotopic composition of the eclogites. In addition, the influence of talc-derived fluid might be evident in a very few eclogites that have low Rb/Sr and Ba/Pb but slightly heavier Mg isotopic compositions. These findings represent an important step toward a broad understanding of the Mg isotope geochemistry in subduction zones, and contributing to understanding why island arc basalts have averagely heavier Mg isotopic compositions than the normal mantle.

Isotope geochemistry of mercury in source rocks, mineral deposits and spring deposits of the California Coast Ranges, USA

NASA Astrophysics Data System (ADS)

Smith, Christopher N.; Kesler, Stephen E.; Blum, Joel D.; Rytuba, James J.

2008-05-01

We present here the first study of the isotopic composition of mercury in rocks, ore deposits, and active spring deposits from the California Coast Ranges, a part of Earth's crust with unusually extensive evidence of mercury mobility and enrichment. The Franciscan Complex and Great Valley Sequence, which form the bedrock in the California Coast Ranges, are intruded and overlain by Tertiary volcanic rocks including the Clear Lake Volcanic Sequence. These rocks contain two types of mercury deposits, hot-spring deposits that form at shallow depths (< 300 m) and silica-carbonate deposits that extend to depths of 1000 m. Active springs and geothermal areas continue to precipitate Hg and Au and are modern analogues to the fossil hydrothermal systems preserved in the ore deposits. The Franciscan Complex and Great Valley Sequence contain clastic sedimentary rocks with higher concentrations of mercury than volcanic rocks of the Clear Lake Volcanic Field. Mean mercury isotopic compositions ( δ202Hg) for all three rock units are similar, although the range of values in Franciscan Complex rocks is greater than in either Great Valley or Clear Lake rocks. Hot spring and silica-carbonate mercury deposits have similar average mercury isotopic compositions that are indistinguishable from averages for the three rock units, although δ202Hg values for the mercury deposits have a greater variance than the country rocks. Precipitates from spring and geothermal waters in the area have similarly large variance and a mean δ202Hg value that is significantly lower than the ore deposits and rocks. These observations indicate that there is little or no isotopic fractionation (< ± 0.5‰) during release of mercury from its source rocks into hydrothermal solutions. Isotopic fractionation does appear to take place during transport and concentration of mercury in deposits, however, especially in their uppermost parts. Boiling of hydrothermal fluids, separation of a mercury-bearing CO 2 vapor or reduction and volatilization of Hg (0) in the near-surface environment are likely the most important processes causing the observed Hg isotope fractionation. This should result in the release of mercury with low δ202Hg values into the atmosphere from the top of these hydrothermal systems. Estimates of mass balance suggest that residual Hg reservoirs are not measurably enriched in heavy Hg isotopes as a result of this process because only a small amount of Hg (< 4%) leaves actively ore-forming systems.

Isotope geochemistry of mercury in source rocks, mineral deposits and spring deposits of the California Coast Ranges, USA

USGS Publications Warehouse

Smith, C.N.; Kesler, S.E.; Blum, J.D.; Rytuba, J.J.

2008-01-01

We present here the first study of the isotopic composition of mercury in rocks, ore deposits, and active spring deposits from the California Coast Ranges, a part of Earth's crust with unusually extensive evidence of mercury mobility and enrichment. The Franciscan Complex and Great Valley Sequence, which form the bedrock in the California Coast Ranges, are intruded and overlain by Tertiary volcanic rocks including the Clear Lake Volcanic Sequence. These rocks contain two types of mercury deposits, hot-spring deposits that form at shallow depths (< 300??m) and silica-carbonate deposits that extend to depths of 1000??m. Active springs and geothermal areas continue to precipitate Hg and Au and are modern analogues to the fossil hydrothermal systems preserved in the ore deposits. The Franciscan Complex and Great Valley Sequence contain clastic sedimentary rocks with higher concentrations of mercury than volcanic rocks of the Clear Lake Volcanic Field. Mean mercury isotopic compositions (??202Hg) for all three rock units are similar, although the range of values in Franciscan Complex rocks is greater than in either Great Valley or Clear Lake rocks. Hot spring and silica-carbonate mercury deposits have similar average mercury isotopic compositions that are indistinguishable from averages for the three rock units, although ??202Hg values for the mercury deposits have a greater variance than the country rocks. Precipitates from spring and geothermal waters in the area have similarly large variance and a mean ??202Hg value that is significantly lower than the ore deposits and rocks. These observations indicate that there is little or no isotopic fractionation (< ?? 0.5???) during release of mercury from its source rocks into hydrothermal solutions. Isotopic fractionation does appear to take place during transport and concentration of mercury in deposits, however, especially in their uppermost parts. Boiling of hydrothermal fluids, separation of a mercury-bearing CO2 vapor or reduction and volatilization of Hg(0) in the near-surface environment are likely the most important processes causing the observed Hg isotope fractionation. This should result in the release of mercury with low ??202Hg values into the atmosphere from the top of these hydrothermal systems. Estimates of mass balance suggest that residual Hg reservoirs are not measurably enriched in heavy Hg isotopes as a result of this process because only a small amount of Hg (< 4%) leaves actively ore-forming systems. ?? 2008 Elsevier B.V. All rights reserved.

A strong control of the South American SeeSaw on the intra-seasonal variability of the isotopic composition of precipitation in the Bolivian Andes

NASA Astrophysics Data System (ADS)

Vimeux, Françoise; Tremoy, Guillaume; Risi, Camille; Gallaire, Robert

2011-07-01

Water stable isotopes (δ) in tropical regions are a valuable tool to study both convective processes and climate variability provided that local and remote controls on δ are well known. Here, we examine the intra-seasonal variability of the event-based isotopic composition of precipitation (δD Zongo) in the Bolivian Andes (Zongo valley, 16°20'S-67°47'W) from September 1st, 1999 to August 31st, 2000. We show that the local amount effect is a very poor parameter to explain δD Zongo. We thus explore the property of water isotopes to integrate both temporal and spatial convective activities. We first show that the local convective activity averaged over the 7-8 days preceding the rainy event is an important control on δD Zongo during the rainy season (~ 40% of the δD Zongo variability is captured). This could be explained by the progressive depletion of local water vapor by unsaturated downdrafts of convective systems. The exploration of remote convective controls on δD Zongo shows a strong influence of the South American SeeSaw (SASS) which is the first climate mode controlling the precipitation variability in tropical South America during austral summer. Our study clearly evidences that temporal and spatial controls are not fully independent as the 7-day averaged convection in the Zongo valley responds to the SASS. Our results are finally used to evaluate a water isotope enabled atmospheric general circulation model (LMDZ-iso), using the stretched grid functionality to run zoomed simulations over the entire South American continent (15°N-55°S; 30°-85°W). We find that zoomed simulations capture the intra-seasonal isotopic variation and its controls, though with an overestimated local sensitivity, and confirm the role of a remote control on δ according to a SASS-like dipolar structure.

Stable carbon and nitrogen isotope analysis of avian uric acid.

PubMed

Bird, Michael I; Tait, Elaine; Wurster, Christopher M; Furness, Robert W

2008-11-01

We report results obtained using a new technique developed to measure the stable-isotope composition of uric acid isolated from bird excreta (guano). Results from a diet-switch feeding trial using zebra finches suggest that the delta(13)C of uric acid in the guano equilibrates with the diet of the bird within 3 days of a change in diet, while the equilibration time for delta(15)N may be longer. The average carbon isotope discrimination between uric acid and food before the diet switch was +0.34 +/- 1 per thousand (1sigma) while after the diet switch this increased slightly to +0.83 +/- 0.7 per thousand (1sigma). Nitrogen isotope discrimination was +1.3 +/- 0.3 per thousand (1sigma) and +0.3 +/- 0.3 per thousand (1sigma) before and after the diet switch; however, it is possible that the nitrogen isotope values did not fully equilibrate with diet switch over the course of the experiment. Analyses of other chemical fractions of the guano (organic residue after uric acid extraction and non-uric acid organics solubilised during extraction) suggest a total range of up to 3 per thousand for both delta(13)C and delta(15)N values in individual components of a single bulk guano sample. The analysis of natural samples from a range of terrestrial and marine species demonstrates that the technique yields isotopic compositions consistent with the known diets of the birds. The results from natural samples further demonstrate that multiple samples from the same species collected from the same location yield similar results, while different species from the same location exhibit a range of isotopic compositions indicative of different dietary preferences. Given that many samples of guano can be rapidly collected without any requirement to capture specimens for invasive sampling, the stable-isotope analysis of uric acid offers a new, simple and potentially powerful tool for studying avian ecology and metabolism.

Origin of uranium isotope variations in early solar nebula condensates.

PubMed

Tissot, François L H; Dauphas, Nicolas; Grossman, Lawrence

2016-03-01

High-temperature condensates found in meteorites display uranium isotopic variations ((235)U/(238)U), which complicate dating the solar system's formation and whose origin remains mysterious. It is possible that these variations are due to the decay of the short-lived radionuclide (247)Cm (t 1/2 = 15.6 My) into (235)U, but they could also be due to uranium kinetic isotopic fractionation during condensation. We report uranium isotope measurements of meteoritic refractory inclusions that reveal excesses of (235)U reaching ~+6% relative to average solar system composition, which can only be due to the decay of (247)Cm. This allows us to constrain the (247)Cm/(235)U ratio at solar system formation to (1.1 ± 0.3) × 10(-4). This value provides new clues on the universality of the nucleosynthetic r-process of rapid neutron capture.

Calcium isotope constraints on the end-Permian mass extinction

PubMed Central

Payne, Jonathan L.; Turchyn, Alexandra V.; Paytan, Adina; DePaolo, Donald J.; Lehrmann, Daniel J.; Yu, Meiyi; Wei, Jiayong

2010-01-01

The end-Permian mass extinction horizon is marked by an abrupt shift in style of carbonate sedimentation and a negative excursion in the carbon isotope (δ13C) composition of carbonate minerals. Several extinction scenarios consistent with these observations have been put forward. Secular variation in the calcium isotope (δ44/40Ca) composition of marine sediments provides a tool for distinguishing among these possibilities and thereby constraining the causes of mass extinction. Here we report δ44/40Ca across the Permian-Triassic boundary from marine limestone in south China. The δ44/40Ca exhibits a transient negative excursion of ∼0.3‰ over a few hundred thousand years or less, which we interpret to reflect a change in the global δ44/40Ca composition of seawater. CO2-driven ocean acidification best explains the coincidence of the δ44/40Ca excursion with negative excursions in the δ13C of carbonates and organic matter and the preferential extinction of heavily calcified marine animals. Calcium isotope constraints on carbon cycle calculations suggest that the average δ13C of CO2 released was heavier than -28‰ and more likely near -15‰; these values indicate a source containing substantial amounts of mantle- or carbonate-derived carbon. Collectively, the results point toward Siberian Trap volcanism as the trigger of mass extinction. PMID:20421502

A rapid method for the sampling of atmospheric water vapour for isotopic analysis.

PubMed

Peters, Leon I; Yakir, Dan

2010-01-01

Analysis of the stable isotopic composition of atmospheric moisture is widely applied in the environmental sciences. Traditional methods for obtaining isotopic compositional data from ambient moisture have required complicated sampling procedures, expensive and sophisticated distillation lines, hazardous consumables, and lengthy treatments prior to analysis. Newer laser-based techniques are expensive and usually not suitable for large-scale field campaigns, especially in cases where access to mains power is not feasible or high spatial coverage is required. Here we outline the construction and usage of a novel vapour-sampling system based on a battery-operated Stirling cycle cooler, which is simple to operate, does not require any consumables, or post-collection distillation, and is light-weight and highly portable. We demonstrate the ability of this system to reproduce delta(18)O isotopic compositions of ambient water vapour, with samples taken simultaneously by a traditional cryogenic collection technique. Samples were collected over 1 h directly into autosampler vials and were analysed by mass spectrometry after pyrolysis of 1 microL aliquots to CO. This yielded an average error of < +/-0.5 per thousand, approximately equal to the signal-to-noise ratio of traditional approaches. This new system provides a rapid and reliable alternative to conventional cryogenic techniques, particularly in cases requiring high sample throughput or where access to distillation lines, slurry maintenance or mains power is not feasible. Copyright 2009 John Wiley & Sons, Ltd.

Seasonal isotope hydrology of a coffee agroforestry watershed in Costa Rica

NASA Astrophysics Data System (ADS)

Welsh Unwala, K.; Boll, J.; Roupsard, O.

2014-12-01

Improved information of seasonal variations in watershed hydrology in the tropics can strengthen models and understanding of hydrology of these areas. Seasonality in the tropics produces rainy seasons versus dry seasons, leading to different hydrologic and water quality processes throughout the year. We questioned whether stable isotopes in water can be used to trace the seasonality in this region, despite experiencing a "drier" season, such as in a Tropical Humid location. This study examines the fluctuations of stable isotope compositions (δ18O and δD) in water balance components in a small (<1 km2) coffee agroforestry watershed located in central Costa Rica on the Caribbean side. Samples were collected in precipitation, groundwater, and stream water for more than two years, across seasons and at an hourly frequency during storm events to better characterize spatial and temporal variations of the isotopic composition and of the respective contribution of surface and deeper groundwater to streamflow in the watershed. Isotope composition in precipitation ranged from -18.5 to -0.3‰ (∂18O) and -136.4 to 13.7‰ (∂D), and data indicate that atmospheric moisture cycling plays an important role in this region. A distinct seasonality was observed in monthly-averaged data between enriched dry season events as compared with the rainy season events. Streamflow data indicate that a deep groundwater system contributes significantly to baseflow, although a shallow, spring-driven system also contributes to stream water within the watershed. During storm events, precipitation contributes to stormflow in the short-term, confirming the role of superficial runoff. These results indicate that isotopes are helpful to partition the water balance even in a Tropical Humid situation where the rainfall seasonality is weak.

Cretaceous shales from the western interior of North America: sulfur/carbon ratios and sulfur-isotope composition.

USGS Publications Warehouse

Gautier, D.L.

1986-01-01

Sulphur/carbon ratios in cores of selected Cretaceous marine shales average 0.67, a value greater than that observed in recent marine sediments and much higher than global values calculated for the Cretaceous. This may be ascribed to generally low levels of bioturbation and enhanced efficiency of sulphate reduction due to low oxygen levels in Cretaceous seaways. Isotopic compositions of pyrite sulphur vary systematically with level of oxygenation of the depositional environment and therefore with organic carbon abundance and type of organic matter. Samples with >4% organic carbon are extremely depleted in 34S (mean delta 34S -31per mille) and contain hydrogen-rich organic matter. Samples containing <1.5% organic carbon display relatively 'heavy' but wide-ranging delta 34S values (-34.6 to +16.8per mille) and contain hydrogen-poor organic matter. Samples with intermediate amounts of organic carbon have average delta 34S of -25.9per mille and contain both types of organic matter. Relations between the nature of these shales, and their sedimentation rate and depositional environment are discussed.-L.C.H.

Use of stable sulfur isotopes to identify sources of sulfate in Rocky Mountain snowpacks

USGS Publications Warehouse

Mast, M.A.; Turk, J.T.; Ingersoll, G.P.; Clow, D.W.; Kester, C.L.

2001-01-01

Stable sulfur isotope ratios and major ions in bulk snowpack samples were monitored at a network of 52 high-elevation sites along and near the Continental Divide from 1993 to 1999. This information was collected to better define atmospheric deposition to remote areas of the Rocky Mountains and to help identify the major source regions of sulfate in winter deposition. Average annual ??34S values at individual sites ranged from + 4.0 to + 8.2??? and standard deviations ranged from 0.4 to 1.6???. The chemical composition of all samples was extremely dilute and slightly acidic; average sulfate concentrations ranged from 2.4 to 12.2 ??eql-1 and pH ranged from 4.82 to 5.70. The range of ??34S values measured in this study indicated that snowpack sulfur in the Rocky Mountains is primarily derived from anthropogenic sources. A nearly linear relation between ??34S and latitude was observed for sites in New Mexico, Colorado, and southern Wyoming, which indicates that snowpack sulfate in the southern part of the network was derived from two isotopically distinct source regions. Because the major point sources of SO2 in the region are coal-fired powerplants, this pattern may reflect variations in the isotopic composition of coals burned by the plants. The geographic pattern in ??34S for sites farther to the north in Wyoming and Montana was much less distinct, perhaps rflecting the paucity of major point sources of SO2 in the northern part of the network.

Nitrogen and carbon isotopic dynamics of subarctic soils and plants in southern Yukon Territory and its implications for paleoecological and paleodietary studies

PubMed Central

Longstaffe, Fred J.; Zazula, Grant; Bennett, Bruce

2017-01-01

We examine here the carbon and nitrogen isotopic compositions of bulk soils (8 topsoil and 7 subsoils, including two soil profiles) and five different plant parts of 79 C3 plants from two main functional groups: herbs and shrubs/subshrubs, from 18 different locations in grasslands of southern Yukon Territory, Canada (eastern shoreline of Kluane Lake and Whitehorse area). The Kluane Lake region in particular has been identified previously as an analogue for Late Pleistocene eastern Beringia. All topsoils have higher average total nitrogen δ15N and organic carbon δ13C than plants from the same sites with a positive shift occurring with depth in two soil profiles analyzed. All plants analyzed have an average whole plant δ13C of −27.5 ± 1.2 ‰ and foliar δ13C of –28.0 ± 1.3 ‰, and average whole plant δ15N of −0.3 ± 2.2 ‰ and foliar δ15N of –0.6 ± 2.7 ‰. Plants analyzed here showed relatively smaller variability in δ13C than δ15N. Their average δ13C after suitable corrections for the Suess effect should be suitable as baseline for interpreting diets of Late Pleistocene herbivores that lived in eastern Beringia. Water availability, nitrogen availability, spacial differences and intra-plant variability are important controls on δ15N of herbaceous plants in the study area. The wider range of δ15N, the more numerous factors that affect nitrogen isotopic composition and their likely differences in the past, however, limit use of the modern N isotopic baseline for vegetation in paleodietary models for such ecosystems. That said, the positive correlation between foliar δ15N and N content shown for the modern plants could support use of plant δ15N as an index for plant N content and therefore forage quality. The modern N isotopic baseline cannot be applied directly to the past, but it is prerequisite to future efforts to detect shifts in N cycling and forage quality since the Late Pleistocene through comparison with fossil plants from the same region. PMID:28813532

Sr, Nd and Pb Isotope Geochemistry of Near-ridge Seamounts in Eastern Pacific: Implications for Upper Mantle Composition and EPR Magmatic Segmentation

NASA Astrophysics Data System (ADS)

Castillo, P. R.; White, W. M.; Batiza, R.

2005-12-01

Near-ridge seamount lavas tend to reflect the true composition of the upper mantle source of MORB because these are generated by relatively smaller degrees of melting of smaller volumes of the mantle compared to nearby axial lavas; they also by-pass the axial chamber mixing and fractionation processes that are responsible for the relatively more uniform chemical and isotopic composition of normal-MORB. New Sr, Nd and Pb isotope data combined with published data for lavas from near-ridge seamounts on either side of the EPR segment between the 11o45' OSC and Orozco Transform at 15o00' show latitudinal isotopic variation very similar to that shown by the rise axial lavas (Castillo et al., G3 1, 1999). Seamount and axial lavas at both ends of the rise segment have on average slightly higher and more limited range of 143Nd/144Nd, but slightly lower 206Pb/204Pb and 87Sr/86Sr ratios than lavas at the center of the segment. Some of the seamounts are located on ~8 Ma rise flank crust although most of the seamount lavas are fairly young (e.g., lavas from Seamount 6 on ~3 Ma crust are only 3 to 900 kyr - Graham et al., Nature 326, 1987). Thus near-ridge seamount isotope data provide the first documentation for a large-scale (~350 km long x ~720 km wide), systematic compositional variation of the upper mantle source of EPR MORB. Such a scale of variation is larger and longer than the size and <1 myr life span of the majority of non-transform offsets, which are supposed to be responsible for the along-axis compositional variations of EPR MORB according to the "bottoms up" model of magmatic segmentation.

[Tracing Sources of Sulfate Aerosol in Nanjing Northern Suburb Using Sulfur and Oxygen Isotopes].

PubMed

Wei, Ying; Guo, Zhao-bing; Ge, Xin; Zhu, Sheng-nan; Jiang, Wen-juan; Shi, Lei; Chen, Shu

2015-04-01

Abstract: To trace the sources of sulfate contributing to atmospheric aerosol, PM2.5 samples for isotopic analysis were collected in Nanjing northern suburb during January 2014. The sulfur and oxygen isotopic compositions of sulfate from these samples were determined by EA-IRMS. Source identification and apportionment were carried out using stable isotopic and chemical evidences, combined with absolute principal component analysis (APCA) method. The Δ34S values of aerosol sulfate ranged from 2.7 per thousand to 6.4 per thousand, with an average of 5.0 per thousand ± 0.9 per thousand, while the Δ18O values ranged from 10.6 per thousand to 16.1 per thousand, with an average of 12.5 per thousand ± 1.37 per thousand. In conjunction with air mass trajectories, the results suggested that aerosol sulfates were controlled by a dominance of local anthropogenic sulfate, followed by the contributions of long-distance transported sulfate. There was a minor effect of some other low-Δ34S valued sulfates, which might be expected from biogenic sources. Absolute principal component analysis results showed that the contributions of anthropogenic sulfate and long-distance transported sulfate were 46.74% and 31.54%, respectively.

A high-resolution geochronological and geochemical study on Aegean carbonate deposits, SW Turkey

NASA Astrophysics Data System (ADS)

Ünal-İmer, Ezgi; Uysal, I. Tonguç; Işık, Veysel; Zhao, Jian-Xin; Shulmeister, James

2014-05-01

Vein and breccia carbonates precipitated in highly fractured/faulted carbonate bedrock were investigated using high-resolution U-series geochronology, as well as through microstructural and geochemical studies including Sr-O-C isotope and REE element analyses. The study area (Kumlubük and Amos vein systems), located south of the town of Marmaris in SW Turkey, is a part of an active large-scale extensional system. Field studies show that the calcite veins generally occur sub-vertically and strike mostly NW and EW, in agreement with the regional N-S extensional stress regime. Microscopic observations indicate that the calcite veins formed through crack-seal mechanism, typically accompanied/initiated by intensive hydraulic fracturing of wall-rock evidenced by the presence of widespread breccia deposits. Vein textures are dominated by elongated, fibrous, and blocky calcites. Successive fracturing and layering of calcite with sharp contacts are traceable along the fluid inclusion bands occurring parallel to the wall rock boundary. In particular, inclusion trails aligned perpendicular to the wall-rock and calcite crystal elongation give information about the vein dilation (crack opening) vector and growth direction. High-resolution U-series dating (11-272 ka BP) and geochemical compositions of the vein and breccia samples were used to investigate the long-term behaviour as well as the general identity of the CO2-bearing fluids within deformed crust. The seismic nature of calcite veining is further assessed by stable isotopic ratio (δ18O and δ13C) plots against vein depths (distance from the wall-rock). The average δ18OPDBvalue for Kumlubük veins is -3.79o, while Amos has an average value of -4.05o. Similarly, average carbon isotope ratio (-8.30o) of the Kumlubük veins is slightly higher than that is observed for the Amos veins (-9.66o). Isotopic compositions are interpreted to reflect cyclic (or episodic) CO2 variations. This suggests the presence of several fluid sources and mechanisms (e.g. luid-rock interaction) indicating the significance of pressure and temperature controls on the evolution of the CO2-bearing fluid system. Sr-isotope ratios (87Sr/86Sr: 0.7082-0.7085) in combination with REE compositions are used to trace fluid sources. REE data of the veins from both regions show typical seawater signatures with distinct negative Ce and positive Y anomalies, which corresponds well with the REE composition of the host limestone. While majority of the samples show similar PAAS-normalised REE variations, some of the veins further display positive Eu anomalies, which could be indicative of contribution from a deeply derived, hot, and reduced fluid component.

A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science

USGS Publications Warehouse

Coplen, Tyler B.; Qi, Haiping

2016-01-01

The hydrogen isotopic composition (δ2HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)–SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ2HVSMOW-SLAPresults when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ2HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised:where mUr = 0.001 = ‰. On average, these revised δ2HVSMOW-SLAP values are 5.7 mUr more positive than those previously measured. It is critical that readers pay attention to the δ2HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ2HVSMOW–SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale.

A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science.

PubMed

Coplen, Tyler B; Qi, Haiping

2016-09-01

The hydrogen isotopic composition (δ(2)HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)-SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ(2)HVSMOW-SLAP results when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ(2)HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised: [Formula: see text] [Formula: see text] where mUr=0.001=‰. On average, these revised δ(2)HVSMOW-SLAP values are 5.7mUr more positive than those previously measured. It is critical that readers pay attention to the δ(2)HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ(2)HVSMOW-SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale. Published by Elsevier Ireland Ltd.

Regulation of Isotopic Composition of Water - way of Improvement of Cosmonauts Drinking Water Functional Properties

NASA Astrophysics Data System (ADS)

Kulikova, Ekaterina; Utina, Dina; Vorozhtsova, Svetlana; Severyuhin, Yuri; Abrosimova, Anna; Sinyak, Yuri; Ivanov, Alexander

The problem in providing drinking water to cosmonauts is solved - at this moment there is a task to improve the functional properties of the water. One of the perspectives of this trend is the use of light isotopic water. The animal studies have shown that long-term consumption of water with a depletion of deuterium and oxygen heavy isotopes accelerates the rise of mass non-irradiated mice, the phase fluctuations reducing or increasing hematological parameters were having adaptive nature. These fluctuations didn’t overcome values beyond the physiological norm of this type of animal. It is established that the therapeutic use of light isotopic water with 35 - 90 ppm in deuterium increases the survival of irradiated mice by an average of 30%, contributes to the preservation of irradiated animals body weight. Treatment of acute radiation sickness with light isotopic water stimulates hematopoietic recovery. At the same time, keeping mice drinking light isotopic water for 7 - 8 days before the irradiation (from 4 to 8.5 Gr) has no effect on the level of radio resistance. Longer keeping mice on light isotopic water, for 14 -21 days - reduction in life expectancy, animal mass, bone marrow cellularity and the level of white blood cells in irradiated animals is noted. It was established that keeping mice on light isotopic water for 14 days before exposure in experimental animals causes an increase in the mitotic index and the frequency of formation of aberrant mitosis after 24 hours of Co(60) gamma radiation in doses of 1 , 2, and 4 Gr. Thus, it is clear that the regulation of the isotopic composition of drinking water - way to improve its functional properties.

Carbon and nitrogen isotopes unravels sources of aerosol contamination at Caribbean rural and urban coastal sites.

PubMed

Morera-Gómez, Yasser; Santamaría, Jesús Miguel; Elustondo, David; Alonso-Hernández, Carlos Manuel; Widory, David

2018-06-15

The constant increase of anthropogenic emissions of aerosols, usually resulting from a complex mixture from various sources, leads to a deterioration of the ambient air quality. The stable isotope compositions (δ 13 C and δ 15 N) of total carbon (TC) and nitrogen (TN) in both PM 10 and emissions from potential sources were investigated for first time in a rural and an urban Caribbean costal sites in Cuba to better constrain the origin of the contamination. Emissions from road traffic, power plant and shipping emissions were discriminated by coupling their C and N contents and corresponding isotope signatures. Other sources (soil, road dust and cement plant), in contrast, presented large overlapping ranges for both C and N isotope compositions. δ 13 C PM10 isotope compositions in the rural (average of -25.4 ± 1.2‰) and urban (average of -24.8 ± 1.2‰) sites were interpreted as a mixture of contributions from two main contributors: i) fossil fuel combustion and ii) cement plant and quarries. Results also showed that this last source is impacting more air quality at the urban site. A strong influence from local wood burning was also identified at the rural site. These conclusions were comforted by a statistical analysis using a conditional bivariate probability function. TN and δ 15 N values from the urban site demonstrated that nitrogen in PM 10 was generated by secondary processes through the formation of (NH 4 ) 2 SO 4 . The exchange in the (NH 4 ) 2 SO 4 molecule between gaseous NH 3 and particle NH 4 + under stoichiometric equilibrium may control the observed 15 N enrichment. At low nitrogen concentrations in the aerosols, representing PM 10 with both the highest primary N and lowest secondary N proportions, comparison with the δ 15 N of potential sources indicate that emissions from diesel car and power plant emissions may represent the major vectors of primary nitrogen. Copyright © 2018 Elsevier B.V. All rights reserved.

Production waters associated with the Ferron coalbed methane fields, central Utah: Chemical and isotopic composition and volumes

USGS Publications Warehouse

Rice, C.A.

2003-01-01

This study investigated the composition of water co-produced with coalbed methane (CBM) from the Upper Cretaceous Ferron Sandstone Member of the Mancos Shale in east-central Utah to better understand coalbed methane reservoirs. The Ferron coalbed methane play currently has more than 600 wells producing an average of 240 bbl/day/well water. Water samples collected from 28 wellheads in three fields (Buzzards Bench, Drunkards Wash, and Helper State) of the northeast-southwest trending play were analyzed for chemical and stable isotopic composition.Water produced from coalbed methane wells is a Na-Cl-HCO3 type. Water from the Drunkards Wash field has the lowest total dissolved solids (TDS) (6300 mg/l) increasing in value to the southeast and northeast. In the Helper State field, about 6 miles northeast, water has the highest total dissolved solids (43,000 mg/l), and major ion abundance indicates the possible influence of evaporite dissolution or mixing with a saline brine. In the southern Buzzards Bench field, water has variable total dissolved solids that are not correlated with depth or spatial distance. Significant differences in the relative compositions are present between the three fields implying varying origins of solutes and/or different water-rock interactions along multiple flow paths.Stable isotopic values of water from the Ferron range from +0.9??? to -11.4??? ?? 18O and -32??? to -90??? ?? 2H and plot below the global meteoric water line (GMWL) on a line near, but above values of present-day meteoric water. Isotopic values of Ferron water are consistent with modification of meteoric water along a flow path by mixing with an evolved seawater brine and/or interaction with carbonate minerals. Analysis of isotopic values versus chloride (conservative element) and total dissolved solids concentrations indicates that recharge water in the Buzzards Bench area is distinct from recharge water in Drunkards Wash and is about 3 ??C warmer. These variations in isotopes along with compositional variations imply that the Ferron reservoir is heterogeneous and compartmentalized, and that multiple flow paths may exist. ?? 2003 Published by Elsevier B.V. All rights reserved.

Evaluating the influence of chemical weathering on the composition of the continental crust using lithium and its isotopes

NASA Astrophysics Data System (ADS)

Rudnick, R. L.; Liu, X.

2011-12-01

The continental crust has an "intermediate" bulk composition that is distinct from primary melts of peridotitic mantle (basalt or picrite). This mismatch between the "building blocks" and the "edifice" of the continental crust points to the operation of processes that preferentially remove mafic to ultramafic material from the continents. Such processes include lower crustal recycling (via density foundering or lower crustal subduction - e.g., relamination, Hacker et al., 2011, EPSL), generation of evolved melts via slab melting, and/or chemical weathering. Stable isotope systems document the influence of chemical weathering on the bulk crust composition: the oxygen isotope composition of the bulk crust is distinctly heavier than that of primary, mantle-derived melts (Simon and Lecuyer, 2005, G-cubed) and the Li isotopic composition of the bulk crust is distinctly lighter than that of mantle-derive melts (Teng et al., 2004, GCA; 2008, Chem. Geol.). Both signatures mark the imprint of chemical weathering on the bulk crust composition. Here, we use a simple mass balance model for lithium inputs and outputs from the continental crust to quantify the mass lost due to chemical weathering. We find that a minimum of 15%, a maximum of 60%, and a best estimate of ~40% of the original juvenile rock mass may have been lost via chemical weathering. The accumulated percentage of mass loss due to chemical weathering leads to an average global chemical weathering rate (CWR) of ~ 8×10^9 to 2×10^10 t/yr since 3.5 Ga, which is about an order of magnitude higher than the minimum estimates based on modern rivers (Gaillardet et al., 1999, Chem. Geol.). While we cannot constrain the exact portion of crustal mass loss via chemical weathering, given the uncertainties of the calculation, we can demonstrate that the weathering flux is non-zero. Therefore, chemical weathering must play a role in the evolution of the composition and mass of the continental crust.

Cloud water in windward and leeward mountain forests: The stable isotope signature of orographic cloud water

USGS Publications Warehouse

Scholl, M.A.; Giambelluca, T.W.; Gingerich, S.B.; Nullet, M.A.; Loope, L.L.

2007-01-01

Cloud water can be a significant hydrologic input to mountain forests. Because it is a precipitation source that is vulnerable to climate change, it is important to quantify amounts of cloud water input at watershed and regional scales. During this study, cloud water and rain samples were collected monthly for 2 years at sites on windward and leeward East Maui. The difference in isotopic composition between volume‐weighted average cloud water and rain samples was 1.4‰ δ18O and 12‰ δ2H for the windward site and 2.8‰ δ18O and 25‰ δ2H for the leeward site, with the cloud water samples enriched in 18O and 2H relative to the rain samples. A summary of previous literature shows that fog and/or cloud water is enriched in 18O and 2H compared to rain at many locations around the world; this study documents cloud water and rain isotopic composition resulting from weather patterns common to montane environments in the trade wind latitudes. An end‐member isotopic composition for cloud water was identified for each site and was used in an isotopic mixing model to estimate the proportion of precipitation input from orographic clouds. Orographic cloud water input was 37% of the total precipitation at the windward site and 46% at the leeward site. This represents an estimate of water input to the forest that could be altered by changes in cloud base altitude resulting from global climate change or deforestation.

The variation of molybdenum isotopes within the weathering system of the black shales

NASA Astrophysics Data System (ADS)

Jianming, Z.

2016-12-01

Jian-Ming Zhu 1,2, De-Can Tan 2, Liang Liang 2, Wang Jing21 State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing, 100083, China 2 State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang, 550002, China Molybdenum (Mo) stable isotopes have been developed as a tracer to indicate the evolution of the atmospheric and oceanic oxygenation related with continent weathering, and to reveal the extent of ancient oceanic euxinia. Molybdenum isotopic variation within the weathering system of basalts has been studied, and was presented the whole trend with heavier isotopes preferentially removed during weathering processes. However, there are few researches to study the variation of Mo isotopes during black shale weathering, especiall on the behavoir of Mo isotopes within the perfect shales' profiles. Here, the weathering profiles of Mo and selenium(Se)-rich carbonaceous rocks in Enshi southwest Hubei Province were selected. The Mo isotopes was measured on Nu Plasma II's MC-ICP-MS using 97Mo-100Mo double spike, and δ98/95Mo was reported relative to NIST 3134. A comprehensive set of Mo isotopic composition and concentration data from the unweathered, weakly and intensely weathered rocks were collected. The δ98/95Mo in fresh shales (220±248 mg/kg Mo, 1SD, n=41) from Shadi and Yutangba drill cores varies from 0.41‰ to 0.99‰ with an average of 0.67±0.16‰, while the strongly weathered shales (19.9±5.8 mg/kg Mo, 1SD, n=5) from Shadi profiles are isotopically heavier with average δ98/95Mo values of 1.03±0.10‰ (1SD, n=5). The Locally altered shales exposed in a quarry at Yutangba are highly enriched in Mo, varing from 31 to 2377 mg/kg with an average of 428 ±605mg/kg (1SD, n=24), approximately 2 times greater than that in fresh shales samples. These rocks are presented a significant variation in δ98/95Mo values varing from -0.24 ‰ to -3.99 ‰ with average -1.67±1.57‰, showing the extremely negative δ98/95Mo values existed in natural samples. This suggested that Mo isotopes can be fractionated during shales weathering processes, with lighter isotopes preferentially removed. This finding is in contrast to the previous knowledge from basalt weathering, and requires further study.

Radioelements and their occurrence with secondary minerals in heated and unheated tuff at the Nevada Test Site

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

Flexser, S.; Wollenberg, H.A.

1992-06-01

Samples of devitrified welded tuff near and away from the site of a heater test in Rainier Mesa were examined with regard to whole-rock radioelement abundances, microscopic distribution of U, and oxygen isotope ratios. Wholerock U averages between 4 and 5 ppM, and U is concentrated at higher levels secondary opaque minerals as well as in accessory grains. U in primary and secondary sites is most commonly associated with Mn phases, which average {approximately}30 ppM U in more uraniferous occurrences. This average is consistent and apparently unaffected by proximity to the heater. The Mn phases differ compositionally from Mn mineralsmore » in other NTS tuffs, usually containing abundant Fe, Ti, and sometimes Ce, and are often poorly crystalline. Oxygen isotope ratios show some depletion in {delta}{sup 18}O in tuff samples very close to the heater; this depletion is consistent with isotopic exchange between the tuff and interstitial water, but it may also reflect original heterogeneity in isotopic ratios of the tuff unrelated to the heater test. Seismic properties of several tuff samples were measured. Significant differences correlating with distance from the heater occur in P- and S-wave amplitudes; these may be due to loss of bound water. Seismic velocities are nearly constant and indicate a lack of significant microcracking. The absence of clearer signs of heater-induced U mobilization or isotopic variations may be due to the short duration of the heater test, and to insufficient definition of pre-heater-test heterogeneities in the tuff.« less

The isotopic composition of authigenic chromium in anoxic marine sediments: A case study from the Cariaco Basin

NASA Astrophysics Data System (ADS)

Reinhard, Christopher T.; Planavsky, Noah J.; Wang, Xiangli; Fischer, Woodward W.; Johnson, Thomas M.; Lyons, Timothy W.

2014-12-01

Chromium (Cr) isotopes are an emerging proxy for tracking redox processes at the Earth's surface. However, there has been limited exploration of the Cr isotope record of modern and recent marine sediments. The basic inorganic chemistry of Cr suggests that anoxic marine basins should factor prominently in the global Cr cycle and that sediments deposited within anoxic basins may offer a valuable Cr isotope archive throughout Earth's history. Here, we present δ53Cr data from sediments of the Cariaco Basin, Venezuela-a 'type' environment for large, perennially anoxic basins with a relatively strong hydrological connection to the global oceans. We document a marked positive shift in bulk δ53Cr values following the termination of the Last Glacial Maximum, followed by relative stasis. Based on a suite of independent redox proxies, this transition marks a switch from oxic to persistently anoxic and sulfidic (euxinic) depositional conditions within the basin. We find good agreement between two independent approaches toward estimating the δ53Cr composition of authigenic Cr in euxinic Cariaco Basin sediments and that these estimates are very similar to the δ53Cr composition of modern open Atlantic Ocean seawater. These data, together with considerations of reaction kinetics and mass balance within the Cariaco Basin, are consistent with the hypothesis that anoxic marine settings can serve as a chemical archive of first-order trends in seawater δ53Cr composition. Additionally, the Cariaco Basin data suggest that there has been secular stability in the average δ53Cr value of Atlantic seawater over the last ∼15 kyr.

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.

Using Stable Isotope Geochemistry to Determine Changing Paleohydrology and Diagenetic Alteration in the Late Cretaceous Kaiparowits Formation, UT USA

NASA Astrophysics Data System (ADS)

Yamamura, Daigo

The Western Interior Basin of the North America preserves one of the best sedimentary and paleontological records of the Cretaceous in the world. The Upper Cretaceous Kaiparowits Formation is a rapidly deposited fluvial sequence and preserves one of the most complete terrestrial fossil record of the North America. Such a unique deposit provides an opportunity to investigate the interaction between the physical environment and ecology. In an effort to decipher such interaction, stable isotope composition of cements in sedimentary rocks, concretions and vertebrate fossils were analyzed. Despite the difference in facies and sedimentary architecture, the isotope composition does not change significantly at 110 m from the base of the formation. Among the well-preserved cement samples, stable isotope composition indicates a significant hydrologic change within the informal Middle unit; a 6.37‰ depletion in delta13C and 3.30‰ enrichment in delta 18O occurs at 300 m above the base of the formation. The isotope values indicate that the sandstone cements below 300 m were precipitated in a mixing zone between marine and terrestrial groundwater, whereas the cements in upper units were precipitated in a terrestrial groundwater. Despite the difference in physical appearance (i.e. color and shape), the isotopic compositions of cements in concretions are similar to well-cemented sandstone bodies in similar stratigraphic positions. Isotope compositions of the host rock are similar to that of mudrock and weathered sandstone, suggesting the origin of cementing fluids for the sandstone and concretions were the same indicating that: 1) the concretions were formed in shallow groundwater and not related to the groundwater migration, or 2) all cements in upper Kaiparowits Formation are precipitated or altered during later stage groundwater migration. Average delta18Oc from each taxon show the same trend as the delta18Op stratigraphic change, suggesting delta18Oc is still useful as a paleoclimatic proxy. Compared to other Campanian formations, fossil delta18O p are depleted for their paleolatitude, suggesting the Kaiparowits Plateau had higher input from high-elevation runoff, consistent with other paleoclimatic studies. Estimated delta18Ow ranged between vadose influenced dry season values of -8.88‰ to high elevation runoff values of -13.76‰ suggesting dynamic hydrologic interactions.

The O and H stable isotope composition of freshwaters in the British Isles. 2. Surface waters and groundwater

NASA Astrophysics Data System (ADS)

Darling, W. G.; Bath, A. H.; Talbot, J. C.

The utility of stable isotopes as tracers of the water molecule has a long pedigree. The study reported here is part of an attempt to establish a comprehensive isotopic "baseline" for the British Isles as background data for a range of applications. Part 1 of this study (Darling and Talbot, 2003) considered the isotopic composition of rainfall in Britain and Ireland. The present paper is concerned with the composition of surface waters and groundwater. In isotopic terms, surface waters (other than some upland streams) are poorly characterised in the British Isles; their potential variability has yet to be widely used as an aid in hydrological research. In what may be the first study of a major British river, a monthly isotopic record of the upper River Thames during 1998 was obtained. This shows high damping of the isotopic variation compared to that in rainfall over most of the year, though significant fluctuations were seen for the autumn months. Smaller rivers such as the Stour and Darent show a more subdued response to the balance between runoff and baseflow. The relationship between the isotopic composition of rainfall and groundwater is also considered. From a limited database, it appears that whereas Chalk groundwater is a representative mixture of weighted average annual rainfall, for Triassic sandstone groundwater there is a seasonal selection of rainfall biased towards isotopically-depleted winter recharge. This may be primarily the result of physical differences between the infiltration characteristics of rock types, though other factors (vegetation, glacial history) could be involved. In the main, however, groundwaters appear to be representative of bulk rainfall within an error band of 0.5‰ δ18O. Contour maps of the δ18O and δ2H content of recent groundwaters in the British Isles show a fundamental SW-NE depletion effect modified by topography. The range of measured values, while much smaller than those for rainfall, still covers some ‰ for δ18O and 30‰ for δ2H. Over lowland areas the "altitude effect" is of little significance, but in upland areas is consistent with a range of -0.2 to -0.3‰ per 100 m increase in altitude. Groundwaters dating from the late Pleistocene are usually modified in δ18O and δ2H owing to the effects of climate change on the isotopic composition of rainfall and thus of recharge. Contour maps of isotopic variability prior to 10 ka BP, based on the relatively limited information available from the British Isles, allow a first comparison between groundwaters now and at the end of the last Ice Age. The position of the British Isles in the context of the stable isotope systematics of NW Europe is reviewed briefly.

[Study on the content and carbon isotopic composition of water dissolved inorganic carbon from rivers around Xi'an City].

PubMed

Guo, Wei; Li, Xiang-Zhong; Liu, Wei-Guo

2013-04-01

In this study, the content and isotopic compositions of water dissolved inorganic carbon (DIC) from four typical rivers (Chanhe, Bahe, Laohe and Heihe) around Xi'an City were studied to trace the possible sources of DIC. The results of this study showed that the content of DIC in the four rivers varied from 0.34 to 5.66 mmol x L(-1) with an average value of 1.23 mmol x L(-1). In general, the content of DIC increased from the headstream to the river mouth. The delta13C(DIC) of four rivers ranged from -13.3 per thousand to -7.2 per thousand, with an average value of -10.1 per thousand. The delta13C(DIC) values of river water were all negative (average value of -12.6 per thousand) at the headstream of four rivers, but the delta13C(DIC) values of downstream water were more positive (with an average value of -9.4 per thousand). In addition, delta13C(DIC) of river water showed relatively negative values (the average value of delta13C(DIC) was -10.5 per thousand) near the estuary of the rivers. The variation of the DIC content and its carbon isotope suggested that the DIC sources of the rivers varied from the headstream to the river mouth. The negative delta13C(DIC) value indicated that the DIC may originate from the soil CO2 at the headstream of the rivers. On the other hand, the delta13C(DIC) values of river water at the middle and lower reaches of rivers were more positive, and it showed that soil CO2 produced by respiration of the C4 plants (like corn) and soil carbonates with positive delta13C values may be imported into river water. Meanwhile, the input of pollutants with low delta13C(DIC) values may result in a decrease of delta13C(DIC) values in the rivers. The study indicated that the DIC content and carbon isotope may be used to trace the sources of DIC in rivers around Xi'an City. Our study may provide some basic information for tracing the sources of DIC of rivers in the small watershed area in the Loess Plateau of China.

The use of Stable Isotopes to Assess Climatic Controls on Groundwater Recharge in the Southern Sacramento Mountains, New Mexico

NASA Astrophysics Data System (ADS)

Newton, B. T.; Timmons, S. S.; Rawling, G. C.; Kludt, T.; Eastoe, C. J.

2008-12-01

We used the stable isotopes of hydrogen and oxygen to relate the temporal variability of groundwater recharge to climatic conditions in the southern Sacramento Mountains as a part of a larger regional hydrogeologic study. The southern Sacramento Mountains are the primary recharge source not only to local aquifers, but also to the Lower Pecos River Basin, the Roswell Artesian aquifer and aquifers in the Salt Basin. Aquifers in the study area mainly consist of fractured limestone. In years prior to 2006, groundwater levels within the study area showed a steady decline. We observed a significant increase in regional groundwater levels and spring discharge during and shortly after the unusually wet 2006 monsoon season. We developed a local meteoric water line (LMWL) in δ18O vs. δD space based on precipitation samples collected from several different elevations over a period of two years. The stable isotopic compositions of streams during base flow conditions define an evaporation line with a slope of 5.5 that intersects the LMWL in the region that represents winter precipitation. Spring and well samples collected in 2003 and spring samples collected in 2008 exhibit isotopic compositions that plot near the evaporation line, indicating that groundwater recharge is largely snow melt that has subsequently undergone evaporation in local streams. After the unusually wet 2006 monsoon season, the isotopic compositions of springs sampled in fall of 2006 and wells sampled in spring of 2007 deviated from the evaporation line, plotting closer to the LMWL. This observed isotopic trend is thought to represent a large input of 2006 monsoon precipitation to the groundwater system via relatively short fracture-dominated flow paths. Stable isotope results indicate that while snow melt is probably the main source of groundwater recharge in the southern Sacramento Mountains, as exhibited by the 2003 and 2008 samples, above average summer precipitation events, such as in 2006, can also contribute to significant groundwater recharge.

First on-line isotopic characterization of N2O above intensively managed grassland

NASA Astrophysics Data System (ADS)

Wolf, B.; Merbold, L.; Decock, C.; Tuzson, B.; Harris, E.; Six, J.; Emmenegger, L.; Mohn, J.

2015-04-01

The analysis of the four main isotopic N2O species (14N14N16O, 14N15N16O, 15N14N16O, 14N14N18O) and especially the intramolecular distribution of 15N ("site preference", SP) has been suggested as a tool to distinguish source processes and to help constrain the global N2O budget. However, current studies suffer from limited spatial and temporal resolution capabilities due to the combination of discrete flask sampling with subsequent laboratory-based mass-spectrometric analysis. Quantum cascade laser absorption spectroscopy (QCLAS) allows the selective high-precision analysis of N2O isotopic species at trace levels and is suitable for in situ measurements. Here, we present results from the first field campaign, conducted on an intensively managed grassland site in central Switzerland. N2O mole fractions and isotopic composition were determined in the atmospheric surface layer (at 2.2 m height) at a high temporal resolution with a modified state-of-the-art laser spectrometer connected to an automated N2O preconcentration unit. The analytical performance was determined from repeated measurements of a compressed air tank and resulted in measurement repeatability of 0.20, 0.12 and 0.11‰ for δ15Nα, δ15Nβ and δ18O, respectively. Simultaneous eddy-covariance N2O flux measurements were used to determine the flux-averaged isotopic signature of soil-emitted N2O. Our measurements indicate that, in general, nitrifier-denitrification and denitrification were the prevalent sources of N2O during the campaign and that variations in isotopic composition were due to alterations in the extent to which N2O was reduced to N2 rather than to other pathways, such as hydroxylamine oxidation. Management and rewetting events were characterized by low values of the intramolecular 15N site preference (SP), δ15Nbulk and δ18O, suggesting that nitrifier-denitrification and incomplete heterotrophic bacterial denitrification responded most strongly to the induced disturbances. The flux-averaged isotopic composition of N2O from intensively managed grassland was 6.9 ± 4.3, -17.4 ± 6.2 and 27.4 ± 3.6‰ for SP, δ15Nbulk and δ18O, respectively. The approach presented here is capable of providing long-term data sets also for other N2O-emitting ecosystems, which can be used to further constrain global N2O inventories.

First on-line isotopic characterization of N2O emitted from intensively managed grassland

NASA Astrophysics Data System (ADS)

Wolf, B.; Merbold, L.; Decock, C.; Tuzson, B.; Harris, E.; Six, J.; Emmenegger, L.; Mohn, J.

2015-01-01

The analysis of the four main isotopic N2O species (14N14N16O, 14N15N16O, 15N14N16O, 14N14N18O) and especially the intramolecular distribution of 15N (site preference, SP) has been suggested as a tool to distinguish source processes and to help constrain the global N2O budget. However, current studies suffer from limited spatial and temporal resolution capabilities due to the combination of discrete flask sampling with subsequent laboratory-based mass spectrometric analysis. Quantum cascade laser absorption spectroscopy (QCLAS) allows selective high-precision analysis of N2O isotopic species at trace levels and is suitable for in situ measurements. Here, we present results from the first field campaign, conducted on an intensively managed grassland in central Switzerland. N2O mole fractions and isotopic composition were determined in the atmospheric surface layer (2 m height) at high temporal resolution with a modified state-of-the-art laser spectrometer connected to an automated N2O preconcentration unit. The analytical performance was determined from repeated measurements of a compressed air tank and resulted in measurement repeatability of 0.20, 0.12 and 0.11‰ for δ15Nα, δ15Nβ and δ18O, respectively. Simultaneous eddy-covariance N2O flux measurements were used to determine the flux-averaged isotopic signature of soil-emitted N2O. Our measurements indicate that in general, nitrifier-denitrification and denitrification were the prevalent sources of N2O during the campaign, and that variations in isotopic composition were rather due to alterations in the extent to which N2O was reduced to N2, than other pathways such as hydroxylamine oxidation. Management and rewetting events were characterized by low values of the intra-molecular 15N site preference (SP), δ15Nbulk and δ18O, suggesting nitrifier denitrification and incomplete heterotrophic bacterial denitrification responded most strongly to the induced disturbances. Flux-averaged isotopic composition of N2O from intensively managed grassland was 6.9 ± 4.3, -17.4 ± 6.2 and 27.4 ± 3.6‰ for SP, δ15Nbulk and δ18O, respectively. The approach presented here is capable of providing long-term datasets also for other N2O emitting ecosystems, which can be used to further constrain global N2O inventories.

Non-zero Δ33S preserved in rocks from the Basal Ultramafic Sequence indicate crustal contamination in the most primitive magma of the Rustenburg Layered Suite (Bushveld Complex, South Africa)

NASA Astrophysics Data System (ADS)

Magalhaes, N.; Wilson, A.; Penniston-Dorland, S.; Farquhar, J.

2017-12-01

The sulfur isotope composition of the Rustenburg Layered Suite (RLS) of the Bushveld Complex is different than expected from a magma sourced from the mantle (Δ33S=0), as measurements indicate the presence of an Archean surface-derived sulfur component. The Basal Ultramafic Sequence (BUS) is thought to be the most primitive magma of the RLS, as it is the lowest in the stratigraphy, has the highest Mg# (>0.92) for primary phases (olivine and orthopyroxene), and is in direct contact with the Magaliesberg quartzite of the Pretoria Group.We have measured the composition of sulfides in rocks from the Lower Zone, Marginal Zone, and the BUS, which were sampled in a 2300m drill core from the Clapham area, in the eastern Bushveld Complex. While the rocks of the Lower Zone have a relatively homogeneous non-zero Δ33S of 0.065‰, comparable to previous findings, there is an abrupt increase in the value of Δ33S (up to +0.301‰) in the Marginal Zone, which may be consistent with the observation in hand sample of assimilation of country rocks. The BUS also shows a surface-derived signal (average of 0.040‰), which is the lowest measured for any zone of the RLS.The non-zero Δ33S found in the Basal Ultramafic Sequence is evidence of the contamination of the magma with surface-derived material. In the upper parts of the intrusion, the Δ33S signature relates to whole-rock Sr and Nd isotopes, and their relationship suggests multiple sources of contamination. However, the relationship between sulfur and in-situ strontium isotope compositions (plagioclase) in this section of the RLS is not as clear as it is further up in the stratigraphy. This might reflect small-scale processes during the magmatic chamber stage, different compositions of local wall rock compared to deeper contaminants, or the presence of decoupled behavior between the isotope systems.These differences in the sulfur isotope composition between the different stratigraphic layers have been preserved regardless of any late magmatic processes that may have occurred, which further supports that the sulfur isotope composition of the RLS was not fully homogenized at a later stage by fluid migration.

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

New stable isotope results for reservoir and above zone monitoring in CCS from the Ketzin pilot site, Germany

NASA Astrophysics Data System (ADS)

Nowak, Martin; van Geldern, Robert; Myrttinen, Anssi; Veith, Becker; Zimmer, Martin; Barth, Johannes

2013-04-01

With rising atmospheric greenhouse gas concentrations, CCS technologies are a feasible option to diminish consequences of uncontrolled anthropogenic CO2 emissions and related climate change. However, application of CCS technologies requires appropriate and routine monitoring tools in order to ensure a safe and effective CO2 injection. Stable isotope techniques have proven as a useful geochemical monitoring tool at several CCS pilot projects worldwide. They can provide important information about gas - water - rock interactions, mass balances and CO2 migration in the reservoir and may serve as a tool to detect CO2 leakage in the subsurface and surface. Since the beginning of injection in 2008 at the Ketzin pilot site in Germany, more than 450 samples of fluids and gases have been analysed for their carbon and oxygen isotopic composition. Analytical advancements were achieved by modifying a conventional isotope ratio mass-spectrometer with a He dilution system. This allowed analyses of a larger number of CO2 gas samples from the injection well and observation wells. With this, a high-resolution monitoring program was established over a time period of one year. Results revealed that two isotopical distinct kinds of CO2 are injected at the Ketzin pilot site. The most commonly injected CO2 is so-called 'technical' CO2 with an average carbon isotopic value of about -31 ‰. Sporadically, natural source CO2 with an average δ13C value of -3 ‰ was injected. The injection of natural source CO2 generated a distinct isotope signal at the injection well that can be used as an ideal tracer. CO2 isotope values analysed at the observation wells indicate a highly dispersive migration of the supercritical CO2 that results in mixing of the two kinds of CO2 within the reservoir. Above-reservoir monitoring includes the first overlying aquifer above the cap rock. An observation well within this zone comprises an U-tube sampling device that allows frequent sampling of unaltered brine. The fluids were analysed among others for their carbon isotopic compositions of dissolved inorganic carbon (DIC). δ13CDIC values allowed to assess impacts of the carbonate-based drilling fluid during well development and helped to monitor successive geochemical re-equilibration processes of the brine. Based on the determined δ13C baseline values of the aquifer fluid, first concepts indicate the scale of change of the δ13CDIC values that would be necessary to detect CO2 leakage from the underlying storage reservoir. Recent efforts aim at applications of new laser-based isotope sensors that allow online measurements in the field. These devices are applied for CO2 gas tracer experiments as well as for monitoring of isotope composition of soil gases in the vicinity of the pilot site. This new development will allow much better temporal and spatial resolution of measurements at a lower price. Therefore, stable isotope analyses can become a strong and promising tool for subsurface as well as surface monitoring at future CCS sites.

Zinc isotope fractionation during mantle melting and constraints on the Zn isotope composition of Earth's upper mantle

NASA Astrophysics Data System (ADS)

Wang, Ze-Zhou; Liu, Sheng-Ao; Liu, Jingao; Huang, Jian; Xiao, Yan; Chu, Zhu-Yin; Zhao, Xin-Miao; Tang, Limei

2017-02-01

The zinc (Zn) stable isotope system has great potential for tracing planetary formation and differentiation processes due to its chalcophile, lithophile and moderately volatile character. As an initial approach, the terrestrial mantle, and by inference, the bulk silicate Earth (BSE), have previously been suggested to have an average δ66Zn value of ∼+0.28‰ (relative to JMC 3-0749L) primarily based on oceanic basalts. Nevertheless, data for mantle peridotites are relatively scarce and it remains unclear whether Zn isotopes are fractionated during mantle melting. To address this issue, we report high-precision (±0.04‰; 2SD) Zn isotope data for well-characterized peridotites (n = 47) from cratonic and orogenic settings, as well as their mineral separates. Basalts including mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) were also measured to avoid inter-laboratory bias. The MORB analyzed have homogeneous δ66Zn values of +0.28 ± 0.03‰ (here and throughout the text, errors are given as 2SD), similar to those of OIB obtained in this study and in the literature (+0.31 ± 0.09‰). Excluding the metasomatized peridotites that exhibit a wide δ66Zn range of -0.44‰ to +0.42‰, the non-metasomatized peridotites have relatively uniform δ66Zn value of +0.18 ± 0.06‰, which is lighter than both MORB and OIB. This difference suggests a small but detectable Zn isotope fractionation (∼0.1‰) during mantle partial melting. The magnitude of inter-mineral fractionation between olivine and pyroxene is, on average, close to zero, but spinels are always isotopically heavier than coexisting olivines (Δ66ZnSpl-Ol = +0.12 ± 0.07‰) due to the stiffer Zn-O bonds in spinel than silicate minerals (Ol, Opx and Cpx). Zinc concentrations in spinels are 11-88 times higher than those in silicate minerals, and our modelling suggests that spinel consumption during mantle melting plays a key role in generating high Zn concentrations and heavy Zn isotopic compositions of MORB. Therefore, preferential melting of spinel in the peridotites may account for the Zn isotopic difference between spinel peridotites and basalts. By contrast, the absence of Zn isotope fractionation between silicate minerals suggests that Zn isotopes are not significantly fractionated during partial melting of spinel-free garnet-facies mantle. If the studied non-metasomatized peridotites represent the refractory upper mantle, mass balance calculation shows that the depleted MORB mantle (DMM) has a δ66Zn value of +0.20 ± 0.05‰ (2SD), which is lighter than the primitive upper mantle (PUM) estimated in previous studies (+0.28 ± 0.05‰, 2SD, Chen et al., 2013b; +0.30 ± 0.07‰, 2SD, Doucet et al., 2016). This indicates that the Earth's upper mantle has a heterogeneous Zn isotopic composition vertically, which is probably due to shallow mantle melting processes.

Correcting speleothem oxygen isotopic variations for growth-rate controlled kinetic fractionation effects

NASA Astrophysics Data System (ADS)

Stoll, Heather; Moreno, Ana; Cacho, Isabel; Mendez Vicence, Ana; Gonzalez Lemos, Saul; Pirla Casasayas, Gemma; Cheng, Hai; Wang, Xianfeng; Edwards, R. Lawrence

2015-04-01

The oxygen isotopic signature may be the most widely used climate indicator in stalagmites, but recent experimental and theoretical studies indicate the potential for kinetic fractionation effects which may be significant, especially in situations where the primary signal from rainfall isotopic composition and cave temperature is limited to a few permil. Here we use a natural set of stalagmites to illustrate the magnitude of such effects and the potential for deconvolving kinetic signals from the primary temperature and rainfall signals. We compare isotopic records from 6 coeval stalagmites covering the interval 140 to 70 ka, from two proximal caves in NW Spain which experienced the same primary variations in temperature and rainfall d18O, but exhibit a large range in growth rates and temporal trends in growth rate. Stalagmites growing at faster rates near 50 microns/year have oxygen isotopic ratios more than 1 permil more negative than coeval stalagmites with very slow (5 micron/year) growth rates. Because growth rate variations also occur over time within any given stalagmite, the measured oxygen isotopic time series for a given stalagmite includes both climatic and kinetic components. Removal of the kinetic component of variation in each stalagmite, based on the dependence of the kinetic component on growth rate, is effective at distilling a common temporal evolution among the oxygen isotopic records of the multiple stalagmites. However, this approach is limited by the quality of the age model. For time periods characterized by very slow growth and long durations between dates, the presence of crypto-hiatus may result in average growth rates which underestimate the instantaneous speleothem deposition rates and which therefore underestimate the magnitude of kinetic effects. We compare the composite corrected oxygen isotopic record with other records of the timing of glacial inception in the North Atlantic realm.

Comment on "The shape and composition of interstellar silicate grains"

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

Bradley, J P; Ishii, H

2007-09-27

In the paper entitled 'The shape and composition of interstellar silicate grains' (A & A, 462, 667-676 (2007)), Min et al. explore non-spherical grain shape and composition in modeling the interstellar 10 and 20 {micro}m extinction features. This progression towards more realistic models is vitally important to enabling valid comparisons between dust observations and laboratory measurements. Min et al. proceed to compare their model results with GEMS (glass with embedded metals and sulfides) from IDPs (interplanetary dust particles) and to discuss the nature and origin of GEMS. Specifically, they evaluate the hypothesis of Bradley (1994) that GEMS are interstellar (IS)more » amorphous silicates. From a comparison of the mineralogy, chemical compositions, and infrared (IR) spectral properties of GEMS with their modeling results, Min et al. conclude: 'GEMS are, in general, not unprocessed leftovers from the diffuse ISM'. This conclusion is based, however, on erroneous and incomplete GEMS data. It is important to clarify first that Bradley (1994) never proposed that GEMS are unprocessed leftovers from the diffuse ISM, nor did he suggest that individual subnanogram mass GEMS are a representative sampling of the enormous mass of silicates in the diffuse ISM. Bradley (1994) simply showed that GEMS properties are consistent with those of IS amorphous silicates. It is widely accepted that circumstellar outflows are important sources of IS silicates, and whether GEMS are processed or not, the circumstellar heritage of some has been rigorously confirmed through measurements of non-solar oxygen (O) isotope abundances (Messenger et al., 2003; Floss et al., 2006). Keller et al. (2000) assert that even GEMS without detectable O isotope anomalies are probably also extrasolar IS silicates because they are embedded in carbonaceous material with non-solar D/H isotopic composition. (Much of the silicate dust in the ISM may be isotopically homogenized (Zhukovska et al., 2007)). Recent measurements show that the elemental compositions of GEMS with non-solar isotopic compositions are 'remarkably similar' to those with solar isotopic compositions (Keller & Messenger, 2007). About 80% of all isotopically anomalous IS silicates identified to date are GEMS with detectable and variable O isotopic memories of a circumstellar ancestry (Messenger, 2007). Bradley (1999) proposed that GEMS are IS silicates from 'a presolar interstellar molecular cloud, presumably the local molecular cloud from which the solar system formed'. Although based on incorrect data (detailed below), Min et al. propose that most GEMS actually formed in the presolar molecular cloud, and they further propose that none of them are IS silicates. IS silicate sources include molecular clouds, circumstellar outflows, supernovae, and even recently discovered black hole winds (Molster & Waters; 2003; Jones, 2005; Zhukovska et al. 2007; Markwick-Kemper et al. 2007). The average IS 10 {micro}m extinction feature observed along lines of sight towards the galactic center (modeled by Min et al.) presumably provides a good average for IS silicates, but it cannot distinguish amorphous silicates originating in the presolar molecular cloud from amorphous silicates originating in other interstellar molecular clouds or indeed other sources of amorphous IS silicates. Even if most GEMS accreted in the presolar molecular cloud, then they must also be representatives of some portion of the IS amorphous silicate population. Laboratory heating experiments indicate it is highly unlikely that GEMS were modified in a protoplanetary accretion disk environment (Brownlee et al. 2005). In summary, Min et al. conclude from their modeling of the shape and composition of IS silicates that the properties of GEMS are generally inconsistent with those of IS silicates. First, it has been rigorously confirmed via ion microprobe measurements that some GEMS are indeed presolar IS silicates. Second, regardless of whether GEMS, or components of GEMS, originated in presolar circumstellar outflows or a presolar molecular cloud they are all IS silicates. Third, key GEMS data reported in Min et al. are inaccurate. Had complete isotopic, chemical, mineralogical and infrared (IR) spectral properties of GEMS been considered, Min et al. may have concluded that the properties of GEMS, although not an exact match, are generally consistent with those of amorphous silicates in the ISM.« less

Biogeochemical Mg cycle in the Barton Peninsula, King George Island, West Antarctica

NASA Astrophysics Data System (ADS)

Choi, H. B.; Ryu, J. S.; Lee, J.; Lim, H. S.; Yoon, H.

2016-12-01

Understanding of biogeochemical Mg cycle is important in terms of plant growth as well as global climate because Mg participates in numerous biogeochemical processes. Here, we collected rock, soil, water and moss samples in the Barton peninsula, King George Island, West Antarctica, and measured their elemental and Mg isotope compositions in order to quantify and understand the biogeochemical processes of the Mg cycle. Elemental results show that the input of seawater derived Mg mainly controls dissolved Mg in meltwater. Mg isotope compositions in rocks and soils are consistent within the error, -0.03 ± 0.15‰ (n=6) and +0.03 ± 0.07‰ (n=8), respectively. However, δ26Mg values of meltwater and moss are -0.69 ± 0.09‰ (n=34) and -0.46 ± 0.19‰ (n=16), respectively, indicating that mosses display higher δ26Mg values compared to meltwater they uptake. This implies an isotope fractionation in favor of heavy isotopes during moss growth. The apparent Mg isotope fractionation between moss and meltwater (Δ26Mgmoss-meltwater) ranges from 0.02‰ to 0.55‰, with an average of +0.29‰ (n=6), which is within the range previously reported during higher plant growth. Our finding suggests that enhanced plant growth in Arctic and Antarctica due to climate change and global warming may play an important role in the biogeochemical Mg cycle globally.

The problem of isotopic baseline: Reconstructing the diet and trophic position of fossil animals

NASA Astrophysics Data System (ADS)

Casey, Michelle M.; Post, David M.

2011-05-01

Stable isotope methods are powerful, frequently used tools which allow diet and trophic position reconstruction of organisms and the tracking of energy sources through ecosystems. The majority of ecosystems have multiple food sources which have distinct carbon and nitrogen isotopic signatures despite occupying a single trophic level. This difference in the starting isotopic composition of primary producers sets up an isotopic baseline that needs to be accounted for when calculating diet or trophic position using stable isotopic methods. This is particularly important when comparing animals from different regions or different times. Failure to do so can cause erroneous estimations of diet or trophic level, especially for organisms with mixed diets. The isotopic baseline is known to vary seasonally and in concert with a host of physical and chemical variables such as mean annual rainfall, soil maturity, and soil pH in terrestrial settings and lake size, depth, and distance from shore in aquatic settings. In the fossil record, the presence of shallowing upward suites of rock, or parasequences, will have a considerable impact on the isotopic baseline as basin size, depth and distance from shore change simultaneously with stratigraphic depth. For this reason, each stratigraphic level is likely to need an independent estimation of baseline even within a single outcrop. Very little is known about the scope of millennial or decadal variation in isotopic baseline. Without multi-year data on the nature of isotopic baseline variation, the impacts of time averaging on our ability to resolve trophic relationships in the fossil record will remain unclear. The use of a time averaged baseline will increase the amount of error surrounding diet and trophic position reconstructions. Where signal to noise ratios are low, due to low end member disparity (e.g., aquatic systems), or where the observed isotopic shift is small (≤ 1‰) the error introduced by time averaging may severely inhibit the scope of one's interpretations and limit the types of questions one can reliably answer. In situations with strong signal strength, resulting from high amounts of end member disparity (e.g., terrestrial settings), this additional error maybe surmountable. Baseline variation that is adequately characterized can be dealt with by applying multiple end-member mixing models.

Constraints on continental crustal mass loss via chemical weathering using lithium and its isotopes

NASA Astrophysics Data System (ADS)

Rudnick, R. L.; Liu, X. M.

2012-04-01

The continental crust has an "intermediate" bulk composition that is distinct from primary melts of peridotitic mantle (basalt or picrite). This mismatch between the "building blocks" and the "edifice" that is the continental crust points to the operation of processes that preferentially remove mafic to ultramafic material from the continents. Such processes include lower crustal recycling (via density foundering or lower crustal subduction - e.g., relamination, Hacker et al., 2011, EPSL), generation of evolved melts via slab melting, and/or chemical weathering. Stable isotope systems point to the influence of chemical weathering on the bulk crust composition: the oxygen isotope composition of the bulk crust is distinctly heavier than that of primary, mantle-derived melts (Simon and Lecuyer, 2005, G-cubed) and the Li isotopic composition of the bulk crust is distinctly lighter than that of mantle-derive melts (Teng et al., 2004, GCA; 2008, Chem. Geol.). Both signatures mark the imprint of chemical weathering on the bulk crust composition. Here, we use a simple mass balance model for lithium inputs and outputs from the continental crust to quantify the mass lost due to chemical weathering. We find that a minimum of 15%, a maximum of 60%, and a best estimate of ~40% of the original juvenile rock mass may have been lost via chemical weathering. The accumulated percentage of mass loss due to chemical weathering leads to an average global chemical weathering rate (CWR) of ~ 1×10^10 to 2×10^10 t/yr since 3.5 Ga, which is about an order of magnitude higher than the minimum estimates based on modern rivers (Gaillardet et al., 1999, Chem. Geol.). While we cannot constrain the exact portion of crustal mass loss via chemical weathering, given the uncertainties of the calculation, we can demonstrate that the weathering flux is non-zero. Therefore, chemical weathering must play a role in the evolution of the composition and mass of the continental crust.

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.

Mapping methane plumes and the delta C-13 composition of anthropogenic sources in southwest Germany

NASA Astrophysics Data System (ADS)

Schmidt, Martina; Yeman, Christiane; Dinger, Florian; Ars, Sebastien; Yver Kwok, Camille

2016-04-01

A mobile analyser based on Cavity-Ring-Down Spectroscopy was installed on a vehicle, together with a GPS receiver. This allows us to measure atmospheric methane and carbon dioxide mole fractions and the C-13 isotopes of both gases while driving. Methane mole fraction measurements show a good repeatability even for high frequency measurements whereas the 13CH4 measurements need a longer averaging time of 1 minute for 1 ‰ repeatability and 15 minutes for 0.23 ‰ repeatability. Driving through an emission plume, the signal is typically only 60 seconds long. To overcome the precision problem for the isotope measurements we filled a 25 m tubing when driving through the plume, which was then flushed back through our analyser during 30 minutes. During several campaigns we visited a land fill site, a biogas plant, a dairy cow farm and a natural gas storage and measured an averaged isotopic methane signature(C-13) of -58.3 ±3 ‰, -62.5 ± 1‰, -62.2 ± 2‰, -51 ± 7‰, respectively.

Impact-induced devolatilization and hydrogen isotopic fractionation of serpentine: Implications for planetary accretion

NASA Technical Reports Server (NTRS)

Tyburczy, James A.; Krishnamurthy, R. V.; Epstein, Samuel; Ahrens, Thomas J.

1988-01-01

Impact-induced devolatilization of porous serpentine was investigated using two independent experimental methods, the gas recovery and the solid recovery method, each yielding nearly identical results. For shock pressures near incipient devolatilization, the hydrogen isotopic composition of the evolved H2O is very close to that of the starting material. For shock pressures at which up to 12 percent impact-induced devolatilization occurs, the bulk evolved gas is significantly lower in deuterium than the starting material. There is also significant reduction of H2O to H2 in gases recovered at these higher shock pressures, probably caused by reaction of evolved H2O with the metal gas recovery fixture. Gaseous H2O-H2 isotopic fractionation suggests high temperature isotopic equilibrium between the gaseous species, indicating initiation of devolatilization at sites of greater than average energy deposition. Bulk gas-residual solid isotopic fractionations indicate nonequilibrium, kinetic control of gas-solid isotopic ratios. Impact-induced hydrogen isotopic fractionation of hydrous silicates during accretion can strongly affect the long-term planetary isotopic ratios of planetary bodies, leaving the interiors enriched in deuterium. Depending on the model used for extrapolation of the isotopic fractionation to devolatilization fractions greater than those investigated experimentally can result from this process.

Real-time analysis of δ13C- and δD-CH4 in ambient air with laser spectroscopy: method development and first intercomparison results

NASA Astrophysics Data System (ADS)

Eyer, S.; Tuzson, B.; Popa, M. E.; van der Veen, C.; Röckmann, T.; Rothe, M.; Brand, W. A.; Fisher, R.; Lowry, D.; Nisbet, E. G.; Brennwald, M. S.; Harris, E.; Zellweger, C.; Emmenegger, L.; Fischer, H.; Mohn, J.

2015-08-01

In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called TRace gas EXtractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, μmole/mole) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. Based on replicate measurements of compressed air during a two-week intercomparison campaign, the repeatability of the TREX-QCLAS was determined to be 0.19 and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass-spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX-QCLAS data and bag/flask sampling-IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. Thus, the intercomparison also reveals the need for reference air samples with accurately determined isotopic composition of CH4 to further improve the interlaboratory compatibility.

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.

The genesis solar-wind sample return mission

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

Wiens, Roger C

2009-01-01

The compositions of the Earth's crust and mantle, and those of the Moon and Mars, are relatively well known both isotopically and elementally. The same is true of our knowledge of the asteroid belt composition, based on meteorite analyses. Remote measurements of Venus, the Jovian atmosphere, and the outer planet moons, have provided some estimates of their compositions. The Sun constitutes a large majority, > 99%, of all the matter in the solar system. The elemental composition of the photosphere, the visible 'surface' of the Sun, is constrained by absorption lines produced by particles above the surface. Abundances for manymore » elements are reported to the {+-}10 or 20% accuracy level. However, the abundances of other important elements, such as neon, cannot be determined in this way due to a relative lack of atomic states at low excitation energies. Additionally and most importantly, the isotopic composition of the Sun cannot be determined astronomically except for a few species which form molecules above sunspots, and estimates derived from these sources lack the accuracy desired for comparison with meteoritic and planetary surface samples measured on the Earth. The solar wind spreads a sample of solar particles throughout the heliosphere, though the sample is very rarified: collecting a nanogram of oxygen, the third most abundant element, in a square centimeter cross section at the Earth's distance from the Sun takes five years. Nevertheless, foil collectors exposed to the solar wind for periods of hours on the surface of the Moon during the Apollo missions were used to determine the helium and neon solar-wind compositions sufficiently to show that the Earth's atmospheric neon was significantly evolved relative to the Sun. Spacecraft instruments developed subsequently have provided many insights into the composition of the solar wind, mostly in terms of elemental composition. These instruments have the advantage of observing a number of parameters simultaneously, including charge state distributions, velocities, and densities, all of which have been instrumental in characterizing the nature of the solar wind. However, these instruments have lacked the ability to make large dynamic range measurements of adjacent isotopes (i.e., {sup 17}O/{sup 16}O {approx} 2500) or provide the permil (tenths of percent) accuracy desirable for comparison with geochemical isotopic measurements. An accurate knowledge of the solar and solar-wind compositions helps to answer important questions across a number of disciplines. It aids in understanding the acceleration mechanisms of the solar wind, gives an improved picture of the charged particle environment near the photosphere, it constrains processes within the Sun over its history, and it provides a database by which to compare differences among planetary systems with the solar system's starting composition, providing key information on planetary evolution. For example, precise knowledge of solar isotopic and elemental compositions of volatile species in the Sun provides a baseline for models of atmospheric evolution over time for Earth, Venus, and Mars. Additionally, volatile and chemically active elements such as C, H, O, N, and S can tell us about processes active during the evolution of the solar nebula. A classic example of this is the oxygen isotope system. In the 1970s it was determined that the oxygen isotopic ratio in refractory inclusions in primitive meteorites was enriched {approx}4% in {sup 16}O relative to the average terrestrial, lunar, and thermally processed meteorite materials. In addition, all processed solar-system materials appeared to each have a unique oxygen isotopic composition (except the Moon and Earth, which are thought to be formed from the same materials), though differences are in the fraction of a percent range, much smaller than the refractory material {sup 16}O enrichment. Several theories were developed over the years to account for the oxygen isotope heterogeneity, each theory predicting a different solar isotopic composition and each invoking a different early solar-system process to produce the heterogeneity. Other volatiles such as C, N, and H may also have experienced similar effects, but with only two isotopes it is often impossible to distinguish with these elements between mass-dependent fractionation and other effects such as mixing or mass-independent fractionation. Table 1 provides a summary of the major measurement objectives of the Genesis mission. Determining the solar oxygen isotopic composition is at the top of the list. Volatile element and isotope ratios constitute six of the top seven priorities. A number of disciplines stand to gain from information from the Genesis mission, as will be discussed later. Based on the Apollo solar-wind foil experiment, the Genesis mission was designed to capture solar wind over orders of magnitude longer duration and in a potentially much cleaner environment than the lunar surface.« less

Origin of isotopically light Zn in lunar samples through vaporization and the Zn isotope composition of the Moon

NASA Astrophysics Data System (ADS)

Kato, C.; Valdes, M. C.; Dhaliwal, J.; Day, J. M.; Moynier, F.

2013-12-01

The origin of the volatile element depletion of the Moon compared to Earth remains a key question in planetary science. It has recently been shown that both high-Ti and low-Ti lunar basalts are enriched in the heavier isotopes of Zn compared to Earth with an effect of ~1.3 permil on the 66Zn/64Zn ratio (Paniello et al., Nature, 2012). In order to obtain a better understanding of Zn behavior in and on the Moon, we present new measurements of lunar basalts, pyroclastic green glass 15426, highland anorthosites, cataclastic dunite 77215, cataclastic norite 72415 and some lunar soils. Samples were analyzed using a Thermo-Fisher Neptune Plus multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) at Washington University in St Louis. The data presented below are reported as the permil deviation of the 66Zn/64Zn ratio from the JMC-Lyon standard (δ66Zn). Four new high Ti basalts and three low Ti basalts confirm the observations of Paniello et al. (2012), that there is an enrichment in the heavier isotopes of Zn compared with chondrites and terrestrial samples. Combining these data together with Paniello et al. (2012) and Herzog et al. (GCA, 2009) we calculate a new average for lunar basalts of δ66Zn= 1.4×0.4 (1sd, n = 27). A few exceptions (5 samples out of 32) are isotopically light and probably represent addition of isotopically light Zn condensed onto the lunar surface from Zn isotopic fractionation during meteoritic impact, creating correspondingly isotopically heavy soils. In contrast to the homogeneity of mare basalts, highland samples show large Zn isotopic variability (δ66Zn -11.4 up to +4.24 permil) which encompasses the entire Zn isotopic variability measured so far in the Solar System. These δ66Zn variations are negatively correlated with the Zn abundance, with the isotopically light samples having the highest Zn concentrations. We interpret these results as the consequence of meteoritic bombardment and volatilization/condensation of Zn at the surface of the Moon. This represents secondary effects and mixing with exogenous Zn, explaining the higher abundance of Zn in highland rocks, relative to mare basalts. The pyroclastic green glass (15426) has a higher measured Zn concentration (~50ppm) compared with mare basalts, but is still depleted in Zn relative to most terrestrial basalts (typically >50 to 100 ppm). 15426 is also isotopically light (δ66Zn= -0.98), which is similar to previous measurements of Zn composition made for high-Ti pyroclastic glass beads (74220). We interpret the composition of the lunar pyroclastic glasses to reflect lava fountaining and coating of the surface of the beads by a volatile rich and isotopically light vapor. Thus, we conclude that mare basalts, which are isotopically heavier than the Earth, best represent the lunar silicate composition.

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.

Lunar basalt chronology, mantle differentiation and implications for determining the age of the Moon

NASA Astrophysics Data System (ADS)

Snape, Joshua F.; Nemchin, Alexander A.; Bellucci, Jeremy J.; Whitehouse, Martin J.; Tartèse, Romain; Barnes, Jessica J.; Anand, Mahesh; Crawford, Ian A.; Joy, Katherine H.

2016-10-01

Despite more than 40 years of studying Apollo samples, the age and early evolution of the Moon remain contentious. Following the formation of the Moon in the aftermath of a giant impact, the resulting Lunar Magma Ocean (LMO) is predicted to have generated major geochemically distinct silicate reservoirs, including the sources of lunar basalts. Samples of these basalts, therefore, provide a unique opportunity to characterize these reservoirs. However, the precise timing and extent of geochemical fractionation is poorly constrained, not least due to the difficulty in determining accurate ages and initial Pb isotopic compositions of lunar basalts. Application of an in situ ion microprobe approach to Pb isotope analysis has allowed us to obtain precise crystallization ages from six lunar basalts, typically with an uncertainty of about ± 10 Ma, as well as constrain their initial Pb-isotopic compositions. This has enabled construction of a two-stage model for the Pb-isotopic evolution of lunar silicate reservoirs, which necessitates the prolonged existence of high-μ reservoirs in order to explain the very radiogenic compositions of the samples. Further, once firm constraints on U and Pb partitioning behaviour are established, this model has the potential to help distinguish between conflicting estimates for the age of the Moon. Nonetheless, we are able to constrain the timing of a lunar mantle reservoir differentiation event at 4376 ± 18 Ma, which is consistent with that derived from the Sm-Nd and Lu-Hf isotopic systems, and is interpreted as an average estimate of the time at which the high-μ urKREEP reservoir was established and the Ferroan Anorthosite (FAN) suite was formed.

Tracing Altiplano-Puna plateau surface uplift via radiogenic isotope composition of Andean arc lavas

NASA Astrophysics Data System (ADS)

Scott, E. M.; Allen, M. B.; Macpherson, C.; McCaffrey, K. J. W.; Davidson, J.; Saville, C.

2016-12-01

We have compiled published geochemical data for Jurassic to Holocene Andean arc lavas from 5oN to 47oS, covering the current extent of the northern, central and southern volcanic zones. Using this dataset we evaluate the spatial and temporal evolution of age corrected Sr- and Nd-radiogenic isotopes in arc lavas at a continental-scale, in order to understand the tectonic and surface uplift histories of the Andean margin. It has long been noted that baseline 87Sr/86Sr and 143Nd/144Nd ratios of Quaternary lavas from the central volcanic zone, located within the Altiplano-Puna plateau, are distinct from volcanic rocks to the north and south. This is commonly attributed to greater crustal thickness, which increases to roughly twice that of the average continental crust within the Altiplano-Puna plateau. By comparing 87Sr/86Sr and 143Nd/144Nd ratios in Quaternary lavas to published crustal thickness models, present day topography and the compositions of basement terranes, we note that Sr- and Nd-isotope values of Quaternary lavas are an effective proxy for present day regional elevation. In contrast, variation in basement terranes has only a small, second order effect on isotopic composition at the scale of our study. Using this isotopic proxy, we infer the spatial extent of the plateau and its surface uplift history from the Jurassic to the present. Our results concur with a crustal thickening model of continued surface uplift, which initiated in the Altiplano, with deformation propagating southwards into the Puna throughout the Neogene and then continuing in central Chile and Argentina up to the present day.

Selective recharge and isotopic composition of shallow groundwater within temperate, epigenic carbonate aquifers

NASA Astrophysics Data System (ADS)

Florea, Lee J.

2013-05-01

This paper considers the variation of δ18O and δ2H (VSMOW) in precipitation and shallow groundwater from carbonate aquifers that lend insight into the source and timing of recharge within temperate, epigenic karst. The shallow groundwater collected during 2010 and 2011 at Stream Cave (SC) and Natural Bridge Caverns (NBC) represent one input to and the primary output from the Redmond Creek karst aquifer in the Cumberland Plateau of southeast Kentucky, respectively. These data are compared with the isotopic composition of concurrent samples of precipitation from the same watershed that covers some 1900 ha. Values of δ18O and δ2H at SC and NBC are statistically similar and cluster at the midpoint of the local meteoric water line. These values remain surprisingly constant despite seasonal changes in temperature regimens and discharge. Samples in 2012 from regional springs that include Redmond Creek are more depleted in the heavier isotope and similarly stable despite coming from aquifers of a range of sizes and physical characteristics. Applying a Priestly-Taylor model for daily values of potential evapotranspiration, only 43% of the 1.10 m of precipitation in the 2010-2011 dataset remains as potential recharge, primarily during cooler months with lower solar insolation. Weighting δ18O and δ2H values of precipitation by potential recharge creates a better match with the isotopic composition of shallow groundwater than by weighting by precipitation amount. The isotopic composition and deuterium excess of precipitation samples are directly and inversely proportional to temperature, respectively. Deuterium excess in this study and displays intra- and inter-annual variation that ranges from a minimum of +11.1‰ to a maximum of +29.5‰ that demonstrate the higher-than-average deuterium excess in greater Appalachia and the shifting latitude of moisture sources, including a significant winter component of re-evaporated, continental moisture.

Nitrification in the euphotic zone as evidenced by nitrate dual isotopic composition: Observations from Monterey Bay, California

USGS Publications Warehouse

Wankel, Scott D.; Kendall, C.; Pennington, J.T.; Chavez, F.P.; Paytan, A.

2007-01-01

Coupled measurements of nitrate (NO3-), nitrogen (N), and oxygen (O) isotopic composition (??15NNO3 and ??18ONO3) were made in surface waters of Monterey Bay to investigate multiple N cycling processes occurring within surface waters. Profiles collected throughout the year at three sites exhibit a wide range of values, suggesting simultaneous and variable influence of both phytoplankton NO3- assimilation and nitrification within the euphotic zone. Specifically, increases ??18ONO3 were consistently greater than those in ??15NN03. A coupled isotope steady state box model was used to estimate the amount of NO3- supplied by nitrification in surface waters relative to that supplied from deeper water. The model highlights the importance of the branching reaction during ammonium (NH4+) consumption, in which NH4+ either serves as a substrate for regenerated production or for nitrification. Our observations indicate that a previously unrecognized proportion of nitrate-based productivity, on average 15 to 27%, is supported by nitrification in surface waters and should not be considered new production. This work also highlights the need for a better understanding of isotope effects of NH4+ oxidation, NH4+ assimilation, and NO4+ assimilation in marine environments.

Characteristics of Heavy Metals and Pb Isotopic Composition in Sediments Collected from the Tributaries in Three Gorges Reservoir, China

PubMed Central

Gao, Bo; Zhou, Huaidong; Huang, Yong; Wang, Yuchun; Gao, Jijun; Liu, Xiaobo

2014-01-01

The concentrations, distribution, accumulation, and potential ecological risk of heavy metals (Cr, Cu, Zn, Ni, As, Pb, Cd, and Hg) in sediments from the Three Gorges Reservoir (TGR) tributaries were determined and studied. Pb isotopic compositions in sediments were also measured to effectively identify the potential Pb sources. The results showed that the average concentrations of heavy metals in sediment of TGR tributaries were higher than the local background values of soils and sediments in China. The assessment by Geoaccumulation Index indicated that Cu, Ni, and Hg were at the “slightly polluted” level and Cd was ranked as the “moderately polluted” level in tributary sediments of TGR. The assessment by Potential Ecological Risk Index showed that Hg and Cd were the predominant elements in tributary sediments in TGR. The Pb isotopic ratios in sediments varied from 1.171 to 1.202 for 206Pb/207Pb and from 2.459 to 2.482 for 208Pb/207Pb in TGR. All Pb isotopic ratios in sediments were similar to those from coal combustion, lead ores (the mining activities and smelting process), and cement material, indicating that these anthropogenic inputs may be the main sources for Pb pollution in sediments of TGR tributaries. PMID:24624045

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.

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.

Barium isotope composition of altered oceanic crust from the IODP Site 1256 at the East Pacific Rise

NASA Astrophysics Data System (ADS)

Nan, X.; Yu, H.; Gao, Y.

2017-12-01

To understand the behavior of Ba isotopes in the oceanic crust during seawater alteration, we analyzed Ba isotopes for altered oceanic crust (AOC) from the IODP Site 1256 at the East Pacific Rise (EPR). The samples include 33 basalts, 5 gabbros, and 1 gabbronorite. This drill profile has four sections from top to bottom, including the volcanic section, transition zone, sheeted dyke complex, and plutonic complex. They display various degrees of alteration with obviously variable temperatures and water/rock ratios (Gao et al., 2012). The volcanic section is slightly to moderately altered by seawater at 100 to 250°; the transition zone is a mixing zone between upwelling hydrothermal fluids and downwelling seawater; and the sheeted dyke complex and plutonic complex are highly altered by hydrothermal fluids (˜250°). Ba isotopes were analyzed on a Neptune Plus MC-ICP-MS at the University of Science and Technology of China. The long-term precision of δ137/134Ba is better than 0.04‰ (2SD). The δ137/134Ba of the volcanic section and the top of the transition zone range between -0.01 and 0.30‰, higher than the δ137/134Ba of fresh MORB and upper mantle (0.020 ± 0.021‰, 2SE, Huang et al., 2015). Similarly, the δ137/134Ba of the sheeted dyke complex ranges from 0.05 to 0.28‰. The plutonic section has δ137/134Ba from -0.17 to -0.05‰, which is lower than the upper mantle, with one exception that has δ137/134Ba of 0.19‰. No correlation exists between Ba contents and δ137/134Ba. The weighted average δ137/134Ba of the AOC samples is 0.13±0.04‰ (2SE), significantly higher than that of the upper mantle. In all, our AOC data reveal obvious Ba isotopic fractionation, reflecting alteration of the AOC by hydrothermal fluids and seawater. The obvious difference of Ba isotope composition between the AOC and the upper mantle further indicates that recycling of the AOC could result in Ba isotope heterogeneity of the mantle. References: Gao Y, Vils F, Cooper K M, et al. (2012) Downhole variation of lithium and oxygen isotopic compositions of oceanic crust at East Pacific Rise, ODP Site 1256. Geochemistry, Geophysics, Geosystems,13(10). Huang F., Nan X., Hu M., Huang S. and Huang J. (2015) Barium isotope compositions of igneous rocks. Goldschm. Abstr.2015, 1331.

Sedimentological and Stable Isotope Changes at the Messinian-Pliocene Boundary Along a West to East Mediterranean Transect.

NASA Astrophysics Data System (ADS)

Pierre, C.; Rouchy, J.; Blanc-Valleron, M.

2001-12-01

During Messinian times, the whole Mediterranean area was submitted to evaporitic conditions which ended by the "Lago-Mare" brackish episode before the reset of open marine conditions in the early Pliocene. These major paleoceanographic changes resulted from regional tectonic reorganizations and global climate changes at this critical time interval, both acting to modify drastically the physiography and the hydrological budget of the Mediterranean basins. There exist outcropping sections and a few deep-sea ODP cores which contain the complete and continuous sedimentary sequence of the Messinian-Pliocene boundary (MPB), making it possible to follow the paleoenvironmental changes at a high resolution scale. We compare here sedimentological and carbonate stable isotope records on three sections for which a high- resolution sampling was applied to the 2 meters thick interval including the MPB. In the Vera section from South Spain, there is no clear change in the carbonate content of the silty clay succession when crossing the MPB. The oxygen and carbon isotopic compositions of calcite both increase by 1 permil across a 40 cm-thick interval which corresponds to the Messinian-Pliocene transition. At ODP Site 968 from the eastern Levantine basin, there is an important sedimentary change between Messinian brown silty clays containing about 20 percent of carbonate and Pliocene gray nannofossil ooze which carbonate content averages 60 percent. Across this 10 cm-thick transitional interval, the oxygen and carbon isotopic compositions of bulk calcite both increase by 4.5 permil. In the Pissouri section from Cyprus, the uppermost Messinian reddish to brown marls with paleosoils are overlain by white Pliocene marls. The carbonate content increases from 20 percent to reach 60 percent across a 40 cm-thick transitional interval. Within this interval corresponding to the MPB, the oxygen and carbon isotopic compositions increase by 4 permil and 2 permil respectively. These results indicate that the MPB is recorded everywhere from W to E Mediterranean by significant and sharp increases in the oxygen and carbon isotopic compositions, which indicate that the early Pliocene marine flooding of the Mediterranean basins was a very abrupt event.

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 ...

Stable Nd isotope variations in the inner Solar System: The effect of sulfide during differentiation?

NASA Astrophysics Data System (ADS)

McCoy-West, A.

2017-12-01

Radiogenic neodymium isotopes have been widely used in studies of planetary accretion to constrain the timescales of early planetary differention [1]. Whereas stable isotope varitaions potentially provide information on the the processes that occur during planet formation. Experimental work suggests that the Earth's core contains a significant proportion of sulfide [2], and recent experimental work shows that under reducing conditions sulfide can incorporate substantial quantities of refractory lithophile elements [including Nd; 3]. If planetary embroyos also contain sulfide-rich cores, Nd stable isotopes have the potential to trace this sulfide segregation event in highly reduced environments, because there is a significant contrast in bonding environment between sulfide and silicate, where heavy isotopes should be preferentially incorporated into high force-constant bonds involving REE3+ (i.e. the silicate mantle). Here we present 146Nd/144Nd data, obtained using a double spike TIMS technique, for a range of planetary bodies formed at variable oxidation states including samples from the Moon, Mars, the asteriod 4Vesta and the Angrite and Aubrite parent bodies. Analyses of chondritic meteorites and terrestrial igneous rocks indicate that the Earth has a Nd stable isotope composition that is indistinguishable from that of chondrites [4]. Eucrites and martian meteorites also have compositons within error of the chondritic average. Significantly more variabilty is observed in the low concentration lunar samples and diogienite meteorites with Δ146Nd = 0.16‰. Preliminary results suggest that the Nd stable isotope composition of oxidised planetary bodies are homogeneous and modifications are the result of subordinate magmatic processes. [1] Boyet & Carlson, Science 309, 576 (2005) [2] Labidi et al. Nature 501, 208 (2013); [3] Wohlers &Wood, Nature 520, 337 (2015); [4] McCoy-West et al. Goldschmidt Ab. 429 (2017).

Calcium isotopic fractionation in mantle peridotites by melting and metasomatism and Ca isotope composition of the Bulk Silicate Earth

NASA Astrophysics Data System (ADS)

Kang, Jin-Ting; Ionov, Dmitri A.; Liu, Fang; Zhang, Chen-Lei; Golovin, Alexander V.; Qin, Li-Ping; Zhang, Zhao-Feng; Huang, Fang

2017-09-01

To better constrain the Ca isotopic composition of the Bulk Silicate Earth (BSE) and explore the Ca isotope fractionation in the mantle, we determined the Ca isotopic composition of 28 peridotite xenoliths from Mongolia, southern Siberia and the Siberian craton. The samples are divided in three chemical groups: (1) fertile, unmetasomatized lherzolites (3.7-4.7 wt.% Al2O3); (2) moderately melt-depleted peridotites (1.3-3.0 wt.% Al2O3) with no or very limited metasomatism (LREE-depleted cpx); (3) strongly metasomatized peridotites (LREE-enriched cpx and bulk rock) further divided in subgroups 3a (harzburgites, 0.1-1.0% Al2O3) and 3b (fertile lherzolites, 3.9-4.3% Al2O3). In Group 1, δ44/40Ca of fertile spinel and garnet peridotites, which experienced little or no melting and metasomatism, show a limited variation from 0.90 to 0.99‰ (relative to SRM 915a) and an average of 0.94 ± 0.05‰ (2SD, n = 14), which defines the Ca isotopic composition of the BSE. In Group 2, the δ44/40Ca is the highest for three rocks with the lowest Al2O3, i.e. the greatest melt extraction degrees (average 1.06 ± 0.04 ‰, i.e. ∼0.1‰ heavier than the BSE estimate). Simple modeling of modal melting shows that partial melting of the BSE with 103 ln ⁡αperidotite-melt ranging from 0.10 to 0.25 can explain the Group 2 data. By contrast, δ44/40Ca in eight out of nine metasomatized Group 3 peridotites are lower than the BSE estimate. The Group 3a harzburgites show the greatest δ44/40Ca variation range (0.25-0.96‰), with δ44/40Ca positively correlated with CaO and negatively correlated with Ce/Eu. Chemical evidence suggests that the residual, melt-depleted, low-Ca protoliths of the Group 3a harzburgites were metasomatized, likely by carbonate-rich melts/fluids. We argue that such fluids may have low (≤0.25‰) δ44/40Ca either because they contain recycled crustal components or because Ca isotopes, similar to trace elements and their ratios, may be fractionated by kinetic and/or chromatographic effects of melt percolation in the mantle. The δ44/40Ca in Group 3b lherzolites (0.83-0.89‰) are lower than in the BSE as well, but the effects of metasomatism on δ44/40Ca are smaller, possibly because of the high Ca contents in their protoliths and/or smaller δ44/40Ca differences between the protoliths and metasomatic agents. The BSE estimates based on fertile peridotites in this study fall in the δ44/40Ca ranges for oceanic and continental basalts, various meteorites (achondrites; carbonaceous, ordinary and enstatite chondrites), Mars, and the Moon. These results provide benchmarks for the application of Ca isotopes to planet formation, mantle evolution, and crustal recycling.

Compound Specific and Enantioselective Stable Isotope Analysis as Tools To Monitor Transformation of Hexachlorocyclohexane (HCH) in a Complex Aquifer System.

PubMed

Liu, Yaqing; Bashir, Safdar; Stollberg, Reiner; Trabitzsch, Ralf; Weiß, Holger; Paschke, Heidrun; Nijenhuis, Ivonne; Richnow, Hans-Hermann

2017-08-15

Technical hexachlorocyclohexane (HCH) mixtures and Lindane (γ-HCH) have been produced in Bitterfeld-Wolfen, Germany, for about 30 years until 1982. In the vicinity of the former dump sites and production facilities, large plumes of HCHs persist within two aquifer systems. We studied the natural attenuation of HCH in these groundwater systems through a combination of enantiomeric and carbon isotope fractionation to characterize the degradation of α-HCH in the areas downstream of a former disposal and production site in Bitterfeld-Wolfen. The concentration and isotope composition of α-HCH from the Quaternary and Tertiary aquifers were analyzed. The carbon isotope compositions were compared to the source signal of waste deposits for the dumpsite and highly contaminated areas. The average value of δ 13 C at dumpsite was -29.7 ± 0.3 ‰ and -29.0 ± 0.1 ‰ for (-) and (+)α-HCH, respectively, while those for the β-, γ-, δ-HCH isomers were -29.0 ± 0.3 ‰, -29.5 ± 0.4 ‰, and -28.2 ± 0.2 ‰, respectively. In the plume, the enantiomer fraction shifted up to 0.35, from 0.50 at source area to 0.15 (well T1), and was found accompanied by a carbon isotope enrichment of 5 ‰ and 2.9 ‰ for (-) and (+)α-HCH, respectively. The established model for interpreting isotope and enantiomer fractionation patterns showed potential for analyzing the degradation process at a field site with a complex history with respect to contamination and fluctuating geochemical conditions.

Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

NASA Technical Reports Server (NTRS)

Freeman, K. H.; Ricci, S. A.; Studley, A.; Hayes, J. M.

1989-01-01

On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

Identification of a Compound Spinel and Silicate Presolar Grain in a Chondritic Interplanetary Dust Particle

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Nakamura-Messenger, K.; Messenger, S.; Keller, L. P.; Kloeck, W.

2014-01-01

Anhydrous chondritic porous interplanetary dust particles (CP IDPs) have undergone minimal parent body alteration and contain an assemblage of highly primitive materials, including molecular cloud material, presolar grains, and material that formed in the early solar nebula [1-3]. The exact parent bodies of individual IDPs are not known, but IDPs that have extremely high abundances of presolar silicates (up to 1.5%) most likely have cometary origins [1, 4]. The presolar grain abundance among these minimally altered CP IDPs varies widely. "Isotopically primitive" IDPs distinguished by anomalous bulk N isotopic compositions, numerous 15N-rich hotspots, and some C isotopic anomalies have higher average abundances of presolar grains (375 ppm) than IDPs with isotopically normal bulk N (<10 ppm) [5]. Some D and N isotopic anomalies have been linked to carbonaceous matter, though this material is only rarely isotopically anomalous in C [1, 5, 6]. Previous studies of the bulk chemistry and, in some samples, the mineralogy of select anhydrous CP IDPs indicate a link between high C abundance and pyroxene-dominated mineralogy [7]. In this study, we conduct coordinated mineralogical and isotopic analyses of samples that were analyzed by [7] to characterize isotopically anomalous materials and to establish possible correlations with C abundance.

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.

Gradients in seasonality and seawater oxygen isotopic composition along the early Permian Gondwanan coast, SE Australia

NASA Astrophysics Data System (ADS)

Beard, J. Andrew; Ivany, Linda C.; Runnegar, Bruce

2015-09-01

Oxygen isotope compositions of marine carbonates are commonly employed for understanding ancient temperatures, but this approach is complicated in the very distant past due to uncertainties about the effects of diagenesis and the isotopic composition of seawater, both locally and globally. Microsampled accretionary calcite from two species of the fossil bivalve Eurydesma Sowerby and Morris 1845 collected from sediments of Cisuralian age in high latitude marine sediments along the SE coast of Australia records cyclic seasonal fluctuations in shell δ18O values during growth, demonstrating the primary nature of the isotope signal and thus allowing investigation of early Permian seawater isotopic composition and water temperature in the high southern latitudes. The mean and seasonal range of δ18Ocarb decreases poleward across about 10° of paleolatitude (∼67°S-77°S). The presence of co-occurring dropstones and stratigraphically associated glendonites constrains winter temperatures across the region to near-freezing, thus permitting calculation of realistic estimates of water composition and summer temperatures. Summer δ18Ocarb values indicate water temperatures between 5 °C and 12 °C, with warmer values at lower latitudes. The decrease in both mean sea surface temperature and seasonal amplitude with increasing latitude on the Gondwanan coast is much like that observed along high-latitude coastlines today. Calculated δ18Owater decreases toward the pole, likely associated with an increasing contribution of isotopically light fresh water derived from summer snow-melt. The gradient in δ18Owater is similar to that documented over a similar span of latitude on the modern SE Greenland coast. We infer the presence of a north-flowing coastal current of cold, O18-depleted water that entrains progressively greater amounts of more typical seawater as it moves away from the pole. δ18O values in SE Australia, however, are about 3‰ lower than those off Greenland, suggesting comparatively lower salinity water or more O18-depleted glacial ice/runoff in the Permian Gondwanan high latitudes, perhaps augmented by more depleted (negative) global average seawater. Conditions in southeastern Australia during the largest of the Permian deglaciations were warmer than present-day Antarctica at similar latitudes, but may approximate those of early-mid Miocene Antarctica, with frozen winters but summers closer to 10 °C.

Novel stable isotope laser spectrometry elucidates changing mechanisms of CH4 production and consumption across a climate change sequence in an arctic wetland

NASA Astrophysics Data System (ADS)

McCalley, C. K.; Wehr, R.; Crill, P. M.; Chanton, J.; Hodgkins, S. B.; Nelson, D. D.; McManus, J. B.; Zahniser, M. S.; Rich, V.; Tyson, G.; Mondav, R.; Frolking, S.; Li, C.; Saleska, S. R.

2011-12-01

Methane flux from high latitude wetlands is both a critical component of the global CH4 budget, and highly sensitive to global climate change, with expected increases in emissions as permafrost thaws. Gaps in our understanding of the mechanisms driving changing CH4 production and consumption dynamics under permafrost thaw, however, limit our ability to predict the magnitude of this response under future climate conditions. To address these gaps, we quantified the isotopic composition of carbon gas fluxes (δ13C of CH4 and CO2) from a high latitude (68° N) wetland in Sweden (Stordalen Mire) to partition net CH4 emissions into its component parts, methanogenesis (including both acetoclastic, and CO2-reductive pathways) and methanotrophy (which consumes CH4 primarily via aerobic metabolism). We used newly developed quantum cascade laser technology, linked to automated chambers, to quantify isotopes at high frequency. Our measurements across a permafrost thaw gradient, going from permafrost-dominated, well-drained palsas to intermediate permafrost sites dominated by Sphagnum spp. to wet sites with no underlying permafrost, dominated by Eriophorum angustifolium, show both large increases in productivity and CH4 emissions as well as shifts in the CH4 production pathway. Across this permafrost thaw gradient the isotopic composition of CH4 becomes 13C enriched, due to increased acetoclastic CH4 production. While the palsa sites have no detectable CH4 emissions, fluxes in the Sphagnum site have an average isotopic composition of -79%, a value indicative of CH4 production dominated by CO2 reduction, in contrast the isotopic composition of CH4 produced in the Eriophorum sites ranged from -71 to -57%, showing increased CH4 production via the acetate pathway. We also observed an increase in acetoclastic methanogenesis as the growing season progressed. Together, these initial results suggest that thaw induced changes in hydrology and plant community composition increase peat lability, stimulating acetate fermentation and yielding increased methane emissions. We conclude that the biological controls on metabolic pathways of methanogenesis, though poorly represented in most ecosystem models, may nonetheless be important, in interaction with permafrost thaw dynamics, in determining future CH4 emissions under changing climate.

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.

Generation and fate of glacial sediments in the central Transantarctic Mountains based on radiogenic isotopes and implications for reconstructing past ice dynamics

NASA Astrophysics Data System (ADS)

Farmer, G. Lang; Licht, Kathy J.

2016-10-01

The Nd, Sr and Pb isotopic compositions of glacial tills from the Byrd and Nimrod Glaciers in the central Transantarctic Mountains (TAM) in East Antarctica were obtained to assess the sources of detritus transported by these ice masses. Tills from lateral moraines along the entire extent of both glaciers have isotopic compositions consistent with their derivation predominately from erosion of adjacent bedrock. Fine- (<63μ) and coarser-grained (0.5 mm-2 mm) sediment from these tills have identical isotopic characteristics, indicating that fine-grained detritus is the product of further comminution of coarser sediments. Comparison of present-day till isotopic data to existing data from fine-grained LGM tills in the central Ross Sea confirm that these were deposited from East Antarctic ice that expanded through the TAM and indicates that the LGM sediments are mixtures of detritus eroded along the entire path of ice transiting the TAM. If specific lithologies were preferentially eroded as ice passed through the TAM, it is not clearly evident in the Ross Sea till isotopic compositions. Our data do demonstrate, however, that glacial tills generated from erosion of inboard regions of the mountain belt yield sediment with a larger component of 560 Ma to 600 Ma detrital zircons and lower average εNd(0) values (<-5) than that produced further downstream. As a result, past retreat of ice grounding-lines up the narrow valleys of the TAM resulting in active erosion of inboard region should recognizable in glacial sediments deposited in the Ross Sea and so provide a means to identify times when the East Antarctic ice sheet was smaller than today. This study highlights both the value and necessity of utilizing multiple provenance methods in evaluating glacial erosion and transport when reconstructing past ice sheet dynamics.

The composition of heavy ions in solar energetic particle events

NASA Technical Reports Server (NTRS)

Fan, C. Y.; Gloeckler, G.; Hovestadt, D.

1983-01-01

Recent advances in determining the elemental, charge state, and isotopic composition of or approximate to 1 to or approximate to 20 MeV per nucleon ions in solar energetic particle (SEP) events and outline our current understanding of the nature of solar and interplanetary processes which may explain the observations. Average values of relative abundances measured in a large number of SEP events were found to be roughly energy independent in the approx. 1 to approx. 20 MeV per nucleon range, and showed a systematic deviation from photospheric abundances which seems to be organized in terms of the first ionization potential of the ion. Direct measurements of the charge states of SEPs revealed the surprisingly common presence of energetic He(+) along with heavy ion with typically coronal ionization states. High resolution measurements of isotopic abundance ratios in a small number of SEP events showed these to be consistent with the universal composition except for the puzzling overabundance of the SEP(22)Ne/(20)Ne relative to this isotopes ratio in the solar wind. The broad spectrum of observed elemental abundance variations, which in their extreme result in composition anomalies characteristic of (3)He rich, heavy ion rich and carbon poor SEP events, along with direct measurements of the ionization states of SEPs provided essential information on the physical characteristics of, and conditions in the source regions, as well as important constraints to possible models for SEP production.

Constraints on Nucleosynthesis from Xenon Isotopes in Presolar Material

NASA Astrophysics Data System (ADS)

Gilmour, J. D.; Turner, G.

2007-03-01

By applying theoretical constraints to three-dimensional fits of xenon isotope data from presolar grains, we show that they strongly suggest a nucleosynthesis process that produces ``r-process'' isotopes without producing s-process isotopes (128Xe, 130Xe) and without producing the conventional r-process isotope 136Xe. It is one of three distinct nucleosynthetic sources that are necessary and sufficient to explain the gross variation in xenon isotopic data across all presolar material. The other source contributing r-process isotopes is responsible for the heavy isotope signature identified in nanodiamonds, which is also present in presolar SiC, and is associated with light isotope enrichment. The relative enrichments of heavy and light isotopes in this component in nanodiamonds and SiC grains are different, implying that the parent nucleosynthetic processes are not inextricably linked. Because minor variations in the isotopic compositions of xenon trapped in nanodiamonds show that two distinct sites contributed nanodiamonds to the early solar system within the average grain lifetime, it is suggested that Type IIa supernovae (SNe IIa) are not the source of the nanodiamonds. The s-process signature derived is consistent with that derived from mixing lines between grain subpopulations for isotopes on the s-process path. This implies that a pure end-member is present in the grains (although not approached in analyses). Our approach is more general and provides a less restrictive set of numerical constraints to be satisfied by proposed theoretical treatments of nucleosynthesis.

Oxygen and strontium isotope tracing of human migration at the Bell Beaker site Le Tumulus des Sables, France.

NASA Astrophysics Data System (ADS)

Willmes, Malte; James, Hannah; Boel, Ceridwen; Courtaud, Patrice; Chancerel, Antoine; McMorrow, Linda; Armstrong, Richard; Kinsley, Les; Aubert, Maxime; Eggins, Stephen; Moffat, Ian; Grün, Rainer

2014-05-01

Oxygen (δ18O) and strontium (87Sr/86Sr) isotopes were used as tools to investigate human migration at the early Bell Beaker site (2500-2000 BC) Le Tumulus des Sables, Saint-Laurent-Médoc, south-west France. The O and Sr isotope ratios measured in tooth enamel record the average dietary isotope signature ingested by that individual during their childhood. When this data is compared to the isotope signature of the burial site it can be used to indicate if the individual migrated into this area during their lifetime. The O isotopic composition of meteoric water changes depending on climate, temperature and quantity of precipitation. O isotope ratios in skeletal and dental remains are related to body water, which in turn is influenced by diet, physiology and climate. Most of the water consumed by large mammals comes from drinking water, typically sourced locally. Sr isotope ratios on the other hand vary between different geologic regions, depending on their age and composition. Sr is released through weathering and transported into the soil, ground and surface water, where it becomes available for uptake by plants, enters the food cycle and eventually ends up in skeletal and dental tissue where it substitutes for calcium. We analysed the teeth of 18 adult and 8 juvenile disarticulated skeletons from Le Tumulus des Sables. O isotopes were analysed in-situ by Sensitive High Resolution Ion Micro Probe (SHRIMP).The Sr isotope analysis involved drilling a 0.2-0.5 mg sample of enamel from the tooth. The Sr was then chemically separated and analysed by Thermal Ionization Mass Spectrometry (TIMS). These results were then compared to the O isoscape of Europe and bioavailable Sr isotope data (fauna, plants, soils) from the IRHUM database. We found that most of the individuals at Le Tumulus des Sables show O and Sr isotope ratios corresponding to the local environmental signal and we interpret these as part of the local population. 3 adults however show slightly higher 87Sr/86Sr ratios, which correspond to a clay and limestone unit in close proximity (

Constraints on the origin of Os-isotope disequilibrium in included and interstitial sulfides in mantle peridotites: Implications for the interpretation of Os-isotope signatures in MORB and Abyssal Peridotites

NASA Astrophysics Data System (ADS)

Lassiter, J. C.

2016-12-01

The use of isotope variations in basalts to probe the composition and evolution of the mantle is predicated on the assumption of local (i.e., grain-scale) isotopic equilibrium during mantle melting (Hofmann & Hart, 1978). However, several studies report Os-isotope disequilibrium in distinct populations of sulfides in some peridotites. In principle, grain-scale isotopic heterogeneity could reflect variable radiogenic ingrowth in ancient sulfides with variable Re/Os, or partial re-equilibration of low-Re/Os sulfides with high-Re/Os silicate phases along grain boundaries during mantle melting (e.g., Alard et al., 2005). Both cases require that sulfides fail to maintain isotopic equilibrium with neighboring phases over geologically long ( Ga) time scales. The preservation of Os-isotope disequilibrium in peridotites has been ascribed to the armoring effect of low-[Os] silicates, which limit diffusive exchange between isolated Os-rich phases. This raises the prospect that peridotite-derived melts may not inherit the Os-isotope composition of their source. The timescale required for diffusive equilibration between separate sulfide grains or between Os-rich sulfides and Os-poor silicates is a function of average sulfide size and spacing, Os diffusivity in armoring silicate minerals, and Os partitioning between silicate and sulfide phases. For typical sulfide abundances and sizes in mantle peridotites, neighboring sulfides are expected to re-equilibrate in less than a few 10s of m.y. at adiabatic mantle temperatures, even for very high (>106) sulfide/silicate KD values. Maintenance of disequilibrium requires very large sulfides (>100 um) separated by several mm and diffusion rates (D < 10-20 m2/s) slower than for most other elements in olivine. Equilibration timescales between sulfides and surrounding silicates are similar, so that large-scale isotopic disequilibrium between sulfides and silicates is also unlikely within the convecting mantle. Instead, observed grain-scale Os-isotope disequilibrium in mantle peridotites likely reflects recent sulfide metasomatism linked to interaction with eclogite- or pyroxenite-derived melts. Interstitial sulfides with radiogenic Os-isotopes provide further evidence for a role of eclogite melting in MORB genesis.

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.

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.

Osmium isotopes suggest fast and efficient mixing in the oceanic upper mantle.

NASA Astrophysics Data System (ADS)

Bizimis, Michael; Salters, Vincent

2010-05-01

The depleted upper mantle (DUM; the source of MORB) is thought to represent the complementary reservoir of continental crust extraction. Previous studies have calculated the "average" DUM composition based on the geochemistry of MORB. However the Nd isotope compositions of abyssal peridotites have been shown to extend to more depleted compositions than associated MORB. While this argues for the presence of both relatively depleted and enriched material within the upper mantle, the extent of compositional variability, length scales of heterogeneity and timescales of mixing in the upper mantle are not well constrained. Model calculations show that 2Ga is a reasonable mean age of depletion for DUM while Hf - Nd isotopes show the persistence of a depleted terrestrial reservoir by the early Archean (3.5-3.8Ga). U/Pb zircon ages of crustal rocks show three distinct peaks at 1.2, 1.9, and 2.7Ga and these are thought to represent the ages of three major crustal growth events. A fundamental question therefore is whether the present day upper mantle retains a memory of multiple ancient depletion events, or has been effectively homogenized. This has important implications for the nature of convection and time scales of survival of heterogeneities in the upper mantle. Here we compare published Os isotope data from abyssal peridotites and ophiolitic Os-Ir alloys with new data from Hawaiian spinel peridotite xenoliths. The Re-Os isotope system has been shown to yield useful depletion age information in peridotites, so we use it here to investigate the distribution of Re-depletion ages (TRD) in these mantle samples as a proxy for the variability of DUM. The probability density functions (PDF) of TRD from osmiridiums, abyssal and Hawaiian peridotites are all remarkably similar and show a distinct peak at 1.2-1.3 Ga (errors for TRD are set at 0.2Ga to suppress statistically spurious age peaks). The Hawaiian peridotites further show a distinct peak at 1.9-2Ga, but no oceanic mantle samples with TRD older than 2Ga have been reported. The TRD age peaks overlap with two major crustal building events recorded in the U/Pb crustal zircon ages. Therefore, peridotites from the convecting upper mantle can retain some memory of ancient depletion events, and these depletions are perhaps linked to major crustal building or large-scale mantle melting events. In the case of the Hawaiian peridotites, an ancient depletion event is further supported by some extremely radiogenic Hf isotope compositions. However, the vast majority of oceanic mantle samples show a narrow rage of Os isotope compositions (187Os/188Os = 0.123-0.126) with TRDs at 300-600 Ma. If the upper mantle has been produced continuously (or episodically) since at least the early Archean, it is then surprising that almost all oceanic mantle samples record such young depletion ages. We suggest that convective mixing in the mantle is rigorous enough that effectively re-homogenizes and resets the Os isotope composition of previously depleted peridotites within short time scales (<500Ma). Similarly recent ages have been derived from modeling the Sr, Nd, Hf, Pb isotopic composition of MORBs. This resetting and homogenization can be due to re-equilibration of depleted mantle with enriched components, e.g. recycled basaltic crust or more fertile mantle. Ancient depletion events are only effectively preserved in the sublithospheric mantle samples (e.g. Kaapval, Slave, Wyoming cratons) because they remain isolated from the convective mantle.

Age, compositional, and isotopic evidence for crustal recycling in a Late Archean arc, Beartooth Mountains

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

Wooden, J.L.; Mueller, P.A.; Graves, M.A.

1985-01-01

Late Archean rocks of the eastern Beartooth Mountains range in composition from basaltic andesite to granite and were emplaced 2.73-2.80 Ga ago in a middle to early Archean terrane as indicated by U-Pb zircon studies. Although trace element abundances are extremely variable for this group of rocks, their initial Pb, Sr, and Nd isotopic compositions are remarkably homogenous. A composite Rb-Sr isochron (>30 samples) yield an age of 2.79/plus minus/0.04 Ga with an initial ratio of 0.7022/plus minus/2 while /epsilon/Nd 2.78 Ga ago ranges from -1.5 to -3.1 (av. -2.2). Whole-rock Pb data for these rocks scatter about a 2.75more » Ga isochron and feldspar Pb data suggest initial 206/204 = 13.88, 207/204 = 14.96, and 208/204 = 34.3. These values lie well above values for average crustal leads 2.78 Ga ago as modeled by Stacey and Kramer (1975) and would require development in a reservior with /mu/= 12 from 3.7-2.8 Ga (/mu/= 7.2, 4.5-3.7 Ga). The marked differences between these values and those of the late Archean mantle require that an early to middle Archean crust played a role in the genesis of these rocks. The compositional variety and isotopic homogeneity may have developed as the result of crust-mantle mixing similar to that observed in modern volcanic-plutonic arcs along continental margins where crustal materials can be subducted, and fluids derived from these materials added to the overlying mantle wedge and lower crust. During this period, contaminated mantle may have been generated on a regional scale as evidenced by the isotopic systematics of young mafic volcanics from the northwestern U.S. (e.g. Snake River Plain, Yellowstone, Columbia River).« less

Reconstructed ancestral enzymes suggest long-term cooling of Earth's photic zone since the Archean

NASA Astrophysics Data System (ADS)

Garcia, Amanda K.; Schopf, J. William; Yokobori, Shin-ichi; Akanuma, Satoshi; Yamagishi, Akihiko

2017-05-01

Paleotemperatures inferred from the isotopic compositions (δ18O and δ30Si) of marine cherts suggest that Earth’s oceans cooled from 70 ± 15 °C in the Archean to the present ˜15 °C. This interpretation, however, has been subject to question due to uncertainties regarding oceanic isotopic compositions, diagenetic or metamorphic resetting of the isotopic record, and depositional environments. Analyses of the thermostability of reconstructed ancestral enzymes provide an independent method by which to assess the temperature history inferred from the isotopic evidence. Although previous studies have demonstrated extreme thermostability in reconstructed archaeal and bacterial proteins compatible with a hot early Earth, taxa investigated may have inhabited local thermal environments that differed significantly from average surface conditions. We here present thermostability measurements of reconstructed ancestral enzymatically active nucleoside diphosphate kinases (NDKs) derived from light-requiring prokaryotic and eukaryotic phototrophs having widely separated fossil-based divergence ages. The ancestral environmental temperatures thereby determined for these photic-zone organisms--shown in modern taxa to correlate strongly with NDK thermostability--are inferred to reflect ancient surface-environment paleotemperatures. Our results suggest that Earth's surface temperature decreased over geological time from ˜65-80 °C in the Archean, a finding consistent both with previous isotope-based and protein reconstruction-based interpretations. Interdisciplinary studies such as those reported here integrating genomic, geologic, and paleontologic data hold promise for providing new insight into the coevolution of life and environment over Earth history.

Reconstructed ancestral enzymes suggest long-term cooling of Earth's photic zone since the Archean.

PubMed

Garcia, Amanda K; Schopf, J William; Yokobori, Shin-Ichi; Akanuma, Satoshi; Yamagishi, Akihiko

2017-05-02

Paleotemperatures inferred from the isotopic compositions (δ 18 O and δ 30 Si) of marine cherts suggest that Earth's oceans cooled from 70 ± 15 °C in the Archean to the present ∼15 °C. This interpretation, however, has been subject to question due to uncertainties regarding oceanic isotopic compositions, diagenetic or metamorphic resetting of the isotopic record, and depositional environments. Analyses of the thermostability of reconstructed ancestral enzymes provide an independent method by which to assess the temperature history inferred from the isotopic evidence. Although previous studies have demonstrated extreme thermostability in reconstructed archaeal and bacterial proteins compatible with a hot early Earth, taxa investigated may have inhabited local thermal environments that differed significantly from average surface conditions. We here present thermostability measurements of reconstructed ancestral enzymatically active nucleoside diphosphate kinases (NDKs) derived from light-requiring prokaryotic and eukaryotic phototrophs having widely separated fossil-based divergence ages. The ancestral environmental temperatures thereby determined for these photic-zone organisms--shown in modern taxa to correlate strongly with NDK thermostability--are inferred to reflect ancient surface-environment paleotemperatures. Our results suggest that Earth's surface temperature decreased over geological time from ∼65-80 °C in the Archean, a finding consistent both with previous isotope-based and protein reconstruction-based interpretations. Interdisciplinary studies such as those reported here integrating genomic, geologic, and paleontologic data hold promise for providing new insight into the coevolution of life and environment over Earth history.

Eddy Covariance measurements of stable isotopes (δD and δ18O) in water vapor

NASA Astrophysics Data System (ADS)

Braden-Behrens, J.; Knohl, A.

2016-12-01

Stable isotopes are a promising tool to enhance our understanding of ecosystem gas exchanges. Studying 18O and 2H (D) in water vapour (H2Ov) can e.g. help partitioning evapotranspiration into its components. With recent developments in laser spectroscopy direct Eddy Covariance (EC) measurements to investigate fluxes of stable isotopologues became feasible. But so far only very few case studies applying the EC method to stable isotopes in water vapor have been carried out worldwide At our micrometeorological EC tower in a managed beech forest in Thuringia, Germany, we continuously measure fluxes of water vapor isotopologues using EC since autumn 2015. The set-up is based on an off-axis cavity output water vapor isotope analyzer (WVIA, Los Gatos Research. Inc, USA) that measures the water vapour concentration and its isotopic composition (δD and δ18O). The instrument is optimized for high flow rates (app. 4slpm) to generate high frequent (2Hz) measurements. The HF-optimized WVIA showed sufficient precision with a minimal Allan Deviation of 0.023 ‰ for δD and 0.02 ‰ for δ18O for averaging periods of app. 700 s and 400 s resp. The instrument is calibrated hourly using a high-flow optimized version of the water vapor isotope standard source (WVISS, Los Gatos Research. Inc, USA) that provides water vapor with known isotopic composition for a large range of different concentrations. Our calibration scheme includes a near continuous concentration range calibration instead of a simple 2 or 3-point calibration to face the analyzers large concentration dependency within a range of app. 6 000 to 16 000 ppm in winter and app. 8 000 to 23 000 ppm in summer. We evaluate the calibration approach, present specific aspects of the set-up such as the HF optimization and compare the measured and averaged spectra and cospectra of the isotopologue analyzer with those of the longterm EC installation (using a LI-6262 as well as a LI-7200 infrared gas analyzer at 10 Hz). Furthermore, we show results for the isotopologue fluxes before and after leaf unfolding in spring/summer 2016. This novel instrument for EC measurements of water vapor isotopologues provides a new exciting opportunity for studying the hydrological cycle in long-term observation networks like Ameriflux and ICOS.

Effects of climatic seasonality on the isotopic composition of evaporating soil waters

NASA Astrophysics Data System (ADS)

Benettin, Paolo; Volkmann, Till H. M.; von Freyberg, Jana; Frentress, Jay; Penna, Daniele; Dawson, Todd E.; Kirchner, James W.

2018-05-01

Stable water isotopes are widely used in ecohydrology to trace the transport, storage, and mixing of water on its journey through landscapes and ecosystems. Evaporation leaves a characteristic signature on the isotopic composition of the water that is left behind, such that in dual-isotope space, evaporated waters plot below the local meteoric water line (LMWL) that characterizes precipitation. Soil and xylem water samples can often plot below the LMWL as well, suggesting that they have also been influenced by evaporation. These soil and xylem water samples frequently plot along linear trends in dual-isotope space. These trend lines are often termed "evaporation lines" and their intersection with the LMWL is often interpreted as the isotopic composition of the precipitation source water. Here we use numerical experiments based on established isotope fractionation theory to show that these trend lines are often by-products of the seasonality in evaporative fractionation and in the isotopic composition of precipitation. Thus, they are often not true evaporation lines, and, if interpreted as such, can yield highly biased estimates of the isotopic composition of the source water.

Baseline shifts in coral skeletal oxygen isotopic composition: a signature of symbiont shuffling?

NASA Astrophysics Data System (ADS)

Carilli, J. E.; Charles, C. D.; Garren, M.; McField, M.; Norris, R. D.

2013-06-01

Decades-long records of the stable isotopic composition of coral skeletal cores were analyzed from four sites on the Mesoamerican Reef. Two of the sites exhibited baseline shifts in oxygen isotopic composition after known coral bleaching events. Changes in pH at the calcification site caused by a change in the associated symbiont community are invoked to explain the observed shift in the isotopic composition. To test the hypothesis that changes in symbiont clade could affect skeletal chemistry, additional coral samples were collected from Belize for paired Symbiodinium identification and skeletal stable isotopic analysis. We found some evidence that skeletal stable isotopic composition may be affected by symbiont clade and suggest this is an important topic for future investigation. If different Symbiodinium clades leave consistent signatures in skeletal geochemical composition, the signature will provide a method to quantify past symbiont shuffling events, important for understanding how corals are likely to respond to climate change.

Lead contamination in cocoa and cocoa products: isotopic evidence of global contamination.

PubMed

Rankin, Charley W; Nriagu, Jerome O; Aggarwal, Jugdeep K; Arowolo, Toyin A; Adebayo, Kola; Flegal, A Russell

2005-10-01

In this article we present lead concentrations and isotopic compositions from analyses of cocoa beans, their shells, and soils from six Nigerian cocoa farms, and analyses of manufactured cocoa and chocolate products. The average lead concentration of cocoa beans was

Lead Contamination in Cocoa and Cocoa Products: Isotopic Evidence of Global Contamination

PubMed Central

Rankin, Charley W.; Nriagu, Jerome O.; Aggarwal, Jugdeep K.; Arowolo, Toyin A.; Adebayo, Kola; Flegal, A. Russell

2005-01-01

In this article we present lead concentrations and isotopic compositions from analyses of cocoa beans, their shells, and soils from six Nigerian cocoa farms, and analyses of manufactured cocoa and chocolate products. The average lead concentration of cocoa beans was ≤ 0.5 ng/g, which is one of the lowest reported values for a natural food. In contrast, lead concentrations of manufactured cocoa and chocolate products were as high as 230 and 70 ng/g, respectively, which are consistent with market-basket surveys that have repeatedly listed lead concentrations in chocolate products among the highest reported for all foods. One source of contamination of the finished products is tentatively attributed to atmospheric emissions of leaded gasoline, which is still being used in Nigeria. Because of the high capacity of cocoa bean shells to adsorb lead, contamination from leaded gasoline emissions may occur during the fermentation and sun-drying of unshelled beans at cocoa farms. This mechanism is supported by similarities in lead isotopic compositions of cocoa bean shells from the different farms (206Pb/207Pb = 1.1548–1.1581; 208Pb/207Pb = 2.4344–2.4394) with those of finished cocoa products (206Pb/207Pb = 1.1475–1.1977; 208Pb/207Pb = 2.4234–2.4673). However, the much higher lead concentrations and larger variability in lead isotopic composition of finished cocoa products, which falls within the global range of industrial lead aerosols, indicate that most contamination occurs during shipping and/or processing of the cocoa beans and the manufacture of cocoa and chocolate products. PMID:16203244

Isotope chemistry of an extensively nitrate-contaminated urban aquifer

NASA Astrophysics Data System (ADS)

Kracht, O.; de Souza, L. C.; de Queiros, M. A.; Stegemann, C.; Hunziker, J.

2003-04-01

The supply of drinking water for the approximately 800.000 inhabitants of the city of Natal (Rio Grande do Norte, Brazil) is strongly dependent on the use of local groundwater from the Barreiras Aquifer. Over 70 % of the public production are served by a system of about 130 tubular wells, that are distributed all over the urban area. Yet, no groundwater protection zones have been declared. In addition, a comparable number of private wells also depend on the cities underground water resources. Depending on the local topography, the groundwater table is located several tens of meters below surface. Useable groundwater occurrences are bound to an up to hundred meters thick series of unconsolidated clastic sediments from the younger tertiary (Barreiras Formation), that is underlain by less permeable cretaceous carbonates. Natals topography is dominated by impressive quaternary dunes formations, that play an important role for the infiltration of rain as the only source of recharge for the local groundwater. During the last decades, an extensive and rapidly growing groundwater-contamination with up to over 100 mg/l nitrate was observed by the local authorities. Hydrochemical data indicate this deterioration to be due to a massive spill of sanitary effluents over septic pits, as only 20 % of the city is yet served by a sewer system. The isotopic composition of Natals groundwater shows only small variations, with an average δ18O value of -2,3 per mill and δ2H value of -10,5 per mill vs. SMOW. Its origin from recent local precipitation is revealed by a good correspondence with the annual weighted means for precipitation in Ceara Mirim (nearest GNIP station, situated 45 km NE of Natal). In contrast, a set of samples from different regional surface waters indicated a strong evaporation trend with systematic enrichment in the oxygen and hydrogen isotopic composition. Samples from 33 production wells with a wide variation of nitrate concentrations were investigated for their isotopic composition of nitrate. The average δ15N value of +9,3 per mill vs. AIR and δ18O value of +10,8 per mill vs. SMOW consist with the assumption of sewage being the primary source of contamination. Observed variations in the oxygen isotope values are in the range of analytical precision, whereas the nitrogen isotope values vary stronger. This effect is assumed to be due to a varying degree of ammonia volatilisation before nitrification in the unsaturated zone. On the contrary, there is no hint for an ongoing bacterial reduction of nitrate, that should have been expressed by a systematic enrichment in both its oxygen and nitrogen isotope values. Degradation of nitrate seems to be inhibited due to the absence of a suitable electron donator and comparable high oxygenated conditions in the aquifer.

Coupling experimental and field-based approaches to decipher carbon sources in the shell of the great scallop, Pecten maximus (L.)

NASA Astrophysics Data System (ADS)

Marchais, V.; Richard, J.; Jolivet, A.; Flye-Sainte-Marie, J.; Thébault, J.; Jean, F.; Richard, P.; Paulet, Y.-M.; Clavier, J.; Chauvaud, L.

2015-11-01

This research investigated how the carbon isotopic composition of food source (δ13Cfood) and dissolved inorganic carbon (δ13CDIC) influences the carbon isotopic composition of Pecten maximus shells (δ13Cshell) under both experimental and natural conditions. The objectives are to better understand the relationship between P. maximus and its environment, and to specifically distinguish conditions under which calcification is influenced by respired CO2 derived from food sources versus conditions in which calcification uses inorganic carbon from seawater. Laboratory experiment investigated carbon incorporation into shell carbonates by maintaining scallops under conditions where the stable carbon isotopic composition of food sources was considerably depleted (-54‰), relative to values observed in the natural environment (-21‰). Laboratory experiment ran for 78 days under three temperature conditions, 15 °C, 21 °C and 25 °C. A survey of the environmental parameters and stable carbon isotopic composition into shell carbonate of natural population of P. maximus was also realized during the same year in the Bay of Brest, France. Data collected from both laboratory experiment and the natural environment confirmed that both δ13CDIC and δ13Cfood influence δ13Cshell values and that organic carbon incorporation (CM) averages about 10% (4.3-6.8% under experimental conditions and 1.9-16.6% in the natural environment). The shift in stable carbon isotopic composition from the uptake of depleted food sources under experimental conditions realized a marked divergence in the predicted equilibrium between calcium carbonate and ambient bicarbonate, relative to the natural environment. This offset was 1.7 ± 0.6‰ for scallops in their natural environment and 2.5 ± 0.5 and 3.2 ± 0.9‰ for scallops under experimental conditions at water temperatures of 15 °C and 21 °C, respectively. The offset of 3‰ for scallops subjected to laboratory experiment could not be explained in light of growth rate but may be related to food supply and/or temperature. Food source and temperature effects may also explain the annual variation observed in CM values measured from scallops in their natural environment. CM estimation from the natural population of P. maximus varied seasonally from around 2% at the end of winter, to 12% in summer. The seasonal variation resembles variability in the carbon isotopic composition of the food sources throughout the year with an exception at the end of winter.

Crustal forensics in arc magmas

NASA Astrophysics Data System (ADS)

Davidson, Jon P.; Hora, John M.; Garrison, Jennifer M.; Dungan, Michael A.

2005-01-01

The geochemical characteristics of continental crust are present in nearly all arc magmas. These characteristics may reflect a specific source process, such as fluid fluxing, common to both arc magmas and the continental crust, and/or may reflect the incorporation of continental crust into arc magmas either at source via subducted sediment, or via contamination during differentiation. Resolving the relative mass contributions of juvenile, mantle-derived material, versus that derived from pre-existing crust of the upper plate, and providing these estimates on an element-by-element basis, is important because: (1) we want to constrain crustal growth rates; (2) we want to quantitatively track element cycling at convergent margins; and (3) we want to determine the origin of economically important elements and compounds. Traditional geochemical approaches for determining the contributions of various components to arc magmas are particularly successful when applied on a comparative basis. Studies of suites from multiple magmatic systems along arcs, for which differentiation effects can be individually constrained, can be used to extrapolate to potential source compositions. In the Lesser Antilles Arc, for example, differentiation trends from individual volcanoes are consistent with open-system evolution. However, such trends do not project back to a common primitive magma composition, suggesting that differentiation modifies magmas that were derived from distinct mantle sources. We propose that such approaches should now be complemented by petrographically constrained mineral-scale isotope and trace element analysis to unravel the contributing components to arc magmas. This innovative approach can: (1) better constrain true end-member compositions by returning wider ranges in geochemical compositions among constituent minerals than is found in whole rocks; (2) better determine magmatic evolution processes from core-rim isotopic or trace element profiles from the phases contained in magmas; and (3) constrain rates of differentiation by applying diffusion-controlled timescales to element profiles. An example from Nguaruhoe Volcano, New Zealand, underscores the importance of such a microsampling approach, showing that mineral isotopic compositions encompass wide ranges, that whole-rock isotopic compositions are consequently simply element-weighted averages of the heterogeneous crystal cargo, and that open-system evolution is proved by core-rim variations in Sr isotope ratios. Nguaruhoe is just one of many systems examined through microanalytical approaches. The overwhelming conclusion of these studies is that crystal cargoes are not truly phenocrystic, but are inherited from various sources. The implication of this realization is that the interpretation of whole-rock isotopic data, including the currently popular U-series, needs careful evaluation in the context of petrographic observations.

Nitrogen isotope geochemistry of basaltic glasses: implications for mantle degassing and structure?

NASA Astrophysics Data System (ADS)

Exley, R. A.; Boyd, S. R.; Mattey, D. P.; Pillinger, C. T.

1987-01-01

The nitrogen isotope geochemistry of 15 basaltic glasses has been investigated using stepped heating and high sensitivity static vacuum mass spectrometry. At low temperature (< 600°C) the glasses release small amounts of nitrogen with δ 15N AIR, averaging -0.3‰, suggesting surficial adsorption of atmospheric nitrogen. At high temperature, usually with a maximum at 1000°C, indigenous nitrogen with a concentration ranging from 0.2 to 2.1 ppm is released. The δ 15N values of this high temperature release show a wide range from -4.5‰ to +15.5‰. There is no correlation between N ppm and δ 15N, and the samples apparently form 3 groups with distinctive δ 15N. Six MORB glasses from the Mid-Atlantic Ridge, East Pacific Rise and Juan de Fuca Ridge define a group with δ 15N = +7.5 ± 1.3‰. In contrast two Indian Ocean MORB glasses (Carlsberg Ridge and Gulf of Aden) gave negative δ 15N averaging -3.2‰. Glasses from Loihi Seamount have high δ 15N averaging +14.0 ± 1.0‰. Comparison of the δ 15N data with the mantle models derived from helium and argon isotope studies suggests that the wide range in δ 15N may reflect in part heterogeneities in the mantle related to its degassing history. It is possible, however, that magmatic degassing processes have also affected nitrogen isotopic compositions, and the data cannot yet be unambiguously interpreted in terms of source variations.

Archival processes of the water stable isotope signal in East Antarctic ice cores

NASA Astrophysics Data System (ADS)

Casado, Mathieu; Landais, Amaelle; Picard, Ghislain; Münch, Thomas; Laepple, Thomas; Stenni, Barbara; Dreossi, Giuliano; Ekaykin, Alexey; Arnaud, Laurent; Genthon, Christophe; Touzeau, Alexandra; Masson-Delmotte, Valerie; Jouzel, Jean

2018-05-01

The oldest ice core records are obtained from the East Antarctic Plateau. Water isotopes are key proxies to reconstructing past climatic conditions over the ice sheet and at the evaporation source. The accuracy of climate reconstructions depends on knowledge of all processes affecting water vapour, precipitation and snow isotopic compositions. Fractionation processes are well understood and can be integrated in trajectory-based Rayleigh distillation and isotope-enabled climate models. However, a quantitative understanding of processes potentially altering snow isotopic composition after deposition is still missing. In low-accumulation sites, such as those found in East Antarctica, these poorly constrained processes are likely to play a significant role and limit the interpretability of an ice core's isotopic composition. By combining observations of isotopic composition in vapour, precipitation, surface snow and buried snow from Dome C, a deep ice core site on the East Antarctic Plateau, we found indications of a seasonal impact of metamorphism on the surface snow isotopic signal when compared to the initial precipitation. Particularly in summer, exchanges of water molecules between vapour and snow are driven by the diurnal sublimation-condensation cycles. Overall, we observe in between precipitation events modification of the surface snow isotopic composition. Using high-resolution water isotopic composition profiles from snow pits at five Antarctic sites with different accumulation rates, we identified common patterns which cannot be attributed to the seasonal variability of precipitation. These differences in the precipitation, surface snow and buried snow isotopic composition provide evidence of post-deposition processes affecting ice core records in low-accumulation areas.

Compound-specific isotopic analyses: a novel tool for reconstruction of ancient biogeochemical processes

NASA Technical Reports Server (NTRS)

Hayes, J. M.; Freeman, K. H.; Popp, B. N.; Hoham, C. H.

1990-01-01

Patterns of isotopic fractionation in biogeochemical processes are reviewed and it is suggested that isotopic fractionations will be small when substrates are large. If so, isotopic compositions of biomarkers will reflect those of their biosynthetic precursors. This prediction is tested by consideration of results of analyses of geoporphyrins and geolipids from the Greenhorn Formation (Cretaceous, Western Interior Seaway of North America) and the Messel Shale (Eocene, lacustrine, southern Germany). It is shown (i) that isotopic compositions of porphyrins that are related to a common source, but which have been altered structurally, cluster tightly and (ii) that isotopic differences between geolipids and porphyrins related to a common source are equal to those observed in modern biosynthetic products. Both of these observations are consistent with preservation of biologically controlled isotopic compositions during diagenesis. Isotopic compositions of individual compounds can thus be interpreted in terms of biogeochemical processes in ancient depositional environments. In the Cretaceous samples, isotopic compositions of n-alkanes are covariant with those of total organic carbon, while delta values for pristane and phytane are covariant with those of porphyrins. In this unit representing an open marine environment, the preserved acyclic polyisoprenoids apparently derive mainly from primary material, while the extractable, n-alkanes derive mainly from lower levels of the food chain. In the Messel Shale, isotopic compositions of individual biomarkers range from -20.9 to -73.4% vs PDB. Isotopic compositions of specific compounds can be interpreted in terms of origin from methylotrophic, chemautotrophic, and chemolithotrophic microorganisms as well as from primary producers that lived in the water column and sediments of this ancient lake.

Seasonality of Oxygen isotope composition in cow (Bos taurus) hair and its model interpretation

NASA Astrophysics Data System (ADS)

Chen, Guo; Schnyder, Hans; Auerswald, Karl

2017-04-01

Oxygen isotopes in animal and human tissues are expected to be good recorders of geographical origin and migration histories based on the isotopic relationship between hair oxygen and annual precipitation and the well-known spatial pattern of oxygen isotope composition in meteoric water. However, seasonal variation of oxygen isotope composition may diminish the origin information in the tissues. Here the seasonality of oxygen isotope composition in tail hair was investigated in a domestic suckler cow (Bos taurus) that underwent different ambient conditions, physiological states, and keeping and feeding strategies during five years. A detailed mechanistic model involving in ambient conditions, soil properties and animal physiology was built to explain this variation. The measured oxygen isotope composition in hair was significantly related (p<0.05) to the isotope composition in meteoric water in a regression analysis. Modelling suggested that this relation was only partly derived from the direct influence of feed moisture. Ambient conditions (temperature, moisture) did not only influence the isotopic signal of precipitation but also affected the animal itself (drinking water demand, transcutaneous vapor etc.). The clear temporal variation thus resulted from complex interactions with multiple influences. The twofold influence of ambient conditions via the feed and via the animal itself is advantageous for tracing the geographic origin because the oxygen isotope composition is then less influenced by variations in moisture uptake; however, it is unfavorable for indicating the production system, e.g. to distinguish between milk produced from fresh grass or from silage.

Isotope composition of secondary hydrogen and helium above the atmosphere measured by the instruments NINA and NINA-2

NASA Astrophysics Data System (ADS)

Bidoli, V.; Casolino, M.; de Pascale, M.; Furano, G.; Iannucci, A.; Morselli, A.; Picozza, P.; Sparvoli, R.; Bakaldin, A.; Galper, A.; Koldashov, S.; Korotkov, M.; Leonov, A.; Mikhailov, V.; Voronov, S.; Boezio, M.; Bonvicini, V.; Vacchi, A.; Zampa, G.; Zampa, N.; Ambriola, M.; Cafagna, F.; Circella, M.; de Marzo, C.; Adriani, O.; Papini, P.; Spillantini, P.; Straulino, S.; Vannuccini, E.; Ricci, M.; Castellini, G.

2003-05-01

In this paper we report on the energy spectra and abundance ratios of hydrogen and helium isotopes of albedo origin, measured by the instruments NINA and NINA-2 in near-equatorial regions. The instrument NINA flew on board the satellite Resurs-01-N4 between 1998 and 1999, at a 830 km average altitude. The NINA-2 apparatus, on board the satellite MITA, was put into orbit in July 2000 at an altitude of about 450 km. NINA and NINA-2 measurements revealed that 2H, 3H, 3He, and 4He are a significant portion of the secondary flux above the atmosphere. The energy spectra of hydrogen isotopes are practically flat across the energy range of 10-40 MeV/n, while the spectra of helium isotopes can be fitted by a power law of spectral indexes γ = 0.8 and γ = 1.5 for 3He and 4He, respectively.

Organismal versus Environmental Control of the Carbon Isotope Composition of Dicot Angiosperm Pollen: Implications for Paleoenvironmental Reconstruction

NASA Astrophysics Data System (ADS)

King, D. P.; Schubert, B.; Foelber, K.; Jahren, H.

2011-12-01

The prevalence and diagenetic resilience of palynomorphs in Proterozoic and Phanerozoic sediments has led researchers to investigate its potential as an environmental proxy based on its stable isotope composition. Towards this, Loader and Hemming (2001), noted that the carbon isotope composition (δ13C) of modern Pinus sylvestris pollen exine correlates with the developmental period temperature (°C) of the pollen (R2=0.68), implying that the δ13C of gymnosperm pollen could be quantitatively utilized as a paleotemperature proxy. However, the majority of pollen-producing organisms during the last ~120 million years have been angiosperms, which are subject to complex internal signaling for reproduction, in addition to environmental triggers. Because these internal signals control the relative proportion of lipids, long-chain fatty acids, and polysaccharides within pollen grains, we hypothesized that the δ13C variability in pollen (δ13Cpollen) from several plants subject to the same external environmental parameters is of the same magnitude as the amount attributed to the environment for gymnosperms. Within growth chambers, the test organism (Brassica rapa) was cultivated under constant light, water, pCO2, and nutrient supply, but exhibited average δ13Cpollen variability = 4.35% within any chamber (n = 6 to 8 plants per chamber). Field experiments were also conducted in which the pollen from the test organism (Hibiscus spp.) was sampled from several botanical gardens within the state of Hawaii. Pollen collected from any one botanical garden exhibited an average δ13Cpollen variability = 4.5% (up to 5 plants per garden). Upon comparing chambers operating at different temperatures (17°C to 32°C), we discovered no correlation (R2=0.01) between the developmental period temperature (°C) and the δ13C of B. rapa pollen; similarly, no correlation was found between the δ13C of Hibiscus pollen and its developmental period temperature (°C) (R2=0.12). This work underscores the lack of consistent environmental control over the δ13C value of pollen, and suggests that the carbon isotope composition of dicot pollen cannot be used to determine paleotemperatures. Future work centers on our hypothesis that the δ13C variability in angiosperm pollen results from differential reproductive potency and associated differences in the percentages of lipids, long-chain fatty acids, and polysaccharides within pollen. Towards this we will quantify the relationship between the chemical composition of flower-aggregate pollen and its δ13C value, given the δ13C value of isolated end-member constituents.

ISOTOPE CONVERSION DEVICE

DOEpatents

Wigner, E.P.; Young, G.J.; Ohlinger, L.A.

1957-12-01

This patent relates to nuclear reactors of tbe type utilizing a liquid fuel and designed to convert a non-thermally fissionable isotope to a thermally fissionable isotope by neutron absorption. A tank containing a reactive composition of a thermally fissionable isotope dispersed in a liquid moderator is disposed within an outer tank containing a slurry of a non-thermally fissionable isotope convertible to a thermally fissionable isotope by neutron absorption. A control rod is used to control the chain reaction in the reactive composition and means are provided for circulating and cooling the reactive composition and slurry in separate circuits.

Petrological, geochemical and isotopic characteristics of lignite and calcified lignite from mining area Pesje, Velenje Basin, Slovenia

NASA Astrophysics Data System (ADS)

Vrabec, Mirijam; Markič, Miloš; Vrabec, Marko; Jaćimović, Radojko; Kanduč, Tjaša

2014-05-01

Lignite (organic rich) and calcified lignite (inorganic rich) samples from excavation field -50c mining area Pesje, Velenje Basin, Slovenia were investigated. During geological and structural mapping lignite and calcified lignite samples were systematically taken for determination of their petrological, geochemical and isotopic characteristics. Lignite is composed of fine detritical gelified matrix. At least five different types of calcified lignite were recognized forming laminations, calcifications after wood, petrified wood and complete replacements of lignite with carbonate. All measured parameters so far indicate geochemical processes during sedimentation of the Velenej Basin. After macroscopic description samples were split to organic and inorganic component (Ward, 1984) and powdered in an agate mortar for geochemical and isotopic analyses. Major and trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Mn, Mo, Sb, Se, Th, U, Zn) in these samples were determined by instrumental neutron activation analysis (INAA) using k-0 standardization method (Jaćimović et al, 2002). The isotopic composition of carbon and nitrogen was determined using a Europa 20-20 continuous flow IRMS ANCA-SL preparation module. A 1 mg amount of a sample was weighed in a tin capsule for carbon and 10 mg for nitrogen analysis. Samples for carbon analyses were pretreated with 1 M HCl to remove carbonates. Carbonate samples from carbonate-rich strata and calcified xylite were first roasted at 450 deg C (Krantz et al., 1987). Three miligrams of carbonate sample was transformed into CO2 by reaction with anhydrous H3PO4 at 55 deg C under vacuum (McCrea, 1950) and measured with GV 2003 isotope ratio mass spectrometer. Measured isotopic composition of oxygen as VPDB values was recalculated to the VSMOW reference standard to enable the comparison with data from other coal basins. SEM/EDXS of carbonate rich sediments was performed with JEOL JSM 5800 electron microanalyzer scanning electron microscope energy dispersive X-ray spectroscopy at the Department of Ceramics at the Jožef Stefan Institute. Geochemical characteristics of major and trace elements indicate that the values of major and trace elements are comparable to world average coal (Zhang et al., 2004). Isotopic composition of carbon and isotopic composition of nitrogen of investigated samples indicate values from to -29.4o to -23.7o and 1.8o to 5.9o respectively. Lower value of isotopic composition of carbon indicates higher gelification (values up to -29.4) and higher value of isotopic composition of nitrogen (values up to 5.9) indicate higher mineralization. The results of SEM/EDXS microscopy revealed that in calcified lignite chemical composition of calcite prevails. Traces of diagenetic pyrite were also found, indicating localized anoxic conditions during sedimentation. Values of isotopic composition of CCaCO3 range from -2 to +13 and indicate temperature of precipitation from 17.3 to 35 deg C, which is similar to results obtained in previous studies (Kanduč et al., 2012). References Krantz, D.E., Williams, D.F., Jones, D.S., 1987: Ecological and paleoenvironmental information using stable isotope profiles from living and fossil mollusks. Palaeogeography, Palaeoclimatology, Palaeoecology 58, 249-266. Kanduč T., Markič M., Zavšek S., McIntosh J. 2012: carbon cycling in the Pliocene Velenje Coal Basin, Slovenia, inferred from stable carbon isotopes. International Journal of Coal Geology 89, 70-83. Jaćimović, R., Lazaru, A., Mihajlović, D., Ilić, R., Stafilov, T., 2002: Determination of major and trace elements in some minerals by k0-instrumental neutron activation analysis. Journal of Radioanalytical Nuclear Chemistry, 253, 427-434. McCrea, JM., 1950. On the isotopic chemistry of carbonates and a paleotemperature scale. Journal of Chemical Physics 18, 849. Ward C.R. (Ed.), 1984: Coal Geology and Coal Technology. Black-well, Oxford, 345 pp. Zhang J.Y., Zheng C.G., Ren D.Y., Chou C.L., Zheng R.S., Wang Z.P., Zhao F. H., Ge Y.T. 2004: Distribution of potentially hazardous trace elements in coals from Shoxi provinces, China. Fuel 83: 129-135.

MAST - A mass spectrometer telescope for studies of the isotopic composition of solar, anomalous, and galactic cosmic ray nuclei

NASA Technical Reports Server (NTRS)

Cook, Walter R.; Cummings, Alan C.; Cummings, Jay R.; Garrard, Thomas L.; Kecman, Branislav; Mewaldt, Richard A.; Selesnick, Richard S.; Stone, Edward C.; Von Rosenvinge, T. T.

1993-01-01

The Mass Spectrometer Telescope (MAST) on SAMPEX is designed to provide high resolution measurements of the isotopic composition of energetic nuclei from He to Ni (Z = 2 to 28) over the energy range from about 10 to several hundred MeV/nuc. During large solar flares MAST will measure the isotopic abundances of solar energetic particles to determine directly the composition of the solar corona, while during solar quiet times MAST will study the isotopic composition of galactic cosmic rays. In addition, MAST will measure the isotopic composition of both interplanetary and trapped fluxes of anomalous cosmic rays, believed to be a sample of the nearby interstellar medium.

Biogeochemical cycling in an organic-rich coastal marine basin. 8. A sulfur isotopic budget balanced by differential diffusion across the sediment-water interface

USGS Publications Warehouse

Chanton, J.P.; Martens, C.S.; Goldhaber, M.B.

1987-01-01

The sulfur isotopic composition of the sulfur fluxes occurring in the anoxic marine sediments of Cape Lookout Bight, N.C., U.S.A., was determined, and the result of isotopic mass balance was obtained via the differential diffusion model. Seasonal pore water sulfate ??34S measurements yielded a calculated sulfate input of 0.6%.. Sulfate transported into the sediments via diffusion appeared to be enriched in the lighter isotope because its concentration gradient was steeper, due to the increase in the measured isotopic composition of sulfate with depth. Similarly, the back diffusion of dissolved sulfide towards the sediment-water interface appeared enriched in the heavier isotope. The isotopic composition of this flux was calculated from measurements of the ??34S of dissolved sulfide and was determined to be 15.9%.. The isotopic composition of buried sulfide was determined to be -5.2%. and the detrital sulfur input was estimated to be -6.2%.. An isotope mass balance equation based upon the fluxes at the sediment-water interface successfully predicted the isotopic composition of the buried sulfur flux within 0.5%., thus confirming that isotopes diffuse in response to their individual concentration gradients. ?? 1987.

Molybdenum Isotopic Composition of Iron Meteorites, Chondrites and Refractory Inclusions

NASA Technical Reports Server (NTRS)

Becker, H.; Walker, R. J.

2003-01-01

Recent Mo isotopic studies of meteorites reported evidence for differences in isotopic compositions for whole rocks of some primitive and differentiated meteorites relative to terrestrial materials. Enrichments of r- and p-process isotopes of up to 3-4 units (e unit = parts in 10(exp 4) over s-process dominated isotopes are the most prominent features. Certain types of presolar grains show large enrichments in s-process isotopes, however, it was concluded on grounds of mass balance that incomplete digestion of such grains cannot explain the enrichments of r- and p-process isotopes in whole rocks of primitive chondrites. If the reported variability in r- and p-process isotope enrichments reflects the true isotopic characteristics of the whole rocks, the implications are quite profound. It would suggest the presence of large scale Mo isotopic heterogeneity within the solar accretion disk with likely collateral effects for other elements. However, such effects were not found for Ru isotopes, nor for Zr isotopes. Another recent Mo isotopic study by multi collector ICP-MS could not confirm the reported deviations in Allende, Murchison or iron meteorites. Here, we present new results for the Mo isotopic composition of iron meteorites, chondrites and CAIs obtained by negative thermal ionization mass spectrometry (NTIMS). We discuss analytical aspects and the homogeneity of Mo isotopic compositions in solar system materials.

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

USGS Publications Warehouse

Yaofa, Jiang; Elswick, E.R.; Mastalerz, Maria

2008-01-01

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur ( 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in ??34S for sulfur species within and between the low-sulfur and high-sulfur coal. The ??34S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the ??34S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the ??34S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of ??34S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in ??34S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition. The ??34S values for fly ash from the high-sulfur Springfield coal (averaging 9.7???) are greatly enriched in 34S relative to those in the parent coal (averaging 2.2???). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the ??34S values for fly-ash samples from the low-sulfur Danville coal average 10.2???, only slightly enriched in 34S relative to those from the parent coal (average 7.5???). The ??34S values for bulk S determined directly from the fly-ash samples show close correspondence with the ??34S values for SO4- 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion. ?? 2007 Elsevier B.V. All rights reserved.

Seasonally Resolved Oxygen Isotope Paleoclimate Proxy in Tree-Ring Cellulose from the Southeastern U.S.

NASA Astrophysics Data System (ADS)

Miller, D. L.; Mora, C. I.; Grissino-Mayer, H. D.; Mock, C. J.

2004-12-01

Stable isotopes in precipitation reflect changes in climate, moisture source, and extreme events such as tropical cyclones, and an oxygen isotope proxy record of these changes through time and space is preserved in tree-ring cellulose. Extreme climate events such as droughts and hurricanes are formidable natural disasters in the southeastern United States, and considerable efforts have been made to understand factors controlling their frequency, whether natural or anthropogenic. Tree rings offer an unusually well-resolved, dateable record of climate events extending beyond modern or historical (documentary) records. Oxygen isotopes in alpha-cellulose of shallowly-rooted conifers predominately reflect the composition of precipitation. Tropical storm convection results in marked 18O depletion in storm precipitation, to -15‰ relative to source seawater (~0‰ ). The depletion increases towards the eyewall of the cyclone, however, isotopically depleted precipitation may extend outward many 100's of km. Storm water 18O depletion translates to soil water 18O depletion that may persist for many weeks until ameliorated by soil water evaporation. Tree growth during that time will take up the anomalous isotopic compositions. Distinctive earlywood (EW ~March-June) versus latewood (LW ~July-October) growth allows the rings to be resolved at an intra-annual (seasonal) scale. By comparison to average soil water, droughts result in 18O-enriched soil water compositions. Seasonal drought or years of continued drought will be similarly captured in the isotope compositions of tree-ring cellulose. A 227-year (1770-1997) seasonally-resolved record of tropical cyclone and drought activity was obtained from cross-sections of felled slash pines (Pinus elliottii Engelm.) and remnant longleaf pines (Pinus palustris Mill.) from southern Georgia. Interpretations of drought or hurricane events were tested by comparison with recent, detailed meteorological records. The 227-year record reveals most previously established hurricane events, including Florence (1953) and the Great Hurricane of 1780. Newly recognized tropical storms such as 1857 are also evident. Significant seasonal droughts such as 1955, 1927, 1904 and 1896, are observed for southeastern Georgia. Larger-scale climate oscillations appear to overprint the EW and LW isotope series, displaying periods of relatively large or small differences in EW and LW δ 18O values. The oscillations are interpreted to reflect dominant climate modes that influence moisture source or seasonal temperature variation. The tree-ring record potentially extends many centuries. A preliminary record through a portion of the North American "Little Ice Age" (1580-1650) indicates a significant reduction in tropical cyclone activity.

Do Hf isotopes in magmatic zircons represent those of their host rocks?

NASA Astrophysics Data System (ADS)

Wang, Di; Wang, Xiao-Lei; Cai, Yue; Goldstein, Steven L.; Yang, Tao

2018-04-01

Lu-Hf isotopic system in zircon is a powerful and widely used geochemical tracer in studying petrogenesis of magmatic rocks and crustal evolution, assuming that zircon Hf isotopes can represent initial Hf isotopes of their parental whole rock. However, this assumption may not always be valid. Disequilibrium partial melting of continental crust would preferentially melt out non-zircon minerals with high time-integrated Lu/Hf ratios and generate partial melts with Hf isotope compositions that are more radiogenic than those of its magma source. Dissolution experiments (with hotplate, bomb and sintering procedures) of zircon-bearing samples demonstrate this disequilibrium effect where partial dissolution yielded variable and more radiogenic Hf isotope compositions than fully dissolved samples. A case study from the Neoproterozoic Jiuling batholith in southern China shows that about half of the investigated samples show decoupled Hf isotopes between zircons and the bulk rocks. This decoupling could reflect complex and prolonged magmatic processes, such as crustal assimilation, magma mixing, and disequilibrium melting, which are consistent with the wide temperature spectrum from ∼630 °C to ∼900 °C by Ti-in-zircon thermometer. We suggest that magmatic zircons may only record the Hf isotopic composition of their surrounding melt during crystallization and it is uncertain whether their Hf isotopic compositions can represent the primary Hf isotopic compositions of the bulk magmas. In this regard, using zircon Hf isotopic compositions to trace crustal evolution may be biased since most of these could be originally from disequilibrium partial melts.

Oxygen Isotope Measurements of a Rare Murchison Type A CAI and Its Rim

NASA Technical Reports Server (NTRS)

Matzel, J. E. P.; Simon, J. I.; Hutcheon, I. D.; Jacobsen, B.; Simon, S. B.; Grossman, L.

2013-01-01

Ca-, Al-rich inclusions (CAIs) from CV chondrites commonly show oxygen isotope heterogeneity among different mineral phases within individual inclusions reflecting the complex history of CAIs in both the solar nebula and/or parent bodies. The degree of isotopic exchange is typically mineral-specific, yielding O-16-rich spinel, hibonite and pyroxene and O-16-depleted melilite and anorthite. Recent work demonstrated large and systematic variations in oxygen isotope composition within the margin and Wark-Lovering rim of an Allende Type A CAI. These variations suggest that some CV CAIs formed from several oxygen reservoirs and may reflect transport between distinct regions of the solar nebula or varying gas composition near the proto-Sun. Oxygen isotope compositions of CAIs from other, less-altered chondrites show less intra-CAI variability and 16O-rich compositions. The record of intra-CAI oxygen isotope variability in CM chondrites, which commonly show evidence for low-temperature aqueous alteration, is less clear, in part because the most common CAIs found in CM chondrites are mineralogically simple (hibonite +/- spinel or spinel +/- pyroxene) and are composed of minerals less susceptible to O-isotopic exchange. No measurements of the oxygen isotope compositions of rims on CAIs in CM chondrites have been reported. Here, we present oxygen isotope data from a rare, Type A CAI from the Murchison meteorite, MUM-1. The data were collected from melilite, hibonite, perovskite and spinel in a traverse into the interior of the CAI and from pyroxene, melilite, anorthite, and spinel in the Wark-Lovering rim. Our objectives were to (1) document any evidence for intra-CAI oxygen isotope variability; (2) determine the isotopic composition of the rim minerals and compare their composition(s) to the CAI interior; and (3) compare the MUM-1 data to oxygen isotope zoning profiles measured from CAIs in other chondrites.

Cosmic-ray isotopic composition of C, N, O, Ne, Mg, Si nuclei in the energy range 50-200 MeV per nucleon measured by the Voyager spacecraft during the solar minimum period

NASA Technical Reports Server (NTRS)

Lukasiak, A.; Ferrando, P.; Mcdonald, F. B.; Webber, W. R.

1994-01-01

The isotopic composition of C, N, O, Ne, Mg, Si cosmic ray nuclei has been measured in the energy range 50-200 MeV per nucleon using data collected by the High-Energy Telescope of the cosmic-ray subsystem experiment on the Voyager 1 and 2 spacecraft. These data were collected during the period of minimum solar activity in 1986-1988 at an average distance of 27 AU with an effective solar modulation that was much less than at the Earth. The isotope analysis, based on the energy loss - total energy method, has a mass resolution of 0.2 amu for carbon and 0.4 amu at silicon. We find a (C-13)/(C-12) ratio slightly lower and a (O-18)/(O-16) ratio slightly enhanced over their solar system value. We also observe the previously reported enhancement of the (Ne-22)/(Ne-20) ratio relative to solar at the cosmic-ray source but only a weak, if any, enhancement of the (Mg-25)/(Mg-24), (Mg-26)/(Mg 24), and (Si-30)/(Si-28) ratios.

Variability of 13C-labeling in plant leaves.

PubMed

Nguyen Tu, Thanh Thuy; Biron, Philippe; Maseyk, Kadmiel; Richard, Patricia; Zeller, Bernd; Quénéa, Katell; Alexis, Marie; Bardoux, Gérard; Vaury, Véronique; Girardin, Cyril; Pouteau, Valérie; Billiou, Daniel; Bariac, Thierry

2013-09-15

Plant tissues artificially labeled with (13)C are increasingly used in environmental studies to unravel biogeochemical and ecophysiological processes. However, the variability of (13)C-content in labeled tissues has never been carefully investigated. Hence, this study aimed at documenting the variability of (13)C-content in artificially labeled leaves. European beech and Italian ryegrass were subjected to long-term (13)C-labeling in a controlled-environment growth chamber. The (13)C-content of the leaves obtained after several months labeling was determined by isotope ratio mass spectrometry. The (13)C-content of the labeled leaves exhibited inter- and intra-leaf variability much higher than those naturally occurring in unlabeled plants, which do not exceed a few per mil. This variability was correlated with labeling intensity: the isotope composition of leaves varied in ranges of ca 60‰ and 90‰ for experiments that led to average leaf (13)C-content of ca +15‰ and +450‰, respectively. The reported variability of isotope composition in (13)C-enriched leaves is critical, and should be taken into account in subsequent experimental investigations of environmental processes using (13)C-labeled plant tissues. Copyright © 2013 John Wiley & Sons, Ltd.

Exploring the Potential of Laser Ablation Carbon Isotope Analysis for Examining Ecology during the Ontogeny of Middle Pleistocene Hominins from Sima de los Huesos (Northern Spain).

PubMed

Garcia, Nuria; Feranec, Robert S; Passey, Benjamin H; Cerling, Thure E; Arsuaga, Juan Luis

2015-01-01

Laser ablation of tooth enamel was used to analyze stable carbon isotope compositions of teeth of hominins, red deer, and bears from middle Pleistocene sites in the Sierra de Atapuerca in northern Spain, to investigate the possibility that this technique could be used as an additional tool to identify periods of physiological change that are not detectable as changes in tooth morphology. Most of the specimens were found to have minimal intra-tooth variation in carbon isotopes (< 2.3‰), suggesting isotopically uniform diets through time and revealing no obvious periods of physiological change. However, one of the two sampled hominin teeth displayed a temporal carbon isotope shift (3.2‰) that was significantly greater than observed for co-occurring specimens. The δ13C value of this individual averaged about -16‰ early in life, and -13‰ later in life. This isotopic change occurred on the canine crown about 4.2 mm from the root, which corresponds to an approximate age of two to four years old in modern humans. Our dataset is perforce small owing to the precious nature of hominid teeth, but it demonstrates the potential utility of the intra-tooth isotope profile method for extracting ontogenetic histories of human ancestors.

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.

Isotopic variability of cave bears (δ15N, δ13C) across Europe during MIS 3

NASA Astrophysics Data System (ADS)

Krajcarz, Magdalena; Pacher, Martina; Krajcarz, Maciej T.; Laughlan, Lana; Rabeder, Gernot; Sabol, Martin; Wojtal, Piotr; Bocherens, Hervé

2016-01-01

Collagen, the organic fraction of bone, records the isotopic parameters of consumed food for carbon (δ13C) and nitrogen (δ15N). This relationship of isotopic signature between diet and tissue is an important tool for the study of dietary preferences of modern and fossil animal species. Since the first information on the isotopic signature of cave bear was reported, numerous data from Europe have become available. The goal of this work is to track the geographical variation of cave bear collagen isotopic values in Europe during Marine Isotopic Stage 3 (about 60,000-25,000 yr BP). In this study the results of new δ13C and δ15N isotopic analyses of cave bear collagen from four Central-Eastern European sites are presented, as well as a review of all published isotopic data for cave bears of the same period. The main conclusion is a lack of geographical East-West pattern in the variations of δ13C and δ15N values of cave bear collagen. Moreover, no relationship was found between cave bear taxonomy and isotopic composition. The cave bears from Central-Eastern Europe exhibit δ13C and δ15N values near the average of the range of Central, Western and Southern European cave bears. Despite the fact that most cave bear sites follow an altitudinal gradient, separate groups of sites exhibit shift in absolute values of δ13C, what disturbs an altitude-related isotopic pattern. The most distinct groups are: high Alpine sites situated over 1500 m a.s.l. - in terms of δ13C; and two Romanian sites Peştera cu Oase and Urşilor - in case of δ15N. Although the cave bear isotopic signature is driven by altitude, the altitudinal adjustment of isotopic data is not enough to explain the isotopic dissimilarity of these cave bears. The unusually high δ15N signature of mentioned Romanian sites is an isolated case in Europe. Cave bears from relatively closely situated Central-Eastern European sites and other Romanian sites are more similar to Western European than to Romanian populations in terms of isotopic composition, and probably ecology.

Geochemical and NdSr isotopic composition of deep-sea turbidites: Crustal evolution and plate tectonic associations

NASA Astrophysics Data System (ADS)

McLennan, S. M.; Taylor, S. R.; McCulloch, M. T.; Maynard, J. B.

1990-07-01

Petrographic, geochemical, and isotopic data for turbidites from a variety of tectonic settings exhibit considerable variability that is related to tectonic association. Passive margin turbidites (Trailing Edge, Continental Collision) display high framework quartz (Q) content in sands, evolved major element compositions (high Si/Al, K/Na), incompatible element enrichments (high Th/Sc, La/Sc, La/Yb), negative Eu-anomalies and variable Th/U ratios. They have low 143Nd /144Nd and high 87Sr /86Sr ( ɛNd = -26 to -10; 87Sr /86Sr = 0.709 to 0.734 ), indicating a dominance of old upper crustal sources. Active margin settings (Fore Arc, Continental Arc, Back Arc, Strike Slip) commonly exhibit quite different compositions. Th/Sc varies from <0.01 to 1.8, and ɛNd varies from -13.8 to +8.3. Eu-anomalies range from no anomaly ( Eu/Eu ∗ = 1.0 ) to Eu-depletions typical of post-Archean shales ( Eu/Eu ∗ = 0.65 ). Active margin data are explained by mixtures of young arc-derived material, with variable composition and old upper crustal sources. Major element data indicate that passive margin turbidites have experienced more severe weathering histories than those from active settings. Most trace elements are enriched in muds relative to associated sands because of dilution effects from quartz and calcite and concentration of trace elements in clays. Exceptions include Zr, Hf (heavy mineral influence) and Tl (enriched in feldspar) which display enrichments in sands. Active margin sands commonly exhibit higher Eu/Eu ∗ than associated muds, resulting from concentration of plagioclase during sorting. Some associated sands and muds, especially from active settings, have systematic differences in Th/Sc ratios and Nd-isotopic composition, indicating that various provenance components may separate into different grain-size fractions during sedimentary sorting processes. Trace element abundances of modern turbidites, from both active and passive settings, differ from Archean turbidites in several important ways. Modern turbidites have less uniformity, for example, in Th/Sc ratios. On average, modern turbidites have greater depletions in Eu (lower Eu/Eu ∗) than do Archean turbidites, suggesting that the processes of intracrustal differentiation (involving plagioclase fractionation) are of greater importance for crustal evolution at modern continental margins than they were during the Archean. Modern turbidites do not display HREE depletion, a feature commonly seen in Archean data. HREE depletion ( Gd N/Yb N > 2.0 ) in Archean sediments results from incorporation of felsic igneous rocks that were in equilibrium (or their sources were in equilibrium) with garnet sometime in their history. Absence of HREE depletion at modern continental margins suggests that processes of crust formation (or mantle source compositions) may have differed. Differences in trace element abundances for Archean and modern turbidites add support to suggestions that upper continental crust compositions and major processes responsible for continental crust differentiation differed during the Archean. Neodymium model ages, thought to approximate average provenance age, are highly variable ( TDMND = 0-2.6 Ga) in modern turbidites, in contrast with studies that indicate Nd-model ages of lithified Phanerozoic sediment are fairly constant at about 1.5-2.0 Ga. This variability indicates that continental margin sediments incorporate new mantle-derived components, as well as continental crust of widely varying age, during recycling. The apparent dearth of ancient sediments with Nd-model age similar to stratigraphic age supports the suggestion that preservation potential of sediments is related to tectonic setting. Many samples from active settings have isotopic compositions similar to or only slightly evolved from mantle-derived igneous rocks. Subduction of active margin turbidites should be considered in models of crust-mantle recycling. For short-term recycling, such as that postulated for island arc petrogenesis, arc-derived turbidites cannot be easily recognized as a source component because of the lack of time available for isotopic evolution. If turbidites were incorporated into the sources of ocean island volcanics, the isotopic signatures would be considerably more evolved since most models call for long mantle storage times (1.0-2.0 Ga), prior to incorporation. Four provenance components are recognized on the basis of geochemistry and Nd-isotopic composition: (1) Old Upper Continental Crust (old igneous/metamorphic terranes, recycled sediment); (2) Young Undifferentiated Arc (young volcanic/plutonic source that has not experienced plagioclase fractionation); (3) Young Differentiated Arc (young volcanic/plutonic source that has experienced plagioclase fractionation); (4) MORB (minor). Relative proportions of these components are influenced by the plate tectonic association of the provenance and are typically (but not necessarily) reflected in the depositional basin. Provenance of quartzose (mainly passive settings) and non-quartzose (mainly active settings) turbidites can be characterized by bulk composition (e.g., Th/Sc) and Nd-isotopic composition (reflecting age).

Carbon Composition of Particulate Organic Carbon in the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Rogers, K.; Montoya, J. P.; Weber, S.; Bosman, S.; Chanton, J.

2016-02-01

The Deepwater Horizon blowout released 5.0x1011 g C from gaseous hydrocarbons and up to 6.0x1011g C from oil into the water column. Another carbon source, adding daily to the water column, leaks from the natural hydrocarbon seeps that pepper the seafloor of the Gulf of Mexico. How much of this carbon from the DWH and natural seeps is assimilated into particulate organic carbon (POC) in the water column? We filtered seawater collected in 2010, 2012, and 2013 from seep and non-seep sites, collecting POC on 0.7µm glass microfiber filters and analyzing the POC for stable and radiocarbon isotopes. Mixing models based on carbon isotopic endmembers of methane, oil, and modern production were used to estimate the percentage of hydrocarbon incorporated into POC. Significant differences were seen between POC from shallow and deep waters and between POC collected from seep, non-seep, and blowout sites; however yearly differences were not as evident suggesting the GOM has a consistent supply of depleted carbon. Stable carbon isotopes signatures of POC in the Gulf averaged -23.7±2.5‰ for shallow samples and -26.65±2.9‰ for deep POC samples, while radiocarbon signatures averaged -100.4±146.1‰ for shallow and -394.6±197‰ for deep samples. POC in the northern Gulf are composed of 23-91% modern carbon, 2-21% methane, and 0-71% oil. Oil plays a major role in the POC composition of the GOM, especially at the natural seep GC600.

Lead Contamination and Source Characterization in Soils Around a Lead-Zinc Smelting Plant in a Near-Urban Environment in Baoji, China.

PubMed

Deng, Wenbo; Li, Xuxiang; An, Zhisheng; Yang, Liu

2016-11-01

Economic reforms in China since 1978 have promoted nationwide socioeconomic advancement but led to a considerable amount of environmental pollution. The distribution and sources of Pb in a typical peri-urban industrial part of Baoji, China, were assessed by determining the Pb contents and isotopic compositions in 52 topsoil samples from the study area. The topsoil samples were polluted averagely with 40.88 mg Pb kg -1 , was 1.86 times higher than the Pb content of local background soil (22.04 mg kg -1 ). Pb isotopic compositions were determined by analyzing samples prepared using total digestion and acid extraction methods. Radiogenic isotopes contributed more to the Pb concentrations in the acid extracts than in the total digests. This was shown by the 207/206 Pb and 208/206 Pb ratios, which were 0.845-0.88 and 2.088-2.128, respectively, in the acid extracts and 0.841-0.875 and 2.086-2.125, respectively, in the total digests. This indicates that anthropogenic sources of Pb could be identified more sensitively in acid extracts than in total digests. The Pb isotope ratios showed that burning coal and smelting ore are the predominant anthropogenic sources of Pb in the study area, i.e., a lead-zinc smelter and a coking plant are major sources of Pb in the study area.

Abundance and Isotopic Composition of Gases in the Martian Atmosphere: First Results from the Mars Curiosity Rover

NASA Technical Reports Server (NTRS)

Mahaffy, Paul; Webster, Chris R.; Atreya, Sushil K.; Franz, Heather; Wong, Michael; Conrad, Pamela G.; Harpold, Dan; Jones, John J.; Leshin, Laurie, A.; Manning, Heidi;

[δ¹⁵N-NO₃⁻ and δ¹⁸O-NO₃⁻ Tracing of Nitrate Sources in Beijing Urban Rivers].

PubMed

Zhao, Qing-liang; Ma, Hui-ya; Ren, Yu-fen; Wang, Xiao-ke; Peng, Jian-feng; He, Cheng-wu; Wu, Jun-hang; Liu, Meng-zhen; Yan, Miao-miao

2016-05-15

In order to quantitatively identify sources of nitrate pollution in Beijing urban area and provide effective guidance for relevant departments to control the pollution of Beijing rivers, δ¹⁵N-NO₃⁻ and δ¹⁸O-NO₃⁻ isotope tracing method was used to analyze the composition of nitrogen and oxygen stable isotopes from nitrate in Beijing urban river. Besides, stable isotope mixing model was adopted to track nitrogen sources of nitrate in Beijing urban rivers and the contribution rates of respective pollution sources were evaluated. The results showed that: (1) NO₃⁻-N pollution was the main inorganic nitrogen pollution in Beijing rivers and pollution of downstream was more serious than that of upstream. (2) δ¹⁵N-NO₃⁻ in Beijing urban surface rivers was in range of 6.26 per thousand-24.94 per thousand, while δ¹⁸O-NO₃⁻ ranged -0.41 per thousand-11.74 per thousand; δ¹⁵N-NO₃⁻ increased from upstream to downstream along the flow of the surface water. (3) The nitrate pollution composition of Beijing rivers could be gained from the stable isotope mixing model. The average contribution rates of manure and sewage, soil nitrate and atmospheric deposition were 61.2%, 31.5% and 7.3%, respectively.

A synthesis of thermokarst lake water balance in high-latitude regions of North America from isotope tracers

USGS Publications Warehouse

MacDonald, Lauren A.; Wolfe, Brent B.; Turner, Kevin W.; Anderson, Lesleigh; Arp, Christopher D.; Birks, Jean; Bouchard, Frédéric; Edwards, Thomas W.D.; Farquharson, Nicole; Hall, Roland I.; McDonald, Ian; Narancic, Biljana; Ouimet, Chantal; Pienitz, Reinhard; Tondu, Jana; White, Hilary

2017-01-01

Numerous studies utilizing remote sensing imagery and other methods have documented that thermokarst lakes are undergoing varied hydrological transitions in response to recent climate changes, from surface area expansion to drainage and evaporative desiccation. Here, we provide a synthesis of hydrological conditions for 376 lakes of mainly thermokarst origin across high-latitude North America. We assemble surface water isotope compositions measured during the past decade at five lake-rich landscapes including Arctic Coastal Plain (Alaska), Yukon Flats (Alaska), Old Crow Flats (Yukon), northwestern Hudson Bay Lowlands (Manitoba), and Nunavik (Quebec). These landscapes represent the broad range of thermokarst environments by spanning gradients in meteorological, permafrost, and vegetation conditions. An isotope framework was established based on flux-weighted long-term averages of meteorological conditions for each lake to quantify water balance metrics. The isotope composition of source water and evaporation-to-inflow ratio for each lake were determined, and the results demonstrated a substantial array of regional and subregional diversity of lake hydrological conditions. Controls on lake water balance and how these vary among the five landscapes and with differing environmental drivers are assessed. Findings reveal that lakes in the Hudson Bay Lowlands are most vulnerable to evaporative desiccation, whereas those in Nunavik are most resilient. However, we also identify the complexity in predicting hydrological responses of these thermokarst landscapes to future climate change.

Tracing subducted crustal materials in the mantle by using magnesium isotopes

NASA Astrophysics Data System (ADS)

Teng, F. Z.

2016-12-01

Recent studies show that some continental basalt, mantle-metasomatised peridotite and cratonic eclogite have heterogeneous Mg isotopic compositions. These isotopically distinct Mg isotopic compositions have been explained by the incorporation of subducted materials in their mantle sources though the detailed mechanisms are still not well understood. In particular, how Mg-poor crustal materials can modify Mg isotopic systematics of Mg-rich mantle is unknown. Subduction zones are the most efficient sites for crust and mantle interactions, hence should be where the most prominent Mg isotopic variation occurs. However, to date, little is known on Mg isotope systematics in the subduction factory. Here I first review and report new Mg isotopic data for arc lava, subarc peridotite and the subducted slab (marine sediment, altered basalt and abyssal peridotite), then use them to constrain the origins of mantle Mg isotopic heterogeneity and lay the foundation for using Mg isotopes as new tools for tracing crust-mantle interactions. The main conclusions are 1) fluid-rock interactions can modify Mg isotopic systematics of abyssal peridotites; 2) island arc lavas have non-MORB Mg isotopic compositions, reflecting distinct surbarc mantle Mg isotopic signature; 3) continental arcs have non-MORB Mg isotopic compositions, likely resulting from crustal contamination and 4) the isotopically heterogeneous continental basalts are mainly produced by mixing of isotopically distinct magmas instead of being partial melting products of metasomatised mantle peridotites.

The role of mantle-hybridization and crustal contamination in the petrogenesis of lithospheric mantle-derived alkaline rocks: constraints from Os and Hf isotopes

NASA Astrophysics Data System (ADS)

Mayer, B.; Jung, S.; Brauns, M.; Münker, C.

2018-06-01

The Rhön area as part of the Central European Volcanic Province (CEVP) hosts an unusual suite of Tertiary 24-Ma old hornblende-bearing alkaline basalts that provide insights into melting and fractionation processes within the lithospheric mantle. These chemically primitive to slightly evolved and isotopically (Sr, Nd, Pb) depleted basalts have slightly lower Hf isotopic compositions than respective other CEVP basalts and Os isotope compositions more radiogenic than commonly observed for continental intraplate alkaline basalts. These highly radiogenic initial 187Os/188Os ratios (0.268-0.892) together with their respective Sr-Nd-Pb isotopic compositions are unlikely to result from crustal contamination alone, although a lack of Os data for lower crustal rocks from the area and limited data for CEVP basalts or mantle xenoliths preclude a detailed evaluation. Similarly, melting of the same metasomatized subcontinental lithospheric mantle as inferred for other CEVP basalts alone is also unlikely, based on only moderately radiogenic Os isotope compositions obtained for upper mantle xenoliths from elsewhere in the province. Another explanation for the combined Nd, Sr and Os isotope data is that the lavas gained their highly radiogenic Os isotope composition through a mantle "hybridization", metasomatism process. This model involves a mafic lithospheric component, such as an intrusion of a sublithospheric primary alkaline melt or a melt derived from subducted oceanic material, sometime in the past into the lithospheric mantle where it metasomatized the ambient mantle. Later at 24 Ma, thermal perturbations during rifting forced the isotopically evolved parts of the mantle together with the peridotitic ambient mantle to melt. This yielded a package of melts with highly correlated Re/Os ratios and radiogenic Os isotope compositions. Subsequent movement through the crust may have further altered the Os isotope composition although this effect is probably minor for the majority of the samples based on radiogenic Nd and unradiogenic Sr isotope composition of the lavas. If the radiogenic Os isotope composition can be explained by a mantle-hybridization and metasomatism model, the isotopic compositions of the hornblende basalts can be satisfied by ca. 5-25% addition of the mafic lithospheric component to an asthenospheric alkaline magma. Although a lack of isotope data for all required endmembers make this model somewhat speculative, the results show that the Re-Os isotope system in continental basalts is able to distinguish between crustal contamination and derivation of continental alkaline lavas from isotopically evolved peridotitic lithosphere that was contaminated by mafic material in the past and later remelted during rifting. The Hf isotopic compositions are slightly less radiogenic than in other alkaline basalts from the province and indicate the derivation of the lavas from low Lu-Hf parts of the lithospheric mantle. The new Os and Hf isotope data constrain a new light of the nature of such metasomatizing agents, at least for these particular rocks, which represent within the particular volcanic complex the first product of the volcanism.

Isotopic signals of denitrification in a northern hardwood forested catchment

NASA Astrophysics Data System (ADS)

Wexler, Sarah; Goodale, Christine

2013-04-01

Water samples from streams, groundwater and precipitation were collected during summer from the hydrologic reference watershed (W3) at Hubbard Brook Experimental Forest in the White Mountains, New Hampshire, and analysed for d15N-NO3 and d18O-NO3. Despite very low nitrate concentrations (<0.5 to 8.8 uM NO3-) dual-isotopic signals of sources and processes were clearly distinguishable. The isotopic composition of nitrate from shallow groundwater showed evidence of dual isotopic fractionation in line with denitrification, with a positive relationship between nitrogen and oxygen isotopic composition, a regression line slope of 0.76 (r2 = 0.68), and an empirical isotope enrichment factor of ɛP-S 15N-NO3 -12.7%. The isotopic composition of riparian groundwater nitrate from time-series samples showed variation in processes over a small spatial scale. The expected isotopic composition of nitrate sources in the watershed was used to distinguish nitrate in rain and nitrate from nitrification of both rainfall ammonium and ammonium from mineralised soil organic nitrogen. Evidence of oxygen exchange with water during nitrification was seen in the isotopic composition of stream and shallow groundwater nitrate. The isotopic composition of streamwater nitrate following a period of storms indicated that 25% of nitrate in the streamwater was of atmospheric origin. This suggests rapid infiltration of rainfall via vertical bypass flow to the saturated zone, enabling transport of atmospheric nitrate to the stream channels. Across the Hubbard Brook basin, the isotopic composition of nitrate from paired samples from watersheds 4-7 indicated a switch between a nitrification and assimilation dominated system, to a system influenced by rainfall nitrogen inputs and denitrification. The dual isotope approach has revealed evidence of denitrification of nitrate from different sources at low concentrations at Hubbard Brook during summer. This isotopic evidence deepens our understanding of the significance and spatial variability of denitrification in environments with low levels of nitrate, represented by this northern hardwood forested catchment.

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

Valysaev, B.M.; Erokhin, V.E.; Grinchenko, Y.I.

A study has been made of the isotopic composition of the carbon in methane and carbon dioxide, as well as hydrogen in the methane, in the gases of mud volcanoes, for all main mud volcano areas in the USSR. The isotopic composition of carbon and hydrogen in methane shows that the gases resemble those of oil and gas deposits, while carbon dioxide of these volcanoes has a heavier isotopic composition with a greater presence of ''ultraheavy'' carbon dioxide. By the chemical and isotopic composition of gases, Azerbaidzhan and South Sakhalin types of mud volcano gases have been identified, as wellmore » as Bulganak subtypes and Akhtala and Kobystan varieties. Correlations are seen between the isotopic composition of gases and the geological build of mud volcano areas.« less

Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data.

PubMed

Estrada, Nubia Luz; Böhlke, J K; Sturchio, Neil C; Gu, Baohua; Harvey, Greg; Burkey, Kent O; Grantz, David A; McGrath, Margaret T; Anderson, Todd A; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B; Jackson, W Andrew

2017-10-01

Natural perchlorate (ClO 4 - ) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ 37 Cl, δ 18 O, and Δ 17 O), indicating that ClO 4 - may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO 4 - , but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO 4 - in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO 4 - was transported from solutions into plants similarly to NO 3 - but preferentially to Cl - (4-fold). The ClO 4 - isotopic compositions of initial ClO 4 - reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO 4 - uptake or accumulation. The ClO 4 - isotopic composition of field-grown snap beans was also consistent with that of ClO 4 - in varying proportions from irrigation water and precipitation. NO 3 - uptake had little or no effect on NO 3 - isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε ( 15 N/ 18 O) ratio of 1.05 was observed between NO 3 - in hydroponic solutions and leaf extracts, consistent with partial NO 3 - reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO 4 - in commercial produce, as illustrated by spinach, for which the ClO 4 - isotopic composition was similar to that of indigenous natural ClO 4 - . Our results indicate that some types of plants can accumulate and (presumably) release ClO 4 - to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO 4 - and NO 3 - in plants may be useful for determining sources of fertilizers and sources of ClO 4 - in their growth environments and consequently in food supplies. Copyright © 2017 Elsevier B.V. All rights reserved.

Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data

USGS Publications Warehouse

Estrada, Nubia Luz; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua; Harvey, Greg; Burkey, Kent O.; Grantz, David A.; McGrath, Margaret T.; Anderson, Todd A.; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B.; Jackson, W. Andrew

2017-01-01

Natural perchlorate (ClO4−) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ37Cl, δ18O, and Δ17O), indicating that ClO4− may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO4−, but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO4− in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO4− was transported from solutions into plants similarly to NO3− but preferentially to Cl− (4-fold). The ClO4− isotopic compositions of initial ClO4− reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO4− uptake or accumulation. The ClO4− isotopic composition of field-grown snap beans was also consistent with that of ClO4− in varying proportions from irrigation water and precipitation. NO3− uptake had little or no effect on NO3− isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε (15N/18O) ratio of 1.05 was observed between NO3− in hydroponic solutions and leaf extracts, consistent with partial NO3− reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO4− in commercial produce, as illustrated by spinach, for which the ClO4− isotopic composition was similar to that of indigenous natural ClO4−. Our results indicate that some types of plants can accumulate and (presumably) release ClO4− to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO4−and NO3− in plants may be useful for determining sources of fertilizers and sources of ClO4− in their growth environments and consequently in food supplies.

Determination of compound-specific Hg isotope ratios from transient signals using gas chromatography coupled to multicollector inductively coupled plasma mass spectrometry (MC-ICP/MS).

PubMed

Dzurko, Mark; Foucher, Delphine; Hintelmann, Holger

2009-01-01

MeHg and inorganic Hg compounds were measured in aqueous media for isotope ratio analysis using aqueous phase derivatization, followed by purge-and-trap preconcentration. Compound-specific isotope ratio measurements were performed by gas chromatography interfaced to MC-ICP/MS. Several methods of calculating isotope ratios were evaluated for their precision and accuracy and compared with conventional continuous flow cold vapor measurements. An apparent fractionation of Hg isotopes was observed during the GC elution process for all isotope pairs, which necessitated integration of signals prior to the isotope ratio calculation. A newly developed average peak ratio method yielded the most accurate isotope ratio in relation to values obtained by a continuous flow technique and the best reproducibility. Compound-specific isotope ratios obtained after GC separation were statistically not different from ratios measured by continuous flow cold vapor measurements. Typical external uncertainties were 0.16 per thousand RSD (n = 8) for the (202)Hg(/198)Hg ratio of MeHg and 0.18 per thousand RSD for the same ratio in inorganic Hg using the optimized operating conditions. Using a newly developed reference standard addition method, the isotopic composition of inorganic Hg and MeHg synthesized from this inorganic Hg was measured in the same run, obtaining a value of delta (202)Hg = -1.49 +/- 0.47 (2SD; n = 10). For optimum performance a minimum mass of 2 ng per Hg species should be introduced onto the column.

Analytical pyrolysis and stable isotope analyses reveal past environmental changes in coralloid speleothems from Easter Island (Chile).

PubMed

Miller, Ana Z; De la Rosa, José M; Jiménez-Morillo, Nicasio T; Pereira, Manuel F C; González-Pérez, José A; Calaforra, José M; Saiz-Jimenez, Cesareo

2016-08-26

This study comprises an innovative approach based on the combination of chromatography (analytical pyrolysis and pyrolysis compound-specific isotope analysis (Py-CSIA)), light stable isotopes, microscopy and mineralogy analyses to characterize the internal layering of coralloid speleothems from the Ana Heva lava tube in Easter Island (Chile). This multidisciplinary proxy showed that the speleothems consist of banded siliceous materials of low crystallinity with different mineralogical compositions and a significant contribution of organic carbon. Opal-A constitutes the outermost grey layer of the coralloids, whereas calcite and amorphous Mg hydrate silicate are the major components of the inner whitish and honey-brown layers, respectively. The differences found in the mineralogical, elemental, molecular and isotopic composition of these distinct coloured layers are related to environmental changes during speleothem development. Stable isotopes and analytical pyrolysis suggested alterations in the water regime, pointing to wetter conditions during the formation of the Ca-rich layer and a possible increase in the amount of water dripping into the cave. The trend observed for δ(15)N values suggested an increase in the average temperature over time, which is consistent with the so-called climate warming during the Holocene. The pyrolysis compound-specific isotope analysis of each speleothem layer showed a similar trend with the bulk δ(13)C values pointing to the appropriateness of direct Py-CSIA in paleoenvironmental studies. The δ(13)C values for n-alkanes reinforced the occurrence of a drastic environmental change, indicating that the outermost Opal layer was developed under drier and more arid environmental conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

NASA Astrophysics Data System (ADS)

McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

2004-10-01

Long-chain, odd-carbon-numbered C25 to C35 n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (

Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

NASA Astrophysics Data System (ADS)

McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

2004-10-01

Long-chain, odd-carbon-numbered C25 to C35n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (

Characteristics of lead isotope ratios and elemental concentrations in PM 10 fraction of airborne particulate matter in Shanghai after the phase-out of leaded gasoline

NASA Astrophysics Data System (ADS)

Zheng, Jian; Tan, Mingguang; Shibata, Yasuyuki; Tanaka, Atsushi; Li, Yan; Zhang, Guilin; Zhang, Yuanmao; Shan, Zuci

The stable lead (Pb) isotope ratios and the concentrations of 23 elements, including heavy metals and toxic elements, were measured in the PM 10 airborne particle samples collected at seven monitoring sites in Shanghai, China, to evaluate the current elemental compositions and local airborne Pb isotope ratio characteristics. Some source-related samples, such as cement, coal and oil combustion dust, metallurgic dust, vehicle exhaust particles derived from leaded gasoline and unleaded gasoline, and polluted soils were analyzed for their Pb content and isotope ratio and compared to those observed in PM 10 samples. Airborne Pb concentration ranged from 167 to 854 ng/m 3 in the seven monitored sites with an average of 515 ng/m 3 in Shanghai, indicating that a high concentration of Pb remains in the air after the phasing out of leaded gasoline. Lead isotopic compositions in airborne particles ( 207Pb/ 206Pb, 0.8608±0.0018; 208Pb/ 206Pb, 2.105±0.005) are clearly distinct from the vehicle exhaust particles ( 207Pb/ 206Pb, 0.8854±0.0075; 208Pb/ 206Pb, 2.145±0.006), suggesting that the automotive lead is not currently the major component of Pb in the air. By using a binary mixing equation, a source apportionment based on 207Pb/ 206Pb ratios, indicates that the contribution from automotive emission to the airborne Pb is around 20%. The Pb isotope ratios obtained in the source-related samples confirmed that the major emission sources are metallurgic dust, coal combustion, and cement.

Isotope variations of dissolved Zn in the Rio Grande watershed, USA: The role of adsorption on Zn isotope composition

NASA Astrophysics Data System (ADS)

Szynkiewicz, Anna; Borrok, David M.

2016-01-01

In order to better understand the factors influencing zinc (Zn) isotope composition in hydrological systems, we analyzed the δ66Zn of dissolved Zn in the streams and groundwater of the Upper and Middle Rio Grande watershed in Colorado and New Mexico, United States. The stream water samples have a wider variation of δ66Zn (-0.57 to + 0.41 ‰ relative to the JMC 3-0749-Lyon standard) than groundwater samples (-0.13 to + 0.12 ‰) and than samples from streams that are in close proximity to abandoned mining sites (+0.24 to + 0.40 ‰). Regional changes of bedrock geology, from primarily igneous rocks to primarily sedimentary rocks, have no resolvable effect on the δ66Zn of aqueous samples. Instead, an increase in water pH from 7.5 to 8.5 corresponds to a considerable decrease in the δ66Zn of dissolved Zn (R2 = - 0.37, p = 0.003, n = 22). Consequently, we link the observed Zn isotope variations to the process of adsorption of Zn onto suspended sediment and bedrock minerals (average Δ66Znadsorbed-dissolved = + 0.31 ‰). Our results are in good agreement with previous experimental and empirical studies suggesting that Zn adsorption leads to a residual dissolved pool enriched in light Zn isotopes. Given that anthropogenic Zn sources can also be responsible for lowering of δ66Zn, and may overlap with the pH/adsorption effect on δ66Zn, the latter needs to be carefully considered in future studies to differentiate between natural and anthropogenic factors influencing Zn isotopes in this and other aquatic systems.

Variable sulfur isotope composition of sulfides provide evidence for multiple sources of contamination in the Rustenburg Layered Suite, Bushveld Complex

NASA Astrophysics Data System (ADS)

Magalhães, Nivea; Penniston-Dorland, Sarah; Farquhar, James; Mathez, Edmond A.

2018-06-01

The Rustenburg Layered Suite (RLS) of the Bushveld Complex (BC) is famous for its platinum group element (PGE) ore, which is hosted in sulfides. The source of sulfur necessary to generate this type of mineralization is inferred to be the host rock of the intrusion. The RLS has a sulfur isotopic signature that indicates the presence of Archean surface-derived material (Δ33 S ≠ 0) in the magma. This signature, with an average value of Δ33 S = 0.112 ± 0.024 ‰, deviates from the expected Δ33 S value of the mantle of 0 ± 0.008 ‰. Previous work suggested that this signature is uniform throughout the RLS, which contrasts with radiogenic isotopes which vary throughout the igneous stratigraphy of the RLS. In this study, samples from key intervals within the igneous stratigraphy were analyzed, showing that Δ33 S values vary in the same stratigraphic levels as Sr and Nd isotopes. However, the variation is not consistent; in some levels there is a positive correlation and in others a negative correlation. This observation suggests that in some cases distinct magma pulses contained assimilated sulfur from different sources. Textural analysis shows no evidence for late addition of sulfur. These results also suggest that it is unlikely that large-scale assimilation and/or efficient mixing of host rock material in a single magma chamber occurred during emplacement. The data do not uniquely identify the source of sulfur in the different layers of the RLS, but the variation in sulfur isotope composition and its relationship to radiogenic isotope data calls for a reevaluation of the models for the formation and evolution of the RLS, which has the potential to impact the knowledge of how PGE deposits form.

Zircon U-Pb chronology, geochemistry and Sr-Nd-Pb isotopic compositions of the Volcanic Rocks in the Elashan area, NW China: petrogenesis and tectonic implications

NASA Astrophysics Data System (ADS)

Zhou, H.; Wei, J.; Shi, W.; Li, P.; Chen, M.; Zhao, X.

2017-12-01

Elashan area is located in the intersection of the East Kunlun Orogenic Belt (EKOB) and the West Qinling Orogenic (WQOB). We present petrology, zircon U-Pb ages, whole-rock geochemistry and Sr-Nd-Pb isotopic compositions from the andesite and felsic volcanic rocks (rhyolite and rhyolitic tuffs) in Elashan group volcanic rock. The LA-ICP-MS zircon U-Pb age data indicate that the volcanic rocks are emplaced at 250 247 Ma. The volcanic rocks have high -K and aluminum - peraluminous characteristics, A/CNK = 1.07 1.82, δ ranges from 1.56 2.95, the main body is calc-alkaline rock. They are enriched in large ion lithophile elements (LILEs) and light rare earth elements (LREEs) and depleted in some high field strength elements (HFSEs, e.g., Nb, Ta, P and Ti), while having a flat heavy REE (HREEs) pattern. The ∑REE values of 178.68 to 298.11 ppm, average 230.50 ppm. The LREE/HREE values of 4.39 to 11.78 ppm, average 6.77 ppm. REE fractionation is obvious, REE distribution curve was right smooth, and have slightly negative Eu anomalies (Eu/Eu*=0.44-0.80, average 0.60), which as similar to the island arc volcanic rocks. The volcanic rocks have initial 87Sr/86Sr ratios of 0.71028-0.71232, ɛNd(t) values of -6.7 to -7.6, with T2DM-Nd ranging from 1561 to 1640 Ma. Pb isotopic composition (206 Pb / 204 Pb)t = 18.055 18.330, (207 Pb / 204 Pb)t = 15.586 15.618, (208 Pb / 204 Pb)t = 37.677 38.332. Geochemical and Sr-Nd-Pb isotopes indicates that Elashan group volcanic magma derived mainly from the lower crust. Elashan group volcanic rocks is the productive East Kunlun block and West Qinling block collision, which makes the thicken crust caused partial melting in the study area. The source rocks is probably from metamorphic sandstone of Bayankala. But with Y-Nb and Rb-(Y+Nb), R1-R2 and Rb/10-Hf-Ta*3 diagrams showing that intermediate-acid rocks mainly formed in volcanic arc-collision environment, probably the collision event is short , therefore rocks retain the original island arc properties. The formation age of intermediate -acidic volcanic rock can represent the time in which the end of transgressive and the beginning of intercontinental evolution in the northeastern Tibetan Plateau.

Hydrological responses of the Chihuahua Desert of Mexico to possible Heinrich Stadials: A study inferred from geochemistry and stable isotopes of lacustrine sediments

NASA Astrophysics Data System (ADS)

Quiroz-Jiménez, J. D.; Roy, P. D.; Lozano-SantaCruz, R.; López Balbiaux, N.; Girón-García, P.

2016-12-01

The Heinrich Stadials (H6-H1) were cooler intervals of different duration characterized by massive discharge of icebergs from the Laurentide Ice Sheet mainly through the Hudson Straight into the Atlantic Ocean. In this paper, we present a proxy record to infer hydrological responses of the Chihuahua Desert of Mexico to all the Heinrich Stadials (HS) from element ratios, CO3 abundance, and oxygen and carbon isotope compositions of lacustrine calcite of the sediments deposited between depths of 560-78 cm ( 66-8 ka) of a new core collected from the Santiaguillo Basin. Sediments deposited during different HS were identified by radiocarbon dating up to 27.3 ka, extrapolation of an average sediment rate and tuning the CO3 abundance record with insolation in rest of the sequence, and oxygen isotope composition of authigenic CO3. Proxies suggest that hydroclimate of the Chihuahua Desert of Mexico responded differently to different HS. The overall runoff and hence precipitation remained below average during H6, H4, H2 and H1. Both of them were above average during H5 and H3. Similarly, runoff during H4 showed the least variability and it was the most variable during H5. Except for H2, negative excursions in δ18O values suggest cooler conditions during all other HS. In general, dissolved HCO3- was mainly sourced from the atmospheric CO2 during arid intervals. Both the lake productivity and atmospheric CO2 influenced the carbon isotope composition of dissolved HCO3- during humid intervals. During the H2, δ13C values indicate dominant influence of lacustrine productivity. Similar to Chihuahua Desert of Mexico, speleothem records from Fort Stanton and Cave of the Bells (Asmerom et al., 2010; Wagner et al., 2010) showed that hydroclimate of southwest USA also experienced millennial-scale variability and some intervals were more homogeneous compared to others. We did not observe concurrency in proxy records of the Chihuahua Desert of Mexico and southwest USA. Instead, we observed a possible hemispheric link between hydroclimate of the Chihuahua Desert of Mexico and the East Asian Monsoon. Characterized by millennial-scale fluctuations, tendencies of runoff into the Santiaguillo Basin and intensity of the East Asian Monsoon inferred from speleothems from the Hulu Cave of China (Wang et al., 2001) across the six HS were similar.

Isotopic composition of recent shark teeth as a proxy for environmental conditions

NASA Astrophysics Data System (ADS)

Vennemann, T. W.; Hegner, E.; Cliff, G.; Benz, G. W.

2001-05-01

The O, C, and Sr isotope compositions of teeth from ten species, belonging to five families, and three orders of sharks were measured to determine the influence of habitat, diet, and possible species-specific fractionation effects on the isotopic composition of biogenic phosphate from fish. The sharks were recently caught in subtropical waters off the KwaZulu-Natal (KZN) coast of South Africa, as well as from cold waters in Prince William Sound (PWS), Alaska, and Victor Bay (VB), Nunavut, Canada. δ 18O values of tooth phosphate (δ 18O P) range from 20.9 to 23.5‰ for the KZN sharks. For most species the range in measured δ 18O P values is about 0.6‰, but it may be as high as 1.1‰ for different teeth from a single shark. Dentine and enameloid within individual teeth have no apparent differences in δ 18O P values. The δ 18O P values of the KZN shark teeth reflect the typical habitat of the studied species, primarily the thermal structure of the water column off KZN at depths between 20 and 280 m. The δ 18O P values of teeth from different Greenland sharks from VB and Pacific sleeper sharks from PWS are very homogeneous, averaging 25.8 and 24.7‰, respectively. These values appear to be in equilibrium with deep (>500 m) ocean waters in each case at temperatures of about -0.3°C or less. There is little discernable evidence for species-specific fractionation effects for the oxygen isotope composition of phosphate in the studied marine fish. The oxygen isotope composition of carbonate in apatite averages about 9.1‰ higher than corresponding δ 18O P values, in agreement with equilibrium fractionation between carbonate and phosphate, but with a large variance (1σ = ±1.5‰). δ 18O C values also vary by up to 1‰ between enameloid and dentine within single teeth, but in a non-systematic way. Differences in δ 13C values between carbonate in enameloid and dentine is also large (up to 8‰) but the δ 13C values vary systematically. Enameloid is always enriched in 13C compared to dentine and the 13C content increases with developmental stage of the teeth. δ 13C values measured for enameloid (1.6 to 4.8‰) appear to approach equilibrium with dissolved inorganic carbon in seawater. In contrast, δ 13C values for dentine range from -6.4 to -2.3‰ for KZN sharks, and -9.0 to -10.8‰ for the cold-water sleeper sharks, and are compatible with a predominantly dietary carbon source. The 87Sr/ 86Sr ratios of teeth from KZN sharks as well as those from PWS and VB are uniform, averaging 0.709167. Sr content varies from 1270 to 2100 ppm, a range that is similar to that in well preserved fossilized teeth. Seawater Sr is thus clearly incorporated in vivo. Concentrations of Sm and Nd are in the ppb range and contrast the ppm range in fossilized teeth, indicating a postmortem incorporation of rare earth elements in apatite of the teeth.

Tracing Cd, Zn and Pb pollution sources in bivalves using isotopes

NASA Astrophysics Data System (ADS)

Shiel, A. E.; Weis, D. A.; Orians, K. J.

2010-12-01

In a multi-tracer study, Cd, Zn and Pb isotopes (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are evaluated as tools to distinguish between natural and anthropogenic sources of these metals in bivalves from western Canada (British Columbia), the eastern USA, Hawaii and France. High Cd concentrations found in BC oysters have elicited economic and health concerns. The source of these high Cd levels is unknown but thought to be largely natural. High Cd levels in BC oysters are largely attributed to the natural upwelling of Cd-rich intermediate waters in the North Pacific as the δ114/110Cd (-0.69 to -0.09‰) and δ66/64Zn (0.28 to 0.36‰) values of BC oysters fall within the range reported for North Pacific seawater. Different contributions from anthropogenic sources account for the variability of Cd isotopic compositions of BC oysters; the lightest of these oysters are from the BC mainland. These oysters also have Pb isotopic compositions that reflect primarily anthropogenic sources (e.g., leaded and unleaded automotive gasoline and smelting of Pb ores, potentially historical). On the contrary, USA East Coast bivalves exhibit relatively light Cd isotopic compositions (δ114/110Cd = -1.20 to -0.54‰; lighter than reported for North Atlantic seawater) due to the high prevalence of industry on this coast. The Pb isotopic compositions of these bivalves indicate contributions from the combustion of coal. The large variability of environmental health among coastal areas in France is reflected in the broad range of Cd isotopic compositions exhibited by French bivalves (δ114/110Cd = -1.08 to -0.20‰). Oysters and mussels from the Marennes-Oléron basin and Gironde estuary have the lightest Cd isotopic compositions of the French oysters consistent with significant historical Cd emissions from the now-closed proximal Zn smelter. In these bivalves, significant declines in the Cd levels between 1984/7 and 2004/5 are not accompanied by a significant shift in the Cd isotopic composition toward natural values. The Mediterranean samples have isotopic compositions within error of the lighter end of the range reported for Mediterranean seawater. The Zn isotopic compositions of French oysters and mussels (δ66/64Zn = 0.39 to 0.46‰) are identical to those reported for North Atlantic seawater, with the exception of the much heavier compositions of oysters (δ66/64Zn = 1.03 to 1.15‰) from the polluted Gironde estuary. In agreement with Cd and Zn isotopic compositions, the Pb isotopic compositions of the French bivalves indicate primarily industrial (as opposed to automotive) sources; this is consistent with the collection of most of the French bivalve samples in 2004, after the complete phase-out of leaded gasoline in France. This study demonstrates the effective use of Cd and Zn isotopes to trace anthropogenic sources in the environment and the benefit of combining these tools with Pb isotope “fingerprinting” techniques to identify processes contributing metals. Use of these new geochemical tools requires site-specific knowledge of potential metal sources and their isotopic compositions.

Hadean Oceanography: Experimental Constraints on the Development of the Terrestrial Hydrosphere and the Origin of Life on Earth

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

Ryerson, F J

The oxygen isotopic compositions of the world's oldest mineral grains, zircon, have recently been used to infer the compositions of the rocks from which they crystallized. The results appear to require a source that had once experienced isotopic fractionation between clay minerals and liquid water, thereby implying the presence of liquid water at the Earth's surface prior to 4.4 billion years ago, less than 2 million years after accretion. This observation has important implications for the development of the Earth's continental crust. The inferred composition of the zircon source rock is directly dependent upon the oxygen isotopic fractionation between zirconmore » and melt, and zircon and water. These fractionation factors have not been determined experimentally, however, constituting the weak link in this argument. A series of experiments to measure these fractionation factors has been conducted. The experiments consist of finely powdered quartz, a polished single crystal of zircon and isotopically-enriched or isotopically normal water to provide a range of isotopic compositions. The experiments will be run until quartz is in isotopic equilibrium with water. Zircon was expected to partially equilibrate producing an oxygen isotopic diffusion profile perpendicular to the surface. Ion probe spot analysis of quartz and depth profiling of zircon will determine the bulk and surface isotopic compositions of the phases, respectively. The well-known quartz-water isotopic fractionation factors can be used to calculate the oxygen isotopic composition of the fluid, and with the zircon surface composition, the zircon-water fractionation factor. Run at temperatures up to 1000 C for as long as 500 hours have not produced diffusion profiles longer than 50 nm. The steep isotopic gradient at the samples surface precludes use of the diffusion profile for estimation on the surface isotopic composition. The short profiles may be the result of surface dissolution, although such dissolution cannot be resolved in SEM images. The sluggish nature of diffusion in zircon may require that fractionation factors be determined by direct hydrothermal synthesis of zircon rather than by mineral-fluid exchange.« less

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.

Vanadium isotopic composition of the sea squirt (Ciona savignyi).

PubMed

Nomura, Masao; Nakamura, Mana; Soeda, Ryosuke; Kikawada, Yoshikazu; Fukushima, Michiko; Oi, Takao

2012-09-01

Vanadium (V) in the sea squirt (Ciona savignyi) from Onagawa Bay, Miyagi, Japan, was isolated and purified through adsorption on a diamine resin and anion and cation exchanges after the dissolution of sea squirt samples with nitric acid and hydrogen peroxide. The (50)V/(51)V isotope ratio of V thus obtained was mass-spectrometrically determined to be from 2.51×10(-3) to 2.55×10(-3) with the average of 2.53×10(-3) by the thermal ionisation technique. This value agreed with those of vanadyl chloride and vanadyl nitrate both prepared from vanadyl sulphate (Wako Pure Chemical Industries, Ltd., Japan) and of V in coastal seawater (Shimokita Peninsula, Aomori, Japan) within experimental uncertainties (standard deviation of±0.04), which suggested that no appreciable V isotope fractionation occurs accompanying V uptake by the sea squirt from sea water.

A 16-ka oxygen-isotope record from Genggahai Lake on the northeastern Qinghai-Tibetan Plateau: Hydroclimatic evolution and changes in atmospheric circulation

NASA Astrophysics Data System (ADS)

Qiang, Mingrui; Song, Lei; Jin, Yanxiang; Li, Yuan; Liu, Li; Zhang, Jiawu; Zhao, Yan; Chen, Fahu

2017-04-01

Moisture source history and changes in atmospheric circulation are the most important attributes for portraying past climate changes and for estimating possible future trends. However, few climate records reflecting these attributes are available from the marginal zones of the Asian summer monsoon. Here, we present a record of the oxygen isotopic composition of authigenic carbonates (δ18Ocarb) of sequential sediments from Genggahai Lake in the northeastern Qinghai-Tibetan Plateau (QTP). Isotopic analyses were performed on the fine-grained carbonate fraction (<38 μm), mollusc shells, and stem encrustations from submerged plants. The stratigraphic variations of the δ18O record from the different carbonate components exhibit a remarkably similar pattern, probably reflecting the fact that δ18Ocarb variability was controlled primarily by changes in the oxygen isotopic composition of the lake water (δ18OLW). Disequilibrium effects and water temperature are precluded as major factors affecting the δ18Ocarb variations. Genggahai Lake is hydrologically open and characterized by a rapid discharge rate, as indicated by analysis of the hydrological setting of the lake system and by the observed significant positive correlation between δ18OLW and the oxygen isotopic composition of the inflowing water (δ18OI). Under such hydrological conditions, we argue that the isotopic signals of different moisture sources should be reflected in the carbonate isotopic composition. Furthermore, placing the δ18Ocarb record in the context of regional palaeoclimate archives, we found that the isotopic signals, particularly the negative shifts from the average values, cannot be interpreted consistently, despite a process of evaporative enrichment at the lake surface. During the early- to mid-Holocene, low δ18Ocarb values during 10.6-9.4 and 7.4-6.3 ka were associated with higher lake levels, and thus the record may have been significantly affected by a strengthened Asian summer monsoon at those times and hence by a positive moisture balance. Isotopic depletions with similar magnitudes occurred at 15-14.5, 13.8-13.3, 12.5-11.4, 5.3-4.8, 3.7-3.4, 2.8-2.3, 1.7, 1.3, and 0.6 ka, i.e., within the Lateglacial and the late Holocene. These negative shifts in δ18Ocarb corresponded to lower lake-level phases, and most likely were a response to intensification of the mid-latitude westerly circulation that may have transported significantly more 18O-depleted moisture to the region, compared to that from the Asian summer monsoon. Overall, our results suggest that the alternating influence of the Asian summer monsoon and the westerlies played a significant role in determining the pattern of atmospheric circulation on the northeastern QTP.

Comparing sulfur and oxygen isotope variability of sulfate in the Mississippi River during high and low discharge from 2009-2011

NASA Astrophysics Data System (ADS)

Killingsworth, B.; Kohl, I. E.; Bao, H.

2011-12-01

S and O isotope compositions of ocean and river sulfate, SO42-, reflect Earth surface processes and can thus be used to understand the Earth's dynamic past. It has been estimated that riverine SO42- is 22% evaporite (SO42-riv-evap), 11% oxidative weathering (SO42-riv-ow), and 54% atmospheric and agricultural pollution [1]. Two parameters are poorly constrained: 1) the ratio of SO42-riv-evap to SO42-riv-ow, and 2) the extent of human influence on SO42- flux. Furthermore, for isotopic modeling, natural riverine SO42- O and S isotope compositions, δ18OSO4-riv and δ34SSO4-riv, have large measured ranges (e.g. δ18OSO4-riv from -2% to +7% [2]) that are based on limited empirical data with variable and unconstrained influence from human activities. In the lower Mississippi River Basin (MRB) we have sampled river water SO42- biweekly since 2009. Our isotope dataset is used in conjunction with US Geological Survey and US Army Corps of Engineers SO42- concentration and river discharge data. In comparison to MRB low discharge periods, the periods of annual high water discharge are characterized by 1) a doubling in water discharge 2) a concomitant high MRB SO42- flux (>1100 kg/s) 3) an average SO42- concentration at 85% of the low discharge concentrations and 4) a more constrained variability of SO42- isotope composition. The δ18OSO4-riv ranges from +3.2% to +5.5% at high discharge and from +2.6% to +8.8% at low discharge. The δ34SSO4-riv ranges from -4.3% to -0.4 at high discharge and from -6.3% to -0.2% at low discharge. Atmospheric SO42- is estimated from 2009 National Atmospheric Deposition Program maps to contribute only ~10% of total MRB SO42-. We conclude that during annual high discharge a large river basin such as the MRB is less sensitive to variable sub-basin input and that average MRB SO42- isotope composition is best represented by a δ18OSO4-riv value of ~+4.0% and δ34SSO4-riv value of ~-3.0%. MRB SO42- concentration during high discharge is diluted less than expected, given the low concentration of SO42- in precipitation, and this result reveals the existence of a spatially dispersed and significant SO42- sink, such as soil, within the MRB. The all-negative range for MRB δ34SSO4-riv indicates that oxidative weathering of both (1) reduced sulfur (e.g. biologically cycled sulfur in soil) and (2) sulfides (e.g. pyrite in coal), is the dominant source of SO42- in the MRB because all other sources of riverine SO42- have positive δ34SSO4-riv values [3]. Moreover, the Upper Ohio (UORB) and Upper Missouri (UMRB) MRB sub-basins both contain significant coalfields which are likely sources of much of the isotopically lighter SO42- in the MRB. The UORB and UMRB contributed ~1/3 of all MRB SO42- during high discharge and low discharge, respectively, and a combined 1/2 of all MRB SO42- each year in the 10-year period 1999-2009. [1]Berner, E. K., and R. A. Berner (1996), Global environment; [2]Turchyn, A. V., and D. P. Schrag (2004), Science, 303(5666), 2004-2007; [3]Rock, L., and B. Mayer (2009), Chem. Geol., 262(3-4), 121-130.

Natural Ca Isotope Composition of Urine as a Rapid Measure of Bone Mineral Balance

NASA Astrophysics Data System (ADS)

Skulan, J.; Gordon, G. W.; Morgan, J.; Romaniello, S. J.; Smith, S. M.; Anbar, A. D.

2011-12-01

Naturally occurring stable Ca isotope variations in urine are emerging as a powerful tool to detect changes in bone mineral balance. Bone formation depletes soft tissue of light Ca isotopes while bone resorption releases isotopically light Ca into soft tissue. Previously published work found that variations in Ca isotope composition could be detected at 4 weeks of bed rest in a 90-day bed rest study (data collected at 4, 8 and 12 weeks). A new 30-day bed rest study involved 12 patients on a controlled diet, monitored for 7 days prior to bed rest and 7 days post bed rest. Samples of urine, blood and food were collected throughout the study. Four times daily blood samples and per void urine samples were collected to monitor diurnal or high frequency variations. An improved chemical purification protocol, followed by measurement using multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) allowed accurate and precise determinations of mass-dependent Ca isotope variations in these biological samples to better than ±0.2% (δ44/42Ca) on <25 μg of Ca. Results from this new study show that Ca isotope ratios shift in a direction consistent with net bone loss after just 7 days, long before detectible changes in bone density by X-ray measurements occur. Consistent with this interpretation, the Ca isotope variations track changes observed in N-teleopeptide, a bone resorption biomarker. Bone-specific alkaline phosphatase, a bone formation biomarker, is unchanged over this period. Ca isotopes can in principle be used to quantify net changes in bone mass. Using a mass-balance model, our results indicate an average loss of 0.62 ± 0.16 % in bone mass over the course of this 30-day study. This is consistent with the rate of bone loss in longer-term studies as seen by X-ray measurements. This Ca isotope technique should accelerate the pace of discovery of new treatments for bone disease and provide novel insights into the dynamics of bone metabolism.

Estimating the Seasonal Importance of Precipitation to Plant Source Water over Time and Space with Water Isotopes

NASA Astrophysics Data System (ADS)

Nelson, D. B.; Kahmen, A.

2017-12-01

The stable isotopic composition of hydrogen and oxygen are physical properties of water molecules that can carry information on their sources or transport histories. This provides a useful tool for assessing the importance of rainfall at different times of the year for plant growth, provided that rainwater values vary over time and that waters do not partially evaporate after deposition. We tested the viability of this approach using data from samples collected at nineteen sites throughout Europe at monthly intervals over two consecutive growing seasons in 2014 and 2015. We compared isotope measurements of plant xylem water with soil water from multiple depths, and measured and modeled precipitation isotope values. Paired analyses of oxygen and hydrogen isotope values were used to screen out a limited number of water samples that were influenced by evaporation, with the majority of all water samples indicating meteoric sources. The isotopic composition of soil and xylem waters varied over the course of an individual growing season, with many trending towards more enriched values, suggesting integration of the plant-relevant water pool at a timescale shorter than the annual mean. We then quantified how soil water residence times varied at each site by calculating the interval between measured xylem water and the most recently preceding match in modeled precipitation isotope values. Results suggest a generally increasing interval between rainfall and plant uptake throughout each year, with source water corresponding to dates in the spring, likely reflecting a combination of spring rain, and mixing with winter and summer precipitation. The seasonally evolving spatial distribution of source water-precipitation lag values was then modeled as a function of location and climatology to develop continental-scale predictions. This spatial portrait of the average date for filling the plant source water pool provides insights on the seasonal importance of rainfall for plant growth. It also permits continental scale predictions of monthly plant source water isotope values, with applications to improving isotopic paleoclimate proxies from plants such as tree rings or sedimentary leaf waxes, and for using oxygen and hydrogen isotopes to track the origins of agricultural products.

Experimental constraints on reconstruction of Archean seawater Ni isotopic composition from banded iron formations

NASA Astrophysics Data System (ADS)

Wang, Shui-Jiong; Wasylenki, Laura E.

2017-06-01

The Ni isotopic systematics in banded iron formations (BIFs) potentially recorded the Ni isotopic composition of ancient seawater over Precambrian geological history. However, the utility of BIFs as proxies requires quantitative knowledge of how Ni isotopes fractionated as dissolved Ni was initially incorporated into iron-rich sediments and how diagenesis may have affected the Ni isotopic systematics. Here we report results of synthesis experiments to investigate the behavior of Ni isotopes during Ni coprecipitation with ferrihydrite and then transformation of ferrihydrite to hematite. Ferrihydrite coprecipitation experiments at neutral pH demonstrated that the dissolved Ni was variably heavier than coprecipitated Ni (likely a mixture of surface-adsorbed and structurally incorporated Ni), with the isotope fractionation becoming larger as the fraction of Ni associated with solid increased (Δ60/58Nisolution-solid = +0.08 to +0.50‰). Further experiments at lower pH (3.7-6.7), in which structurally incorporated Ni likely dominated in solids, documented a decrease in Δ60/58Nisolution-solid from +0.44‰ to -0.18‰ as the pH decreased. The negative value for Δ60/58Nisolution-solid at low pH indicates the enrichment of heavier isotopes in incorporated Ni relative to dissolved and adsorbed Ni, possibly as a result of the presence of a small amount of tetrahedral Ni2+ in addition to octahedral Ni2+ in the ferrihydrite structure. The results of the ferrihydrite experiments thus reflect equilibrium isotope fractionation between three pools of Ni, with δ60/58Ni values in the order of incorporated > dissolved > adsorbed. Hematite was synthesized by transformation of Ni-bearing ferrihydrite in aqueous solution at ∼100 °C. A significant amount of Ni (up to 60%) was released (desorbed) from solids into solutions as pH dropped from ∼7 to 4.5-5.5 upon phase transformation. Rinsing of the synthesized hematite in 2 M acetic acid released only very small amounts of Ni (<4% of total Ni, presumably surface-adsorbed) that were isotopically heavier (δ60/58Ni = +0.11 ± 0.06‰) than the residues (presumably dominated by incorporated Ni), which had δ60/58Ni of -0.26 ± 0.07‰. The preference of lighter isotopes for the incorporated Ni relative to the surface-adsorbed Ni after phase transformation (most had been released into solution) is probably due to distortion of Nisbnd O octahedra in the hematite structure, with weaker Nisbnd O bond strengths on average. Hence, the more variable Δ60/58Nisolution-solid values (-0.04 to +0.77‰) observed in hematite experiments most likely reflect thermodynamically driven Rayleigh fractionation, with incorporated Ni unavailable to exchange with dissolved Ni due to continuous reduction in size of the highly reactive surface pool of Ni, through which all solid-solution exchange must occur. Overall, the synthesized hematite was isotopically lighter than the ferrihydrite by ∼0.08‰ in δ60/58Ni, which is however within the current analytical uncertainties (±0.09‰). This implies that earliest diagenesis of BIFs results in very limited change in the isotopic composition of solid-associated Ni. Our experimental results, although conducted in a very simple system that differs from Archean seawater, represent an important step toward reconstruction of the Ni isotopic composition of ancient seawater from Ni isotopic signatures in BIFs.

Magnesium and Titanium Isotopic Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende: It Is Fun

NASA Technical Reports Server (NTRS)

Liu, M.-C.; Keller, L. P.; McKeegan, K. D.

2016-01-01

Introduction: Hibonite-rich refractory inclusions are among the first solids that formed in the solar nebula, and thus provide constraints on the earliest environment in the Solar System. An unusual hibonite-perovskite inclusion from Allende, SHAL, consists of a large (approximately 500 by 200 microns) single hibonite crystal and coexisting blocky perovskite (approximately 200 microns in size). The hibonite is characterized by chemical and oxygen isotopic compositions similar to those in the FUN (Fractionated and Unknown Nuclear anomalies) inclusion HAL. However, the rare earth element (REE) patterns measured at different spots of SHAL hibonite are highly variable, ranging from Group II-like (light REEs enriched relative to heavy REEs) to Group III-like (relatively flat with slight Eu depletions), but overall contrast largely with that of HAL, especially in the Ce and Yb abundances. This implies that SHAL hibonite formed and underwent distillation processes under more reducing conditions. Interestingly, the accompanying perovskite has uniform, unfractionated oxygen isotopic compositions (averaging delta (sup 17) O equals delta (sup 18) O equals -7 per mille) and REE abundances that are completely different from those of SHAL hibonite. This has been interpreted that perovskite and hibonite may not be co-genetic. Here we performed Al-Mg and Ti isotopic measurements of SHAL hibonite and perovskite to determine if the FUN characteristics are observed in these two isotope systems, and to further constrain the origin and evolution of SHAL. Results: Isotopic measurements of Al-Mg and Ti in SHAL were performed on the UCLA CAMECA ims-1290 ion microprobe by following the analytical protocols described in [1]. The Al-Mg and Ti data obtained in both terrestrial standards and SHAL hibonite and perovskite are shown below. Both SHAL hibonite and perovskite, despite very high (sup 27) Al to (sup 24) Mg ratios, are devoid of (sup 26) Mg excesses that can be attributed to the decay of (sup 26) Al. Delta (sup 25) Mg (mass-dependent fractionation) in hibonite is approximately -5 per mille per atomic mass unit relative to Madagascar hibonite, but is not well constrained for perovskite due to very large uncertainties owing to extremely low Mg contents. Similar to Mg isotopes, SHAL hibonite and perovskite show essentially the same Ti isotopic compositions, with anomalies in (sup 50) Ti of approximately 14 per mille, but the former shows greater Ti isotope fractionation than the latter (2.5 per mille per atomic mass unit versus 0 per mille). Discussion and Conclusions: The Al-Mg and Ti isotopic compositions of SHAL hibonite are consistent with those of HAL, suggesting that SHAL hibonite is a FUN inclusion and likely formed prior to homogenization of (sup 26) Al and Ti isotope variations in the solar nebula. However, the formation mechanisms for SHAL and HAL differ, given the differences in the REE patterns and degrees of oxygen mass-dependent fractionation. The Group-II to Group-III like REE patterns, the Yb depletions, and negative delta (sup 25) Mg observed in SHAL hibonite are all consistent with condensation of the hibonite precursor in a reducing environment.. The lack of large Ce depletions in SHAL hibonite implies that distillation processes that fractionated hibonite's oxygen isotopes must have taken place under a reducing condition, but the extent to which SHAL hibonite was distilled appears to be less than HAL because of the smaller degree of oxygen mass-dependent fractionation. The perovskite shares essentially the same Ti and Mg isotopic compositions as hibonite and probably formed in the same reservoir.. The ultrarefractory REE pattern seen in perovskite likely resulted from gas-solid fractionation which depleted HREEs in this reservoir. This process also explains why SHAL hibonite is generally depleted in HREEs relative to LREEs.

Reconstruction of the Nd isotope composition of seawater on epicontinental seas: Testing the potential of Fe-Mn oxyhydroxide coatings on foraminifera tests for deep-time investigations

NASA Astrophysics Data System (ADS)

Charbonnier, Guillaume; Pucéat, Emmanuelle; Bayon, Germain; Desmares, Delphine; Dera, Guillaume; Durlet, Christophe; Deconinck, Jean-François; Amédro, Francis; Gourlan, Alexandra T.; Pellenard, Pierre; Bomou, Brahimsamba

2012-12-01

The Fe-Mn oxide fraction leached from deep-sea sediments has been increasingly used to reconstruct the Nd isotope composition of deep water masses, that can be used to track changes in oceanic circulation with a high temporal resolution. Application of this archive to reconstruct the Nd isotope composition of bottom seawater in shallow shelf environments remained however to be tested. Yet as the Nd isotope composition of seawater on continental margins is particularly sensitive to changes in erosional inputs, establishment of neritic seawater Nd isotope evolution around areas of deep water formation would be useful to discriminate the influence of changes in oceanic circulation and in isotopic composition of erosional inputs on the Nd isotope record of deep waters. The purpose of this study is to test the potential of Fe-Mn coatings leached from foraminifera tests to reconstruct the Nd isotope composition of seawater in shelf environments for deep-time intervals. Albian to Turonian samples from two different outcrops have been recovered, from the Paris Basin (Wissant section, northern France) and from the Western Interior Seaway (Hot Spring, South Dakota, USA), that were deposited in epicontinental seas. Rare Earth Element (REE) spectra enriched in middle REEs in the foraminifera leach at Wissant highlight the presence of Fe-Mn oxides. The similarity of the Nd isotopic signal of the Fe-Mn oxide fraction leached from foraminifera tests with that of fish teeth suggests that Fe-Mn oxides coating foraminifera can be good archives of shelf bottom seawater Nd isotopic composition. Inferred bottom shelf water Nd isotope compositions at Wissant range from -8.5 to -9.7 ɛ-units, about 1.5-2 ɛ-units higher than that of the contemporaneous local detrital fraction. At Hot Spring, linear REE spectra characterizing foraminifera leach may point to an absence of authigenic marine Fe-Mn oxide formation in this area during the Late Cenomanian-Early Turonian, consistent with dysoxic to anoxic conditions at Hot Spring, contemporaneous to an Oceanic Anoxic Event. The similarity of the Nd isotopic signal of the carbonate matrix of foraminifera with that of fish teeth suggests that it records the Nd isotope composition of bottom shelf seawater as well. Inferred bottom shelf water Nd isotope compositions at Hot Spring are quite radiogenic, between -7 and -6 ɛ-units, about 2.5-4 ɛ-units higher than that of the contemporaneous local detrital fraction. In contrast, in both sections Fe-Mn oxides leached directly from the decarbonated sediment tend to yield a less radiogenic Nd isotopic composition, typically between 0.2 and 0.8 ɛ-units lower, that is intermediate between that of fish teeth and of the detrital fraction. This suggests the contribution of pre-formed continental Fe-Mn oxides to the Nd isotopic signal, along with authigenic marine oxides, or a detrital contamination during leaching.

Variation of brine compositions resulting from flow from matrix or fracture permeability, investigated by high pressure laboratory experiments

NASA Astrophysics Data System (ADS)

Poszwa, A. C.; Coleman, M. L.; Pouya, A.; Ader, M.; Bounenni, A.

2003-04-01

Planning oil production from a chalk reservoir oilfield is difficult because the matrix usually has low permeability despite its high porosity. Most oil is thought to come from fracture porosity but the matrix contribution should increase as compaction occurs during production. To better understand the respective contributions from matrix and fracture, we studied the geochemical characteristics of fluids using high-pressure brine flow experiments on chalk cores. During the experiment axial load was changed relative to confining pressure to induce fractures and to close them again. We used chlorine stable isotope variations to study fluid pathway, because chlorine is a chemically conservative element in sedimentary systems and its isotopes fractionate only with physical processes like diffusion or adsorption that could occur mainly in the chalk matrix. A first experiment was performed on a very porous chalk from Henley (on-shore UK) and using a low-salinity brine. Large variations of brine Cl isotope composition were observed (from -0.56 to +0.08 per mil). The variations were correlated positively with the brine flux through the chalk and the permeability of the rock, both parameters controlled by the rock fracturing. A second experiment used brine with salinity similar to that of seawater. In this case, chemical and isotopic variations were not significant. From the beginning, the chalk structure seems to have been destroyed very quickly (induced fracture porosity collapsed) possibly because of the fluid nature, so that whatever pressure was applied, the permeability did not change significantly. Using Valhall reservoir chalk (offshore Norwegian North Sea) and fluid half the salinity of seawater in a third experiment, we obtained a large range of permeabilities. Brine isotopic trends were very similar on average to those of the first experiment even though variations were smaller (Cl isotopes from -0.09 to +0.29 per mil) and not significantly correlated simply to permeability values. The highest isotopic values were in brine flowed through chalk when the permeability was high and fractures opened; the lowest values were in brine flowed through the chalk when its permeability was reduced by closing fractures and increasing the relative contribution from matrix flow where diffusion processes fractionated chlorine isotopes. From this work it seems that the relative contributions from fracture and matrix permeability in reservoirs can be estimated from the geochemical compositions of brines that flowed from them.

Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

NASA Astrophysics Data System (ADS)

Nielson, Kristine E.; Bowen, Gabriel J.

2010-03-01

Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

Isotopologue Distributions of Peptide Product Ions by Tandem Mass Spectrometry: Quantitation of Low Levels of Deuterium Incorporation1

PubMed Central

Wang, Benlian; Sun, Gang; Anderson, David R.; Jia, Minghong; Previs, Stephen; Anderson, Vernon E.

2007-01-01

Protonated molecular peptide ions and their product ions generated by tandem mass spectrometry appear as isotopologue clusters due to the natural isotopic variations of carbon, hydrogen, nitrogen, oxygen and sulfur. Quantitation of the isotopic composition of peptides can be employed in experiments involving isotope effects, isotope exchange, isotopic labeling by chemical reactions, and studies of metabolism by stable isotope incorporation. Both ion trap and quadrupole-time of flight mass spectrometry are shown to be capable of determining the isotopic composition of peptide product ions obtained by tandem mass spectrometry with both precision and accuracy. Tandem mass spectra obtained in profile-mode of clusters of isotopologue ions are fit by non-linear least squares to a series of Gaussian peaks (described in the accompanying manuscript) which quantify the Mn/M0 values which define the isotopologue distribution (ID). To determine the isotopic composition of product ions from their ID, a new algorithm that predicts the Mn/M0 ratios is developed which obviates the need to determine the intensity of all of the ions of an ID. Consequently a precise and accurate determination of the isotopic composition a product ion may be obtained from only the initial values of the ID, however the entire isotopologue cluster must be isolated prior to fragmentation. Following optimization of the molecular ion isolation width, fragmentation energy and detector sensitivity, the presence of isotopic excess (2H, 13C, 15N, 18O) is readily determined within 1%. The ability to determine the isotopic composition of sequential product ions permits the isotopic composition of individual amino acid residues in the precursor ion to be determined. PMID:17559791

Long-Term Precipitation Isotope Ratios (δ18O, δ2H, d-excess) in the Northeast US Reflect Atlantic Ocean Warming and Shifts in Moisture Sources

NASA Astrophysics Data System (ADS)

Puntsag, T.; Welker, J. M.; Mitchell, M. J.; Klein, E. S.; Campbell, J. L.; Likens, G.

2014-12-01

The global water cycle is exhibiting dramatic changes as global temperatures increase resulting in increases in: drought extremes, flooding, alterations in storm track patterns with protracted winter storms, and greater precipitation variability. The mechanisms driving these changes can be difficult to assess, but the spatial and temporal patterns of precipitation water isotopes (δ18O, δ2H, d-excess) provide a means to help understand these water cycle changes. However, extended temporal records of isotope ratios in precipitation are infrequent, especially in the US. In our study we analyzed precipitation isotope ratio data from the Hubbard Brook Experimental Forest in New Hampshire that has the longest US precipitation isotope record, to determine: 1) the monthly composited averages and trends from 1967 to 2012 (45 years); ; 2) the relationships between abiotic properties such as local temperatures, precipitation type, storm tracks and isotope ratio changes; and 3) the influence of regional shifts in moisture sources and/or changes in N Atlantic Ocean water conditions on isotope values. The seasonal variability of Hubbard Brook precipitation isotope ratios is consistent with other studies, as average δ18O values are ~ -15‰ in January and ~ -5 ‰ in July. However, over the 45 year record there is a depletion trend in the δ 18O values (becoming isotopically lighter with a greater proportion of 16O), which coupled with less change in δ 2H leads to increases in d-excess values from ~ -10‰ around 1970 to greater than 10‰ in 2009. These changes occurred during a period of warming as opposed to cooling local temperatures indicating other processes besides temperature are controlling long-term water isotope traits in this region. We have evidence that these changes in precipitation isotope traits are controlled in large part by an increases in moisture being sourced from a warming N Atlantic Ocean that is providing evaporated, isotopically-depleted precipitation to the region. Thus, the warming of the N Atlantic Ocean appears to influence the climate and the precipitation isotopes of Northeastern coastal regions and could be a larger water source to watersheds in this North American region.

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.

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile - Marine sources and diagenetic effects.

PubMed

Lucassen, Friedrich; Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A

2017-01-01

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very heavy values generate a compositionally unique material. These compositions trace the presence of guano in natural ecosystems and its use as fertilizer in present and past agriculture.

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile – Marine sources and diagenetic effects

PubMed Central

Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A.

2017-01-01

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very heavy values generate a compositionally unique material. These compositions trace the presence of guano in natural ecosystems and its use as fertilizer in present and past agriculture. PMID:28594902

Seasonality of Leaf Carbon Isotopic Composition and Leaf Water Isotopic Enrichment in a Mixed Evergreen Forest in Southern California

NASA Astrophysics Data System (ADS)

Santiago, L. S.; Sickman, J. O.; Goulden, M.; DeVan, C.; Pasquini, S. C.; Pivovaroff, A. L.

2011-12-01

Leaf carbon isotopic composition and leaf water isotopic enrichment reflect physiological processes and are important for linking local and regional scale processes to global patterns. We investigated how seasonality affects the isotopic composition of bulk leaf carbon, leaf sugar carbon, and leaf water hydrogen under a Mediterranean climate. Leaf and stem samples were collected monthly from four tree species (Calocedrus decurrens, Pinus lambertiana, Pinus ponderosa, and Quercus chrysolepis) at the James San Jacinto Mountain Reserve in southern California. Mean monthly bulk leaf carbon isotopic composition varied from -34.5 % in P. ponderosa to -24.7 % in P. lambertiana and became more depleted in 13C from the spring to the summer. Mean monthly leaf sugar varied from -29.3 % in P. ponderosa to -21.8 % in P. lambertiana and was enriched in 13C during the winter, spring and autumn, but depleted during the mid-summer. Leaf water hydrogen isotopic composition was 28.4 to 68.8 % more enriched in deuterium than source water and this enrichment was greater as seasonal drought progressed. These data indicate that leaf carbon and leaf water hydrogen isotopic composition provide sensitive measures that connect plant physiological processes to short-term climatic variability.

Isotopic composition of atmospheric moisture from pan water evaporation measurements.

PubMed

Devi, Pooja; Jain, Ashok Kumar; Rao, M Someshwer; Kumar, Bhishm

2015-01-01

A continuous and reliable time series data of the stable isotopic composition of atmospheric moisture is an important requirement for the wider applicability of isotope mass balance methods in atmospheric and water balance studies. This requires routine sampling of atmospheric moisture by an appropriate technique and analysis of moisture for its isotopic composition. We have, therefore, used a much simpler method based on an isotope mass balance approach to derive the isotopic composition of atmospheric moisture using a class-A drying evaporation pan. We have carried out the study by collecting water samples from a class-A drying evaporation pan and also by collecting atmospheric moisture using the cryogenic trap method at the National Institute of Hydrology, Roorkee, India, during a pre-monsoon period. We compared the isotopic composition of atmospheric moisture obtained by using the class-A drying evaporation pan method with the cryogenic trap method. The results obtained from the evaporation pan water compare well with the cryogenic based method. Thus, the study establishes a cost-effective means of maintaining time series data of the isotopic composition of atmospheric moisture at meteorological observatories. The conclusions drawn in the present study are based on experiments conducted at Roorkee, India, and may be examined at other regions for its general applicability.

Stable Isotope Systematics in Grasshopper Assemblages Along an Elevation Gradient, Colorado

NASA Astrophysics Data System (ADS)

Kohn, M. J.; Evans, S.; Dean, J.; Nufio, C.

2012-12-01

Insects comprise over three quarters of all animal species, yet studies of body water isotopic composition are limited to only the cockroach, the hoverfly, and chironomid flies. These studies suggest that oxygen and hydrogen isotopic compositions in body water are primarily controlled by dietary water sources, with modification from respiratory and metabolic processes. In particular, outward diffusion of isotopically depleted water vapor through insect spiracles at low humidity enriches residual body water in 18O and 2H (D). Stable isotope compositions (δ18O and δD) also respond to gradients in elevation and humidity, but these influences remain poorly understood. In this study, we measured grasshopper body water and local vegetation isotopic compositions along an elevation gradient in Colorado to evaluate three hypotheses: 1) Insect body water isotopic composition is directly related to food source water composition 2) Water vapor transport alters body water isotopic compositions relative to original diet sources, and 3) Elevation gradients influence isotopic compositions in insect body water. Thirty-five species of grasshopper were collected from 14 locations in Colorado grasslands, ranging in elevation from 450 to 800 meters (n=131). Body water was distilled from previously frozen grasshopper specimens using a vacuum extraction line, furnaces (90 °C), and liquid nitrogen traps. Water samples were then analyzed for δ18O and δD on an LGR Liquid Water Isotope Analyzer, housed in the Department of Geosciences, Boise State University. Grasshopper body water isotopic compositions show wide variation, with values ranging between -76.64‰ to +42.82‰ in δD and -3.06‰ to +26.78‰ in δ18O. Precipitation δ18O values over the entire Earth excluding the poles vary by approximately 30‰, comparable to the total range measured in our single study area. Most grasshopper values deviate from the global meteoric water line relating δ18O and δD in precipitation, consistent with evaporative enrichment in food (plants) due to plant transpiration. However, grasshopper body water from any given location is further enriched in 18O and D relative to food. Isotopic values decrease slightly with increasing elevation, but some specific grasshopper species appear more sensitive to elevation. Overall, evaporative enrichment of 18O and D in this relatively dry environment appears the strongest factors influencing grasshopper compositions.

Nitrogen Isotope Evidence for a Shift in Eastern Beringian Nitrogen Cycle after the Terminal Pleistocene

NASA Astrophysics Data System (ADS)

Tahmasebi, F.; Longstaffe, F. J.; Zazula, G.

2016-12-01

The loess deposits of eastern Beringia, a region in North America between 60° and 70°N latitude and bounded by Chukchi Sea to the west and the Mackenzie River to the east, are a magnificent repository of Late Pleistocene megafauna fossils. The stable carbon and nitrogen isotope compositions of these fossils are measured to determine the paleodiet of these animals, and hence the paleoenvironment of this ecosystem during the Quaternary. For this approach to be most successful, however, requires consideration of possible changes in nutrient cycling and hence the carbon and nitrogen isotopic compositions of vegetation in this ecosystem. To test for such a shift following the terminal Pleistocene, we analyzed the stable carbon and nitrogen isotope compositions of modern plants and bone collagen of Arctic ground squirrels from Yukon Territory, and fossil plants and bones recovered from Late Pleistocene fossil Arctic ground squirrel nests. The data for modern samples provided a measure of the isotopic fractionation between ground squirrel bone collagen and their diet. The over-wintering isotopic effect of decay on typical forage grasses was also measured to evaluate its role in determining fossil plant isotopic compositions. The grasses showed only a minor change ( 0-1 ‰) in carbon isotope composition, but a major change ( 2-10 ‰) in nitrogen isotope composition over the 317-day experiment. Based on the modern carbon isotope fractionation between ground squirrel bone collagen and their diet, the modern vegetation carbon isotopic baseline provides a suitable proxy for the Late Pleistocene of eastern Beringia, after accounting for the Suess effect. However, the predicted nitrogen isotope composition of vegetation comprising the diet of fossil ground squirrels remains 2.5 ‰ higher than modern grasslands in this area, even after accounting for possible N-15 enrichment during decay. This result suggests a change in N cycling in this region since the Late Pleistocene.

Deciphering the iron isotope message of the human body

NASA Astrophysics Data System (ADS)

Walczyk, Thomas; von Blanckenburg, Friedhelm

2005-04-01

Mass-dependent variations in isotopic composition are known since decades for the light elements such as hydrogen, carbon or oxygen. Multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS) and double-spike thermal ionization mass spectrometry (TIMS) permit us now to resolve small variations in isotopic composition even for the heavier elements such as iron. Recent studies on the iron isotopic composition of human blood and dietary iron sources have shown that lighter iron isotopes are enriched along the food chain and that each individual bears a certain iron isotopic signature in blood. To make use of this finding in biomedical research, underlying mechanisms of isotope fractionation by the human body need to be understood. In this paper available iron isotope data for biological samples are discussed within the context of isotope fractionation concepts and fundamental aspects of human iron metabolism. This includes evaluation of new data for body tissues which show that blood and muscle tissue have a similar iron isotopic composition while heavier iron isotopes are concentrated in the liver. This new observation is in agreement with our earlier hypothesis of a preferential absorption of lighter iron isotopes by the human body. Possible mechanisms for inducing an iron isotope effect at the cellular and molecular level during iron uptake are presented and the potential of iron isotope effects in human blood as a long-term measure of dietary iron absorption is discussed.

A Sm-Nd isotopic study of atmospheric dusts and particulates from major river systems

NASA Technical Reports Server (NTRS)

Goldstein, S. L.; Onions, R. K.; Hamilton, P. J.

1984-01-01

Nd-143/Nd-144 ratios, together with Sm and Nd abundances, are given for particulates from major and minor rivers as well as continental sediments and aeolian dusts collected over the Atlantic, Pacific, and Indian Oceans. In combination with data from the literature, the present results have implications for the age, history, and composition of the sedimentary mass and the continental crust. It is noted that the average ratio of Sm/Nd is about 0.19 in the upper continental crust, and has remained so since the early Archean, thereby precluding the likelihood of major mafic-to-felsic or felsic-to-mafic trends in the overall composition of the upper continental crust through earth history. The average 'crustal residence age' of the entire sedimentary mass is about 1.9 Ga.

Ammunition is the principal source of lead accumulated by California condors re-introduced to the wild.

PubMed

Church, Molly E; Gwiazda, Roberto; Risebrough, Robert W; Sorenson, Kelly; Chamberlain, C Page; Farry, Sean; Heinrich, William; Rideout, Bruce A; Smith, Donald R

2006-10-01

The endangered California Condor (Gymnogyps californianus) was reduced to a total population of 22 birds by the end of 1982. Their captive-bred descendants are now being released back into the wild in California, Arizona, and Baja California, where monitoring indicates they may accumulate lead to toxic levels. Fragments of ammunition in the carcasses of game animals such as deer, elk, and feral pigs not retrieved by hunters or in gut piles left in the field have been considered a plausible source of the lead, though little direct evidence is available to support this hypothesis. Here, we measured lead concentrations and isotope ratios in blood from 18 condors living in the wild in central California, in 8 pre-release birds, and in diet and ammunition samples to determine the importance of ammunition as a source of exposure. Blood lead levels in pre-release condors were low (average 27.7 ng/mL, SD 4.9 ng/ mL) and isotopically similar to dietary and background environmental lead in California. In contrast, blood lead levels in free-flying condors were substantially higher (average 246 ng/mL, SD 229 ng/mL) with lead isotopic compositions that approached or matched those of the lead ammunition. A two-endmember mixing model defined by the background 207Pb/206Pb ratio of representative condor diet samples (0.8346) and the upper 207Pb/206Pb ratio of the ammunition samples (0.8184) was able to account for the blood lead isotopic compositions in 20 out of the 26 live condors sampled in this study (i.e., 77%). Finally, lead in tissues and in a serially sampled growing feather recovered postmortem from a lead-poisoned condor in Arizona evidence acute exposure from an isotopically distinct lead source. Together, these data indicate that incidental ingestion of ammunition in carcasses of animals killed by hunters is the principal source of elevated lead exposure that threatens the recovery in the wild of this endangered species.

Oxygen, deuterium, and strontium isotope characteristics of the Indus River water system

NASA Astrophysics Data System (ADS)

Sharma, Anupam; Kumar, Kamlesh; Laskar, Amzad; Singh, Sunil Kumar; Mehta, Pankaj

2017-05-01

Understanding the sources and compositional characteristics of waters and sediments in the Indus River system is extremely important as its water availability is one of the primary factors for sustenance of the irrigation activities and the socioeconomic status of a very densely populated region of the world. Here we used stable isotopic compositions (δD and δ18O) and strontium isotopic ratio (87Sr/86Sr) in the Indus River water, its tributaries and its small streams (nallahs) in the Indian territory to understand the regional hydrology, water sources, and catchment processes (evaporation, transpiration, recycling, and mixing). The δ18O values in the Indus River system (IRS) ranges from - 16.9‰ to - 12.5‰ and δD from - 122.8‰ to - 88.5‰. The Indus River and its major tributaries (such as the Zanskar, Nubra and Shyok rivers) are characterized by relatively lower δ18O values, whereas TangTse and other small streams contributing to the Indus are relatively enriched in 18O. The local meteoric water line for the IRS was found to be δD = 7.87 × δ18O + 11.41, which is similar to the Global Meteoric Water Line (GMWL) indicating meteoric origin of the water and insignificant secondary evaporation in the catchment. The Deuterium excess (d-excess) in the IRS varies between 6.5‰ and 14.9‰ with an average of 11.7‰, which is mostly higher than the long-term average for the Indian summer monsoon ( 8‰). The higher d-excess value is because of the contribution of moisture from westerlies; a simple mass balance shows 26% water in the main Indus channel is contributed by the westerlies originated from the Mediterranean Sea. The Sr isotope ratio in IRS varies between 0.70515 and 0.71291; wherein the Indus, and its tributary rivers Shyok and Nubra, are characterized by relatively high Sr isotope ratios (avg. 0.71086-0.71243) compared to the Zanskar and TangTse tributaries (Sr 0.709) because of the variation in silicate rock weathering component and carbonate rock weathering component ratios respectively.

Tooth enamel maturation reequilibrates oxygen isotope compositions and supports simple sampling methods

NASA Astrophysics Data System (ADS)

Trayler, Robin B.; Kohn, Matthew J.

2017-02-01

Oxygen isotope and major element zoning patterns of several disparate ungulate teeth were collected to evaluate the timing and geometry of enamel formation, records of isotope zoning, and tooth enamel sampling strategies. Isotopic zoning in mammalian tooth enamel encodes a sub-annual time series of isotopic variation of an animal's body water composition, with a damping factor that depends on the specifics of how enamel mineralizes. Enamel formation comprises two stages: precipitation of appositional enamel with a high CO3:PO4 ratio, followed by precipitation of maturational enamel with a lower CO3:PO4. If appositional and maturational enamel both contribute to isotope compositions (but with different CO3:PO4), and if isotope compositions vary seasonally, paired δ18O values from CO3 and PO4 profiles should show a spatial separation. CO3 isotope patterns should be shifted earlier seasonally than PO4 isotope patterns. Such paired profiles for new and published data show no resolvable shifts, i.e. CO3 and PO4 δ18O profiles show coincident maxima and minima. This coincidence suggests that enamel maturation reequilibrates appositional isotope compositions. If enamel maturation establishes enamel isotope compositions, the geometry of maturation, not apposition, should be considered when devising sampling protocols. X-ray maps of Ca zoning show that the majority of enamel (inner and middle layers) mineralizes heavily at a high angle to the external tooth surface and the enamel-dentine junction over length scales of 2-4 mm, while the outer enamel surface mineralizes more slowly. These data suggest that isotopic sampling strategies should parallel maturational geometry and focus on interior enamel to improve data fidelity. The magnitude of isotopic damping is also smaller than implied in previous studies, so tooth enamel zoning more closely reflects original body water isotopic variations than previously assumed.

Isotopic Compositions of the Elements, 2001

NASA Astrophysics Data System (ADS)

Böhlke, J. K.; de Laeter, J. R.; De Bièvre, P.; Hidaka, H.; Peiser, H. S.; Rosman, K. J. R.; Taylor, P. D. P.

2005-03-01

The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the "best measurement" of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001.

Trace Elements and Oxygen Isotope Zoning of the Sidewinder Skarn

NASA Astrophysics Data System (ADS)

Draper, C.; Gevedon, M. L.; Barnes, J.; Lackey, J. S.; Jiang, H.; Lee, C. T.

2016-12-01

Skarns of the Verde Antique Quarry and White Horse Mountain areas of the Sidewinder Range give insight into the paleohydrothermal systems operating in the California's Jurassic arc in the Southwestern Mojave Desert. Garnet from these skarns is iron rich: Xand= 55-100. Laser fluorination measurements show oxygen isotope (δ18O) compositions of garnet crystals and crystals domains have large ranges: -3.1‰ to +4.4‰ and -8.9‰ to +3.4‰, respectively. In general, the garnet cores have more negative δ18O values than rims, although oscillations are present. Negative values have been interpreted as influx of meteoric fluid and positive values as increased magmatic input. Here we report major and trace element concentrations for 17 core to rim Sidewinder garnet transects. REEs concentrations are low in all crystals, with total REE concentrations ranging from 0.710 ppm to 33.7 ppm, values that are lower than Cretaceous skarn garnets in the Sierra Nevada in the White Chief and Empire Mt skarns. Such low concentrations are likely due to the higher fraction of meteoric fluids during formation of the Sidewinder skarns. REE concentrations decrease from core to rim (REE core average=12.2ppm, REE rim average=7.21ppm). This is slightly more pronounced in the LREEs than in the HREEs (LaN/YbN core average= 10.9; rim average= 9.73, normalized to Chondrite). X­and tends to decrease core to rim in the Verde Antique skarn, whereas, Xand of the White Horse skarn does not correlate with distance from core. A large positive Eu anomaly (Eu/Eu* = 3­-30) in garnet from both skarns suggests oxidizing fluid conditions. Oxygen isotope data from garnet in these same skarns show periods of time with increased proportion of magmatic derived fluids in the total fluid budget. However, there is no corresponding widespread increase in total REE concentrations. Other studies of skarns from the western Sierra Nevadan arc (White Chief and Empire Mountain) observe complete decoupling of d18O values and trace element compositions. Future modeling should consider modal abundance of fluid soluble minerals in cooling and altering plutons to probe the REE budget.

Constraining N2O emissions since 1940 using firn air isotope measurements in both hemispheres

NASA Astrophysics Data System (ADS)

Prokopiou, Markella; Martinerie, Patricia; Sapart, Célia J.; Witrant, Emmanuel; Monteil, Guillaume; Ishijima, Kentaro; Bernard, Sophie; Kaiser, Jan; Levin, Ingeborg; Blunier, Thomas; Etheridge, David; Dlugokencky, Ed; van de Wal, Roderik S. W.; Röckmann, Thomas

2017-04-01

N2O is currently the third most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes over the past decades, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using new and previously published firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290 ± 1) nmol mol-1 in 1940 to (322 ± 1) nmol mol-1 in 2008, the isotopic composition of atmospheric N2O decreased by (-2.2 ± 0.2) ‰ for δ15Nav, (-1.0 ± 0.3) ‰ for δ18O, (-1.3 ± 0.6) ‰ for δ15Nα, and (-2.8 ± 0.6) ‰ for δ15Nβ over the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric box and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to fix at 123 years. The average isotopic composition over the investigated period is δ15Nav = (-7.6 ± 0.8) ‰ (vs. air-N2), δ18O = (32.2 ± 0.2) ‰ (vs. Vienna Standard Mean Ocean Water - VSMOW) for δ18O, δ15Nα = (-3.0 ± 1.9) ‰ and δ15Nβ = (-11.7 ± 2.3) ‰. δ15Nav, and δ15Nβ show some temporal variability, while for the other signatures the error bars of the reconstruction are too large to retrieve reliable temporal changes. Possible processes that may explain trends in 15N are discussed. The 15N site preference ( = δ15Nα - δ15Nβ) provides evidence of a shift in emissions from denitrification to nitrification, although the uncertainty envelopes are large.

Factors Controlling the Stable Nitrogen Isotopic Composition (δ15N) of Lipids in Marine Animals

PubMed Central

Svensson, Elisabeth; Schouten, Stefan; Hopmans, Ellen C.; Middelburg, Jack J.; Sinninghe Damsté, Jaap S.

2016-01-01

Lipid extraction of biomass prior to stable isotope analysis is known to cause variable changes in the stable nitrogen isotopic composition (δ15N) of residual biomass. However, the underlying factors causing these changes are not yet clear. Here we address this issue by comparing the δ15N of bulk and residual biomass of several marine animal tissues (fish, crab, cockle, oyster, and polychaete), as well as the δ15N of the extracted lipids. As observed previously, lipid extraction led to a variable offset in δ15N of biomass (differences ranging from -2.3 to +1.8 ‰). Importantly, the total lipid extract (TLE) was highly depleted in 15N compared to bulk biomass, and also highly variable (differences ranging from -14 to +0.7 ‰). The TLE consisted mainly of phosphatidylcholines, a group of lipids with one nitrogen atom in the headgroup. To elucidate the cause for the 15N-depletion in the TLE, the δ15N of amino acids was determined, including serine because it is one of the main sources of nitrogen to N-containing lipids. Serine δ15N values differed by -7 to +2 ‰ from bulk biomass δ15N, and correlated well with the 15N depletion in TLEs. On average, serine was less depleted (-3‰) than the TLE (-7 ‰), possibly due to fractionation during biosynthesis of N-containing headgroups, or that other nitrogen-containing compounds, such as urea and choline, or recycled nitrogen contribute to the nitrogen isotopic composition of the TLE. The depletion in 15N of the TLE relative to biomass increased with the trophic level of the organisms. PMID:26731720

Constraints on Earth degassing history from the argon isotope composition of Devonian atmosphere

NASA Astrophysics Data System (ADS)

Stuart, F. M.; Mark, D.

2012-04-01

The primordial and radiogenic isotopes of the noble gases combine to make them a powerful tool for determining the time and tempo of the outgassing of the Earth's interior. The outgassing history of the Earth is largely constrained from measurements of the isotopic composition of He, Ne, Ar and Xe in samples of modern mantle, crust and atmosphere. There have been few unequivocal measurement of the isotopic composition of noble gases in ancient atmosphere. We have re-visited whether ancient Ar is trapped in the ~400 Ma Rhynie chert [1]. We have analysed samples of pristine Rhynie chert using the ARGUS multi-collector mass spectrometer calibrated against the new determination of atmospheric Ar isotope ratios [2]. 40Ar/36Ar ratios are low, with many lower than the modern air value (298.8). Importantly these are accompanied by atmospheric 38Ar/36Ar ratios indicating that the low 40Ar/36Ar are not due to mass fractionation. We conclude that the Rhynie chert has captured Devonian atmosphere-derived Ar. The data indicate that the Devonian atmosphere 40Ar/36Ar was at least 3 % lower than the modern air value. Thus the Earth's atmosphere has accumulated at least 5 ± 0.2 x 1016 moles of 40Ar in the last 400 million years, at an average rate of 1.24 ± 0.06 x 108 mol 40Ar/year. This overlaps the rate determined from ice cores for the last 800,000 years [3] and implies that there has been no resolvable temporal change in Earth outgassing rate since mid-Palaeozoic times. The new data require the Earth outgassed early, and suggests that pristine samples of Archaean and Proterozoic chert may prove useful as palaeo-atmosphere tracers. [1] G. Turner, J. Geol. Soc. London 146, 147-154 (1989) [2] D. Mark, F.M. Stuart, M. de Podesta, Geochim. Cosmochim. Acta 75, 7494-7501 [3] M. Bender et al., Proc. Nat. Acad. Sci. 105, 8232-8237 (2008)

Barium isotopic compositions of oceanic basalts from São Miguel, Azores Archipelago

NASA Astrophysics Data System (ADS)

Yu, H.; Nan, X.; Huang, F.

2016-12-01

Oceanic island basalts (OIB) provide important information to decipher the processes of mantle convection and crustal material recycling1. OIBs from São Miguel, Azores Archipelago have extreme radiogenic isotope compositions2-3, representing an enriched component in their mantle source. However, the origins of the enriched mantle are still in debate. Previous studies proposed that the enriched component could be subducted terrigenous sediments2,4, delaminated subcontinental lithosphere5-6, recycled oceanic crust with evolved compositions (such as a subducted seamount)7, or enriched (E-MORB type) under-plated basalts which infiltrated the oceanic mantle lithosphere8. In this study, we use Ba isotopes to constrain the origin of enriched component beneath São Miguel because Ba isotopes can be significantly fractionated at the Earth's surface with low temperature environment than in the mantle with high temperature9-10. We analyzed Ba isotopes of 15 basalts from São Miguel. Although these samples have large variations of 87Sr/86Sr (0.703440-0.705996), 206Pb/204Pb (19.319-20.095) and 187Os/188Os (0.127-0.161), they have limited variation of 137Ba/134Ba (-0.003 to +0.048‰). The average 137Ba/134Ba of São Miguel basalts is 0.019±0.033‰ (n=15, 2SD), which is in the range of mantle (0.026±0.090‰, n=32, 2SD)9, indicating there is no surface material in the mantle source of São Miguel. The enriched source of São Miguel could be evolved material from the mantle. 1. Hofmann, 1997, Nature; 2. Hawkesworth et al., 1979, Nature; 3. White et al., 1979, CMP; 4. Turner et al., 1997, CG; 5. Widom et al., 1997, CG; 6. Moreira et al., 1999, EPSL; 7. Beier et al., 2007, EPSL; 8. Elliott et al., 2007, GCA; 9. Huang et al., 2015, Goldschmidt abs 1331; 10. Nan et al., 2016, Goldschmidt abs 2246.

Nature and origin of the sedimentary pile subducting in the Nankai Through

NASA Astrophysics Data System (ADS)

Chauvel, C.; Garcon, M.; Yobregat, E.; Chipoulet, C.; Labanieh, S.

2013-12-01

Nd-Hf isotopes and trace and major element concentrations were measured on bulk sediments recovered at Site C0012 during IODP Expedition 322 and 333 in the Shikoku basin. We analyzed the composition of different lithologies such as clay, claystone, sand, sandstone, and ash layers, all through the sedimentary pile, from the surface to the sediment-basalt interface, in order to identify compositional trends and source variations with depth. Major and trace element contents of the background sediments (hemipelagic mudstone) are very homogenous and span a relatively small range of values throughout the entire sedimentary pile. Their composition resembles that of the average upper continental crust of Rudnick and Gao (2003, Treatise on Geochemistry, Vol.3, p. 1-64). Nd and Hf isotopes are more variable, relatively unradiogenic (-8 < ɛNd < -3 ; -4 < ɛHf < +5) but display no systematic variations with depth (Fig. 1). Such isotopic compositions indicate that the background sedimentation of the Shikoku basin may consist of volcaniclastic material from the Izu-Bonin and/or Ryukyu arcs, detrital material eroded from SW Japan and relatively high amount of an evolved continental-derived component, probably Chinese loess as already suggested by Mahomet (2005, Sediment. Geol., 182, p.183-199). Compared to the background sedimentation, volcanic ash layers and volcaniclastic sandstones have very different trace element patterns and more radiogenic Nd-Hf isotopic signature (Fig. 1). Our results allow us to distinguish at least two different volcanic sources for these deposits. At the bottom of the sedimentary pile, siliciclastic sandstones with a mid-Miocene age are present; they have remarkably low ɛNd and ɛHf values (i.e. ɛNd < -8 and ɛHf < -5). Such isotopic compositions clearly demonstrate that their source cannot be the Japanese mainland, as suggested by previous studies (e.g. Underwood et al, 2009, Exp.322 PR ; Fergusson, 2003, Proc. ODP, Sci. Results 190/196). These sandstones are also too coarse to result from an accumulation of Chinese loess transported by wind (particles usually finer than 40 μm). Given the location of the Shikoku basin at 15Ma, we suggest that the siliciclastic sandstones mainly consists of detrital materials transported by Chinese rivers up to the sea in the Shikoku basin. Variations of ɛNd as a function of depth. Potential sediment sources are indicated by color bands

Spatial patterns of throughfall isotopic composition at the event and seasonal timescales

Treesearch

Scott T. Allen; Richard F. Keim; Jeffrey J. McDonnell

2015-01-01

Spatial variability of throughfall isotopic composition in forests is indicative of complex processes occurring in the canopy and remains insufficiently understood to properly characterize precipitation inputs to the catchment water balance. Here we investigate variability of throughfall isotopic composition with the objectives: (1) to quantify the spatial variability...

The Effects of Core Composition on Iron Isotope Fractionation During Planetary Differentiation

NASA Astrophysics Data System (ADS)

Elardo, S. M.; Shahar, A.; Caracas, R.; Mock, T. D.; Sio, C. K. I.

2018-05-01

High pressure and temperature isotope exchange experiments and density functional theory calculations show how the composition of planetary cores affects the fractionation of iron isotopes during planetary differentiation.

Using oxygen isotopes to establish freshwater sources in Bedford Basin, Nova Scotia, a Northwestern Atlantic fjord

NASA Astrophysics Data System (ADS)

Kerrigan, Elizabeth A.; Kienast, Markus; Thomas, Helmuth; Wallace, Douglas W. R.

2017-12-01

A weekly time-series of oxygen isotope (δ18O) measurements was collected over a 16-month period from near-surface (1 m) and near-bottom (60 m) waters of Bedford Basin, a coastal fjord adjacent to the Scotian Shelf, off eastern Canada. The time-series was complemented with δ18O measurements of local precipitation (rain and snow), river, and wastewater runoff. The isotopic composition of precipitation displayed strong seasonality with an average (volume-weighted) δ18O value of -5.39‰ (±0.96) for summer and a depleted value of -10.37‰ (±2.96) over winter. Winter precipitation exhibited more depleted and variable δ18O of solid precipitation relative to rainfall. The annual, amount-weighted average δ18O of Sackville River discharge (-6.49‰ ± 0.82) was not statistically different from precipitation (-7.24‰ ± 0.92), but exhibited less seasonal variation. Freshwater end-members (zero-salinity intercepts) estimated from annual and seasonal regressions of δ18O versus salinity (S) for Bedford Basin near-surface samples were consistent with the δ18O of summer precipitation and the annual, amount-weighted average for the Sackville River. However, the isotopically depleted signature of winter precipitation was not observed clearly in near-surface waters of Bedford Basin, which might reflect isotope enrichment during sublimation from accumulated snowfall prior to melting and discharge, or retention and mixing within the drainage basin. In near bottom waters, most of the δ18O-S variation (average freshwater end-member: 7.47‰ ± 2.17) could be explained by vertical mixing with near-surface waters (average freshwater end-member: -6.23‰ ± 0.34) and hence with locally-derived freshwater. However the near-bottom δ18O-S variation suggested an additional contribution of a freshwater end-member with a δ18O of -15.55‰ ± 2.3, consistent with a remotely-derived freshwater end-member identified previously for the Scotian Shelf. Residuals from a long-term regression of δ18O-S were generally within the range expected due to analytical uncertainty (±0.05); however near-surface waters exhibited seasonal variability of small amplitude, which was consistent with the timing and δ18O variability of local freshwater inputs.

Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

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

Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.

Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotopemore » observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ 18O v ranged from –40.2 to –15.9 ‰ and δ 2H v ranged from –278.7 to –113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess ( d v) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in d v, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol –1) indicate that regional evaporation can account for 40 to 60 % of the PBL water vapor. These estimates are in relatively good agreement with that derived from numerical weather model simulations. This relatively large fraction of evaporation-derived water vapor implies that evaporation has an important impact on the precipitation recycling ratio within the region. In conclusion, based on multiple constraints, we estimate that the summer season recycling fraction is about 30 %, indicating a potentially important link with convective precipitation.« less

δ18O and δD of lake waters across the Coast Range and Cascades, central Oregon: Modern insights from hydrologically open lakes into the control of landscape on lake water composition in deep time

NASA Astrophysics Data System (ADS)

Finkelstein, D. B.; Curtin, T.

2016-12-01

Reconstructing the stable isotopic composition of paleolake water normally requires an assumption of paleotemperature. However, hydrologically open paleolakes with short water residence times may have recorded paleoprecipitation along topographic gradients that are independent of lake water temperature. To identify the environmental and geographic controls on the isotopic composition of lake water, we sampled 22 natural lakes and reservoirs along a longitudinal and elevation gradient from the Pacific Ocean up and over the Coast and Cascade Ranges of central Oregon to the High Lava Plains in 2013 and 2015. The transect spans lakes of different origins, 6 geomorphic regions and an elevation range of 2-1942 m absl. The Coast Range lakes are sand hosted whereas the remaining are bedrock (volcanic and sedimentary) hosted. The lakes are hydrologically open and dominated by meteoric recharge. The water residence time ranges from months to decades. Samples were analyzed for temperature, pH, and total dissolved solids (TDS) in the field, and alkalinity and major cations and anions and stable isotopes of D and O in the lab. The pH ranges from 7 to 9.8 and shows no systematic variation based on substrate type or elevation. The lakes are dilute (avg. TDS = 35.8 ppm) and have low alkalinties (18.9 mg/L CaCO3) except for those in the High Lava Plains (avg. TDS = 337 ppm, alk: 291.2 mg/L CaCO3). In the Coast Range, Na is the major cation on an equivalent basis, reflecting proximity to the ocean. The easternmost lakes within the Coast Range are dominated by Ca, reflecting different drainage basins and substrate type. Lakes in the Western and High Cascades are dominated by Ca. The dominant cation and stable isotopic analyses clearly differentiate waters from different geomorphic regions. The δ18O ranges from -5.7 to -9.3 ‰ (VSMOW), and δD ranges from -37.8 to -63.6 ‰ (VSMOW) in the Coast Range whereas the δ18O ranges from -9.7 to -12.1 ‰ (VSMOW) and δD ranges from -71.5 to -86.5‰ (VSMOW) in the Cascades. Stable isotopic differences between mountain ranges reflect distance from the ocean and increasing elevation. Stable isotopes of water show no correlation with air or lake water temperatures. Average annual precipitation and bedrock across this topographic gradient controls the major ions and stable isotopic composition of these lakes.

Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

DOE PAGES

Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.; ...

2016-04-25

Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotopemore » observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ 18O v ranged from –40.2 to –15.9 ‰ and δ 2H v ranged from –278.7 to –113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess ( d v) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in d v, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol –1) indicate that regional evaporation can account for 40 to 60 % of the PBL water vapor. These estimates are in relatively good agreement with that derived from numerical weather model simulations. This relatively large fraction of evaporation-derived water vapor implies that evaporation has an important impact on the precipitation recycling ratio within the region. In conclusion, based on multiple constraints, we estimate that the summer season recycling fraction is about 30 %, indicating a potentially important link with convective precipitation.« less

The absence of lithium isotope fractionation during basalt differentiation: New measurements by multicollector sector ICP-MS

USGS Publications Warehouse

Tomascak, P.B.; Tera, F.; Helz, R.T.; Walker, R.J.

1999-01-01

We report measurements of the isotopic composition of lithium in basalts using a multicollector magnetic sector plasma-source mass spectrometer (MC-ICP-MS). This is the first application of this analytical technique to Li isotope determination. External precision of multiple replicate and duplicate measurements for a variety of sample types averages ??1.1??? (2?? population). The method allows for the rapid (???8 min/sample) analysis of small samples (???40 ng Li) relative to commonly used thermal ionization methods. The technique has been applied to a suite of samples from Kilauea Iki lava lake, Hawaii. The samples range from olivine-rich cumulitic lava to SiO2 - and K2O-enriched differentiated liquids, and have ??7Li (per mil deviation of sample 7Li/6Li relative to the L-SVEC standard) of +3.0 to +4.8. The data indicate a lack of per mil-level Li isotope fractionation as a result of crystal-liquid fractionation at temperatures greater than 1050??C. This conclusion has been tacitly assumed but never demonstrated, and is important to the interpretation of Li isotope results from such geochemically complex environments as island arcs. Copyright ?? 1999 Elsevier Science Ltd.

Weathering and vegetation controls on nickel isotope fractionation in surface ultramafic environments (Albania)

NASA Astrophysics Data System (ADS)

Estrade, Nicolas; Cloquet, Christophe; Echevarria, Guillaume; Sterckeman, Thibault; Deng, Tenghaobo; Tang, YeTao; Morel, Jean-Louis

2015-08-01

The dissolved nickel (Ni) isotopic composition of rivers and oceans presents an apparent paradox. Even though rivers represent a major source of Ni in the oceans, seawater is more enriched in the heavier isotopes than river-water. Additional sources or processes must therefore be invoked to account for the isotopic budget of dissolved Ni in seawater. Weathering of continental rocks is thought to play a major role in determining the magnitude and sign of isotopic fractionation of metals between a rock and the dissolved product. We present a study of Ni isotopes in the rock-soil-plant systems of several ultramafic environments. The results reveal key insights into the magnitude and the control of isotopic fractionation during the weathering of continental ultramafic rocks. This study introduces new constraints on the influence of vegetation during the weathering process, which should be taken into account in interpretations of the variability of Ni isotopes in rivers. The study area is located in a temperate climate zone within the ophiolitic belt area of Albania. The serpentinized peridotites sampled present a narrow range of heavy Ni isotopic compositions (δ60Ni = 0.25 ± 0.16 ‰, 2SD n = 2). At two locations, horizons within two soil profiles affected by different degrees of weathering all presented light isotopic compositions compared to the parent rock (Δ60Nisoil-rock up to - 0.63 ‰). This suggests that the soil pool takes up the light isotopes, while the heavier isotopes remain in the dissolved phase. By combining elemental and mineralogical analyses with the isotope compositions determined for the soils, the extent of fractionation was found to be controlled by the secondary minerals formed in the soil. The types of vegetation growing on ultramafic-derived soils are highly adapted and include both Ni-hyperaccumulating species, which can accumulate several percent per weight of Ni, and non-accumulating species. Whole-plant isotopic compositions were found to be isotopically heavier than the soil (Δ60Niwhole plant-soil up to 0.40‰). Fractions of Ni extracted by DTPA (diethylenetriaminepentaacetic acid) presented isotopically heavy compositions compared to the soil (Δ60NiDTPA-soil up to 0.89‰), supporting the hypothesis that the dissolved Ni fraction controlled by weathering has a heavy isotope signature. The non-hyperaccumulators (n = 2) were inclined to take up and translocate light Ni isotopes with a large degree of fractionation (Δ60Nileaves-roots up to - 0.60 ‰). For Ni-hyperaccumulators (n = 7), significant isotopic fractionation was observed in the plants in their early growth stages, while no fractionation occurred during later growth stages, when plants are fully loaded with Ni. This suggests that (i) the high-efficiency translocation process involved in hyperaccumulators does not fractionate Ni isotopes, and (ii) the root uptake process mainly controls the isotopic composition of the plant. In ultramafic contexts, vegetation composed of hyperaccumulators can significantly influence isotopic compositions through its remobilization in the upper soil horizon, thereby influencing the isotopic balance of Ni exported to rivers.

Influences on the stable oxygen and carbon isotopes in gerbillid rodent teeth in semi-arid and arid environments: Implications for past climate and environmental reconstruction

NASA Astrophysics Data System (ADS)

Jeffrey, Amy; Denys, Christiane; Stoetzel, Emmanuelle; Lee-Thorp, Julia A.

2015-10-01

The stable isotope composition of small mammal tissues has the potential to provide detailed information about terrestrial palaeoclimate and environments, because their remains are abundant in palaeontological and archaeological sites, and they have restricted home ranges. Applications to the Quaternary record, however, have been sparse and limited by an acute lack of understanding of small mammal isotope ecology, particularly in arid and semi-arid environments. Here we document the oxygen and carbon isotope composition of Gerbillinae (gerbil) tooth apatite across a rainfall gradient in northwestern Africa, in order to test the relative influences of the 18O/16O in precipitation or moisture availability on gerbil teeth values, the sensitivity of tooth apatite 13C/12C to plant responses to moisture availability, and the influence of developmental period on the isotopic composition of gerbil molars and incisors. The results show that the isotopic composition of molars and incisors from the same individuals differs consistent with the different temporal periods reflected by the teeth; molar teeth are permanently rooted and form around the time of birth, whereas incisors grow continuously. The results indicate that tooth choice is an important consideration for applications as proxy Quaternary records, but also highlights a new potential means to distinguish seasonal contexts. The oxygen isotope composition of gerbil tooth apatite is strongly correlated with mean annual precipitation (MAP) below 600 mm, but above 600 mm the teeth reflect the oxygen isotope composition of local meteoric water instead. Predictably, the carbon isotope composition of the gerbil teeth reflected C3 and C4 dietary inputs, however arid and mesic sites could not be distinguished because of the high variability displayed in the carbon isotope composition of the teeth due to the microhabitat and short temporal period reflected by the gerbil. We show that the oxygen isotope composition of small mammal teeth strongly reflects moisture availability in semi-arid and arid environments and would provide an excellent record of palaeo-aridity in a terrestrial setting. The results illustrate that an understanding of an animal's physiology is essential for interpreting the animal's isotopic responses to external contexts, especially in arid zones.

Stable lead isotopic analyses of historic and contemporary lead contamination of San Francisco Bay estuary

USGS Publications Warehouse

Ritson, P.I.; Bouse, R.M.; Flegal, A.R.; Luoma, S.N.

1999-01-01

Variations in stable lead isotopic composition (240Pb, 206Pb, 207Pb, 208Pb) in three sediment cores from the San Francisco Bay estuary document temporal changes in sources of lead during the past two centuries. Sediment, with lead from natural geologic sources, and relatively homogeneous lead isotopic compositions are overlain by sediments whose isotopic compositions indicate change in the sources of lead associated with anthropogenic modification of the estuary. The first perturbations of lead isotopic composition in the cores occur in the late 1800s concordant with the beginning of industrialization around the estuary. Large isotopic shifts, toward lower 206Pb/207Pb, occur after the turn of the century in both Richardson and San Pablo Bays. A similar relationship among lead isotopic compositions and lead concentrations in both Bays suggest contamination from the same source (a lead smelter). The uppermost sediments (post 1980) of all cores also have a relatively homogenous lead isotopic composition distinct from pre-anthropogenic and recent aerosol signatures. Lead isotopic compositions of leachates from fourteen surface sediments and five marsh samples from the estuary were also analyzed. These analyses suggest that the lead isotopic signature identified in the upper horizons of the cores is spatially homogeneous among recently deposited sediments throughout the estuary. Current aerosol lead isotopic compositions [Smith, D.R., Niemeyer, S., Flegal, A.R., 1992. Lead sources to California sea otters: industrial inputs circumvent natural lead biodepletion mechanisms. Environmental Research 57, 163-175] are distinct from the isotopic compositions of the surface sediments, suggesting that the major source of lead is cycling of historically contaminated sediments back through the water column. Both the upper core sediments and surface sediments apparently derive their lead predominantly from sources internal to the estuary. These results support the idea that geochemical cycling of lead between sediments and water accounts for persistently elevated lead concentrations in the water column despite 10-fold reduction of external source inputs to San Francisco Bay [Flegal, A.R., Rivera-Duarte, I., Ritson, P.I., Scelfo, G., Smith, G.J., Gordon, M., Sanudo-Wilhelmy, S.A., 1996. Metal contamination in San Francisco Waters: historic perturbations, contemporary concentrations, and future considerations in San Francisco Bay. In: Hollobaugh, J.T. (Ed.), The Ecosystem. AAAS, pp. 173-188].

Isotopic compositions of the elements, 2001

USGS Publications Warehouse

Böhlke, J.K.; De Laeter, J. R.; De Bievre, P.; Hidaka, H.; Peiser, H.S.; Rosman, K.J.R.; Taylor, P.D.P.

2005-01-01

The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the “best measurement” of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E)">Ar(E)Ar(E) and its uncertainty U[Ar(E)]">U[Ar(E)]U[Ar(E)] recommended by CAWIA in 2001.

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.

Mercury emissions and stable isotopic compositions at Vulcano Island (Italy)

NASA Astrophysics Data System (ADS)

Zambardi, T.; Sonke, J. E.; Toutain, J. P.; Sortino, F.; Shinohara, H.

2009-01-01

Sampling and analyses methods for determining the stable isotopic compositions of Hg in an active volcanic system were tested and optimized at the volcanic complex of Vulcano (Aeolian Islands, Italy). Condensed gaseous fumarole Hg (fum)T, plume gaseous elemental Hg (g)0 and plume particulate Hg (p)II were obtained at fumaroles F0, F5, F11, and FA. The average total Hg emissions, based on Hg T/SO 2 in condensed fumarolic gases and plumes, range from 2.5 to 10.1 kg y - 1 , in agreement with published values [Ferrara, R., Mazzolai, B., Lanzillotta, E., Nucaro, E., Pirrone, N., 2000. Volcanoes as emission sources of atmospheric mercury in the Mediterranean Basin. Sci. Total Environ. 259(1-3), 115-121; Aiuppa, A., Bagnato, E., Witt, M.L.I., Mather, T.A., Parello, F., Pyle, D.M., Martin, R.S., 2007. Real-time simultaneous detection of volcanic Hg and SO 2 at La Fossa Crater, Vulcano (Aeolian Islands, Sicily). Geophys. Res. Lett. 34(L21307).]. Plume Hg (p)II increases with distance from the fumarole vent, at the expense of Hg (g)0 and indicates significant in-plume oxidation and condensation of fumarole Hg (fum)T. Relative to the NIST SRM 3133 Hg standard, the stable isotopic compositions of Hg are δ 202Hg (fum)T = - 0.74‰ ± 0.18 (2SD, n = 4) for condensed gaseous fumarole Hg (fum)T, δ 202Hg (g)0 = - 1.74‰ ± 0.36 (2SD, n = 1) for plume gaseous elemental Hg (g)0 at the F0 fumarole, and δ 202Hg (p)II = - 0.11‰ ± 0.18 (2SD, n = 4) for plume particulate Hg (p)II. The enrichment of Hg (p)II in the heavy isotopes and Hg (g)0 in the light isotopes relative to the total condensed fumarolic Hg (fum)T gas complements the speciation data and demonstrates a gas-particle fractionation occurring after the gas expulsion in ambient T° atmosphere. A first order Rayleigh equilibrium condensation isotope fractionation model yields a fractionation factor α cond-gas of 1.00135 ± 0.00058.

Chlorophyll-a Photosynthesis and Mg Isotope Fractionation

NASA Astrophysics Data System (ADS)

Black, J.; Yin, Q.; Casey, B. H.

2006-12-01

Mg is the metal center of all the chlorophyll pigments and therefore at the center of the process of photosynthesis. Chlorophyll (Chl) is often used as a biomarker of photosynthesis and is an enormous contributor to the global carbon cycle. Biosynthetic processes fractionate isotopes of light elements and this led us to examine the isotopic composition of Mg in Chl, as another potential biomarker. Here we detail the Mg isotopic composition of Chl-a, extracted from cultures of Synechococcus elongatus, and the culture medium (Black et al., 2006). After Chl extraction, the Mg was liberated from Chl and purified on cation-exchange columns, with a final yield of 100 ± 5%. ^{26}Mg/^{24}Mg and ^{25}Mg/^{24}Mg, were measured relative to Cambridge 1 and DSM3 standards by a standard-sample-bracketing technique on an MC-ICP-MS (Nu Instruments Ltd). We have measured the average isotopic fractionation of Mg from six samples of Chl-a from early growth phase and 4 samples from late growth phase, 9 samples of the culture medium and the Cambridge 1 Std, all relative to the DSM3 Std. We demonstrate for the first time that there is a clearly resolved depletion in the heavy isotopes of Mg in Chl-a relative to the culture medium (Δ^{26}Mg =-0.61‰; Δ^{25}Mg =-0.30‰). The heavy isotope depletion observed may be caused by chelation effects during the biosynthesis of Chl-a. We are now evaluating two hypotheses about the cause of the fractionation. One hypothesis is that the insertion step induces a fractionation via the Mg- chelatase enzyme. The second is that transport into the cell, such as via an ion channel, causes the fractionation. In either case, no difference between Chl-a and Chl-b is anticipated. Experiments and field studies are underway to examine these ideas. References Black, J., Yin, Q.-Z., Casey, W.H., 2006. Geochim. Cosmochim. Acta, 70, 4072-4079.

Thallium isotope variations in an ore-bearing continental igneous setting: Collahuasi Formation, northern Chile

NASA Astrophysics Data System (ADS)

Baker, R. G. A.; Rehkämper, M.; Ihlenfeld, C.; Oates, C. J.; Coggon, R.

2010-08-01

Thallium is a highly incompatible element and a large fraction of the bulk silicate Earth Tl budget is, therefore, expected to reside in the continental crust. Nonetheless, the Tl isotope systematics of continental rocks are essentially unexplored at present. Here, we present new Tl isotope composition and concentration data for a suite of 36 intrusive and extrusive igneous rocks from the vicinity of porphyry Cu deposits in the Collahuasi Formation of the Central Andes in northern Chile. The igneous lithologies of the rocks are variably affected by the hydrothermal alteration that accompanied the formation of the Cu deposits. The samples display Tl concentrations that vary by more than an order of magnitude, from 0.1 to 3.2 μg/g, whilst ɛ 205Tl ranges between -5.1 and +0.1 (ɛ 205Tl is the deviation of the 205Tl/ 203Tl isotope ratio of a sample from a standard in parts per 10 4). These variations are primarily thought to be a consequence of hydrothermal alteration processes, including metasomatic transport of Tl, and formation/breakdown of Tl-bearing minerals, which are associated with small but significant Tl isotope effects. The Tl abundances show excellent correlations with both K and Rb concentrations but no co-variation with Cu. This demonstrates that Tl displays only limited chalcophile affinity in the continental crust of the Collahuasi Formation, but behaves as a lithophile element with a distribution that is primarily governed by partitioning of Tl + into K +-bearing phases. Collahuasi samples with propylitic alteration features, which are derived from the marginal parts of the hydrothermal systems, have, on average, slightly lighter Tl isotope compositions than rocks from the more central sericitic and argillic alteration zones. This small but statistically significant difference most likely reflects preferential retention of isotopically heavy Tl in alteration phases, such as white micas and clays, which formed during sericitic and argillic alteration.

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence.

PubMed

Berhanu, Tesfaye A; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S K; Johnson, Matthew S; Savarino, Joël

2014-06-28

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ((15)N, (17)O, and (18)O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ(15)N, δ(18)O, and Δ(17)O). From these measurements an average photolytic isotopic fractionation of (15)ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of (15)ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of (14)NO3 (-) and (15)NO3 (-) in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well reproduced the values obtained in the laboratory study. These cross sections can be used in isotopic models to reproduce the stable isotopic composition of nitrate found in Antarctic snow profiles.

Eddy Covariance measurements of stable isotopes (δD and δ18O) in water vapor

NASA Astrophysics Data System (ADS)

Braden-Behrens, Jelka; Knohl, Alexander

2017-04-01

Stable isotopes are a promising tool to enhance our understanding of ecosystem gas exchanges. Studying 18O and 2H in water vapour (H2Ov) can e.g. help partitioning evapotranspiration into its components. With recent developments in laser spectroscopy direct Eddy Covariance (EC) measurements for investigating fluxes of stable isotopologues became feasible. So far very few case studies have applied the EC method to measure stable isotopes in water vapor. We continuously measure fluxes of water vapor isotopologues with the EC method in a managed beech forest in Thuringia, Germany, since autumn 2015 using the following setup: An off-axis integrated cavity output water vapor isotope analyzer (WVIA, Los Gatos Research. Inc, USA) measures the water vapour concentration and its isotopic composition (δD and δ18O). The instrument, that was optimized for high flow rates (app. 4slpm) to generate high frequency (2Hz) measurements, showed sufficient precision with Allan Deviations of app. 0.12 ‰ for δD and 0.06 ‰ for δ18O for averaging periods of 100s. The instrument was calibrated hourly using a high-flow optimized version of the water vapor isotope standard source (WVISS, Los Gatos Research. Inc, USA) that provides water vapor with known isotopic composition for a large range of different concentrations. Our calibration scheme includes a near continuous concentration range calibration instead of a simple 2 or 3-point calibration to face the analyzers strong concentration dependency within a range of app. 6 000 to 16 000 ppm in winter and app. 8 000 to 23 000 ppm in summer. In the used setup, the high-flow and high-frequency optimized water vapor isotope analyzer (WVIA) showed suitable characteristics (Allan deviation and spectral energy distribution) to perform Eddy covariance measurements of stable isotopes in H2Ov. Thus, this novel instrument for EC measurements of water vapor isotopologues provides a new opportunity for studying the hydrological cycle in long-term observation networks like Fluxnet and ICOS.

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.

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

NASA Astrophysics Data System (ADS)

Berhanu, Tesfaye A.; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S. K.; Johnson, Matthew S.; Savarino, Joël

2014-06-01

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate (15N, 17O, and 18O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ15N, δ18O, and Δ17O). From these measurements an average photolytic isotopic fractionation of 15ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of 15ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of 14NO3- and 15NO3- in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well reproduced the values obtained in the laboratory study. These cross sections can be used in isotopic models to reproduce the stable isotopic composition of nitrate found in Antarctic snow profiles.

Human Provenancing: It's Elemental…

NASA Astrophysics Data System (ADS)

Meier-Augenstein, Wolfram; Kemp

2009-04-01

Forensic science already uses a variety of methods often in combination to determine a deceased person's identity if neither personal effects nor next of kin (or close friends) can positively identify the victim. While disciplines such as forensic anthropology are able to work from a blank canvass as it were and can provide information on age, gender and ethnical grouping, techniques such as DNA profiling do rely on finding a match either in a database or a comparative sample presumed to be an ante-mortem sample of the victim or from a putative relation. Chances for either to succeed would be greatly enhanced if information gained from a forensic anthropological examination and, circumstances permitting a facial reconstruction could be linked to another technique that can work from a blank canvass or at least does not require comparison to a subject specific database. With the help of isotope ratio mass spectrometry even the very atoms from which a body is made can be used to say something about a person that will help to focus human identification using traditional techniques such as DNA, fingerprints and odontology. Stable isotope fingerprinting works on the basis that almost all chemical elements and in particular the so-called light elements such as carbon (C) that comprise most of the human body occur naturally in different forms, namely isotopes. 2H isotope abundance values recorded by the human body through food and drink ultimately reflect averaged isotopic composition of precipitation or ground water. Stable isotope analysis of 2H isotopic composition in different human tissue such as hair, nails, bone and teeth enables us to construct a time resolved isotopic profile or ‘fingerprint' that may not necessarily permit direct identification of a murder victim or mass disaster victim but in conjunction with forensic anthropological information will provide sufficient intelligence to construct a profile for intelligence lead identification stating where a victim was from (point of origin), how old they were, what their ‘life style' was and even if and where they had recently travelled. Data from several criminal investigations are presented to illustrate potential and limitation of stable isotope analysis of human tissue in aid of victim identification.

Investigating the Influence of Vegetation Type on Modern Leaf Wax Hydrogen Isotopes from a High Latitude Ombrotrophic Bog to Inform Paleoclimate Interpretation

NASA Astrophysics Data System (ADS)

Balascio, N.; D'Andrea, W. J.; Anderson, R. S.

2016-12-01

Leaf wax hydrogen isotopes have been used to track changes in the isotopic composition of meteoric waters in a variety of locations. However, leaf wax compounds preserved in sedimentary environments reflect a mix of plant sources that can have a large range of molecular distributions and biosynthetic fractionation factors potentially complicating paleoclimate interpretations. Here we attempt to constrain the influence of vegetation type on leaf wax hydrogen isotope values at an ombrotrophic bog in northern Norway. We present: (i) δD values of n-alkanes from modern bog vegetation to establish the influence of vegetation type on n-alkane distributions and to provide a site-specific assessment of the biosynthetic isotopic fractionation, and (ii) δD values of n-alkanes from a sediment core spanning the last 10 ka where vegetation changes have been reconstructed based on pollen analysis. We found 14 different vegetation types growing on the bog surface that have average chain lengths from 25 to 30.5 and δD values of n-C25 to n-C33 ranging from -197‰ to -116‰. These samples also have a range of δD values among n-alkane homologues, from 1‰ to 33‰. Based on isotopic measurements of modern bog water, we calculate the average apparent fractionation of n-alkanes to be -108 ± 22‰. Sedimentary δD values of n-C25 to n-C33 over the last 10 ka range from -229 to -158‰ with distinct trends among mid- and long-chain length homologues. Changes in chain lengths and δD values, at times, correspond to vegetation shifts documented by pollen data, but also show unique trends that we interpret to represent variations in local precipitation isotopes related to past hydroclimate change.

Exploring the Potential of Laser Ablation Carbon Isotope Analysis for Examining Ecology during the Ontogeny of Middle Pleistocene Hominins from Sima de los Huesos (Northern Spain)

PubMed Central

Garcia, Nuria; Feranec, Robert S.; Passey, Benjamin H.; Cerling, Thure E.; Arsuaga, Juan Luis

2015-01-01

Laser ablation of tooth enamel was used to analyze stable carbon isotope compositions of teeth of hominins, red deer, and bears from middle Pleistocene sites in the Sierra de Atapuerca in northern Spain, to investigate the possibility that this technique could be used as an additional tool to identify periods of physiological change that are not detectable as changes in tooth morphology. Most of the specimens were found to have minimal intra-tooth variation in carbon isotopes (< 2.3‰), suggesting isotopically uniform diets through time and revealing no obvious periods of physiological change. However, one of the two sampled hominin teeth displayed a temporal carbon isotope shift (3.2‰) that was significantly greater than observed for co-occurring specimens. The δ13C value of this individual averaged about -16‰ early in life, and -13‰ later in life. This isotopic change occurred on the canine crown about 4.2 mm from the root, which corresponds to an approximate age of two to four years old in modern humans. Our dataset is perforce small owing to the precious nature of hominid teeth, but it demonstrates the potential utility of the intra-tooth isotope profile method for extracting ontogenetic histories of human ancestors. PMID:26673156

A multidisciplinary approach to define the hydrogeological model of the carbonate aquifer system in the Versilia River basin (Tuscany, Italy)

NASA Astrophysics Data System (ADS)

Menichini, M.; Doveri, M.; Giannecchini, R.; Raco, B.; Rosi, M.

2012-12-01

A hydrogeological study was carried out on important fractured/karst aquifer systems located in the Versilia River basin (Tuscany, Italy), in order to optimize the groundwater resources management. The main aim was the individuation of the feeding areas of the most important springs by means of a multidisciplinary approach using geological, hydrogeological and geochemical-isotopic tools. Some hydrogeological sections were elaborated in order to define the geometry of the main hydrostructures and to individuate possible groundwater divides. The elaboration of geochemical data allowed at identifying 3 main chemical facies: Ca-HCO3, Ca-SO4 and Na-Cl. The first two highlight the interaction of water with limestone/dolostone and carbonate-evaporite rocks for a time sufficient to acquire these chemical compositions and to achieve saturation/supersaturation in calcite and dolomite. The Na-Cl groundwater shows low salinity and a composition similar to rainwater, indicating a circulation in rocks containing minerals not very reactive and/or short interaction time with carbonate rocks. These two main types of water-rock interaction are confirmed by the isotopic ratio δ13C: for the Ca-HCO3 and Ca-SO4 types, δ13C value requires a significant contribution of carbon derived from dissolution of calcite, while for Na-Cl water, δ13C values are consistent with the addition of biogenic CO2 in rainwater. Stable water isotopes (δ18O and δ2H) confirm that groundwaters have a meteoric origin and that the wide range of values essentially depends on the different average altitude of feeding zone. Comparing the geological and hydrogeological features with the results of the geochemical processing, it is reasonable to assume that: the Na-Cl springs are representative of the superficial circuits, with small feeding zones and very low residence times in aquifer; whereas the Ca-HCO3 and Ca-SO4 springs are representative of relatively deep circuits developed in extensive aquifers with high permeability. The first type of springs was used to obtain the relationship between the δ18O ratio and the altitude of rainwater infiltration. Taking into account that they drain a small basin and considering the regulator effect of the aquifers, the isotopic composition of these springs are very similar to the annual average isotopic values of the local meteoric water. This relationship was used to evaluate the average altitude of the feeding area of the second type of springs. All these elements, and some tracer test results available in literature, allowed us to delimit the hydrogeological basins likely drained by the most important springs under study. In addition, for each hydrogeological system, a simplified water balance using meteorological data and the effective infiltration coefficients reported in the literature was performed, verifying that the delimited catchment areas are entirely consistent with the flow rate data of the springs.

Determination of the NPP Kr\\vsko spent fuel decay heat

NASA Astrophysics Data System (ADS)

Kromar, Marjan; Kurinčič, Bojan

2017-07-01

Nuclear fuel is designed to support fission process in a reactor core. Some of the isotopes, formed during the fission, decay and produce decay heat and radiation. Accurate knowledge of the nuclide inventory producing decay heat is important after reactor shut down, during the fuel storage and subsequent reprocessing or disposal. In this paper possibility to calculate the fuel isotopic composition and determination of the fuel decay heat with the Serpent code is investigated. Serpent is a well-known Monte Carlo code used primarily for the calculation of the neutron transport in a reactor. It has been validated for the burn-up calculations. In the calculation of the fuel decay heat different set of isotopes is important than in the neutron transport case. Comparison with the Origen code is performed to verify that the Serpent is taking into account all isotopes important to assess the fuel decay heat. After the code validation, a sensitivity study is carried out. Influence of several factors such as enrichment, fuel temperature, moderator temperature (density), soluble boron concentration, average power, burnable absorbers, and burnup is analyzed.

Response of carbon isotopic compositions of Early-Middle Permian coals in North China to palaeo-climate change

NASA Astrophysics Data System (ADS)

Ding, Dianshi; Liu, Guijian; Sun, Xiaohui; Sun, Ruoyu

2018-01-01

To investigate the magnitude to which the carbon isotopic ratio (δ13C) varies in coals in response to their contemporary terrestrial environment, the Early-Middle Permian Huainan coals (including coals from the Shanxi Formation, Lower Shihezi Formation and Upper Shihezi Formation) in North China were systematically sampled. A 2.5‰ variation range of δ13C values (-25.15‰ to -22.65‰) was observed in Huainan coals, with an average value of -24.06‰. As coal diagenesis exerts little influence on carbon isotope fractionation, δ13C values in coals were mainly imparted by those of coal-forming flora assemblages which were linked to the contemporary climate. The δ13C values in coals from the Shanxi and Lower Shihezi Formations are variable, reflecting unstable climatic oscillations. Heavy carbon isotope is enriched in coals of the Capitanian Upper Shihezi Formation, implying a shift to high positive δ13C values of coeval atmospheric CO2. Notably, our study provides evidence of the Kamura event in the terrestrial environment for the first time.

Long-term variations of fluxes of solar protons and helium isotopes

NASA Astrophysics Data System (ADS)

Anufriev, G. S.

2012-11-01

The fluxes of hydrogen and helium isotopes in the solar wind are reconstructed over a long time scale since the present time up to 600 million years back. Abundances of helium isotopes, obtained in the helium isotopic analysis made for 8 lunar soil samples, were used as initial data in the reconstruction procedure. Samples were taken off from various levels of the 1.6-m core of lunar soil delivered by the automatic Luna-24 station in 1976. The data on modern hydrogen and helium fluxes were used as well. The developed reconstruction procedure allowed one to select various solar wind components in a "gross" composition. Proton flux variations over the interval of 600 million years do not exceed a value of 40 %. Helium flux variations reach a value of 1.5-2 relative to the average value. Most likely, this circumstance is caused by considerable variations of a number of coronal mass ejections ( CME) enriched by helium. The arguments in favor of solar activity polycyclicity on a long time scale are discussed.

Mercury Isotopes as Proxies to Identify Sources and Environmental Impacts of Mercury in Sphalerites

PubMed Central

Yin, Runsheng; Feng, Xinbin; Hurley, James P.; Krabbenhoft, David P.; Lepak, Ryan F.; Hu, Ruizhong; Zhang, Qian; Li, Zhonggen; Bi, Xianwu

2016-01-01

During the past few years, evidence of mass independent fractionation (MIF) for mercury (Hg) isotopes have been reported in the Earth’s surface reservoirs, mainly assumed to be formed during photochemical processes. However, the magnitude of Hg-MIF in interior pools of the crust is largely unknown. Here, we reported significant variation in Hg-MIF signature (Δ199Hg: −0.24 ~ + 0.18‰) in sphalerites collected from 102 zinc (Zn) deposits in China, indicating that Hg-MIF can be recorded into the Earth’s crust during geological recycling of crustal material. Changing magnitudes of Hg-MIF signals were observed in Zn deposits with different formations, evidence that Hg isotopes (especially Hg-MIF) can be a useful tracer to identify sources (syngenetic and epigenetic) of Hg in mineral deposits. The average isotopic composition in studied sphalerites (δ202Hgaverage: −0.58‰; Δ199Hgaverage: +0.03‰) may be used to fingerprint Zn smelting activities, one of the largest global Hg emission sources. PMID:26728705

Multiple sulfur isotope evidence for massive oceanic sulfate depletion in the aftermath of Snowball Earth

PubMed Central

Sansjofre, Pierre; Cartigny, Pierre; Trindade, Ricardo I. F.; Nogueira, Afonso C. R.; Agrinier, Pierre; Ader, Magali

2016-01-01

The terminal Neoproterozoic Era (850–542 Ma) is characterized by the most pronounced positive sulfur isotope (34S/32S) excursions in Earth's history, with strong variability and maximum values averaging δ34S∼+38‰. These excursions have been mostly interpreted in the framework of steady-state models, in which ocean sulfate concentrations do not fluctuate (that is, sulfate input equals sulfate output). Such models imply a large pyrite burial increase together with a dramatic fluctuation in the isotope composition of marine sulfate inputs, and/or a change in microbial sulfur metabolisms. Here, using multiple sulfur isotopes (33S/32S, 34S/32S and 36S/32S ratios) of carbonate-associated sulfate, we demonstrate that the steady-state assumption does not hold in the aftermath of the Marinoan Snowball Earth glaciation. The data attest instead to the most impressive event of oceanic sulfate drawdown in Earth's history, driven by an increased pyrite burial, which may have contributed to the Neoproterozoic oxygenation of the oceans and atmosphere. PMID:27447895

Assessing modern climatic controls on southern Sierra Nevada precipitation and speleothem δ18O

NASA Astrophysics Data System (ADS)

McCabe-Glynn, S. E.; Johnson, K. R.; Berkelhammer, M. B.

2012-12-01

Precipitation in the southwestern United States (SW US) is highly seasonal and exhibits inter-annual to inter-decadal variability. A 1154-year δ18O time series obtained from a southwestern Sierra Nevada Mountain stalagmite from Crystal Cave, CRC-3, (36.58°N; 118.56°W; 1540 m) reveals substantial decadal to multi-decadal variability closely linked to the Pacific Decadal Oscillation (PDO), and more specifically, to sea surface temperatures (SSTs) in the Kuroshio Extension region, which impact the atmospheric trajectory and isotopic composition of moisture reaching the study site. The instrumental portion of the CRC-3 δ18O time series suggests that more negative precipitation δ18O values are delivered from higher latitudes during positive phases of the PDO and/or when SSTs in the Kuroshio Extension region are anomalously cool, such as during La Niña events. In order to improve our understanding of the controls on speleothem δ18O in this region, we have conducted a detailed modern study of the climate, hydrology, and stable isotopic composition of meteoric waters (precipitation and drip water) at the cave. Here we present Crystal Cave drip logger results from 2010 to 2012, the isotopic composition of North American Deposition Program precipitation samples collected from 2001 to 2012 from several locations near our site including Ash Mountain (ASM), Sequoia National Park-Giant Forest (Ca75), and Yosemite National Park (Ca99), and isotopic composition of cave drip water and glass plate calcite. We also compare the δ18O values in the precipitation to satellite imagery, NCAR/NCEP data, and NOAA Hysplit Model backward trajectories between the sites. Results indicate that this site is particularly sensitive to "Pineapple Express" type storms, a persistent flow of atmospheric moisture and heavy rainfall extending from near the Hawaiian Islands to the coast of North America, which average about twice as much precipitation as other storms in the Sierra Nevada during winter. Crystal Cave drip logger results indicate a low drip rate variability in the cave between July 2010 and July 2011, averaging between ~25 drips/hour but we observe a significant increase during three "Pineapple Express" type storms (PE) during the 2010-2011 winter. Analysis of the δ18O of precipitation samples collected during these storms events exhibit significantly more negative values which could complicate the interpretation of speleothem δ18O if the relative contribution of PE moisture varies on interannual to multi-decadal timescales.

Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

NASA Astrophysics Data System (ADS)

Xie, Xueshu; Zubarev, Roman A.

2015-03-01

Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p << 10-15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas.

[Sources of Methane in the Boreal Region

NASA Technical Reports Server (NTRS)

1998-01-01

In determining the global methane budget the sources of methane must be balanced with the sinks and atmospheric inventory. The approximate contribution of the different methane sources to the budget has been establish showing the major terrestrial inputs as rice, wetlands, bogs, fens, and tundra. Measurements and modeling of production in these sources suggest that temperature, water table height and saturation along with substratum composition are important in controlling methane production and emission. The isotopic budget of 13 C and D/H in methane can be used as a tool to clarify the global budget. This approach has achieved success at constraining the inputs. Studies using the isotopic approach place constraints on global methane production from different sources. Also, the relation between the two biogenic production pathways, acetate fermentation and CO2 reduction, and the effect of substratum composition can be made using isotope measurements shows the relation between the different biogenic, thermogenic and anthropogenic sources of methane as a function of the carbon and hydrogen isotope values for each source and the atmosphere, tropospheric composition. Methane emissions from ponds and fens are a significant source in the methane budget of the boreal region. An initial study in 1993 and 1994 on the isotopic composition of this methane source and the isotopic composition in relation to oxidation of methane at the sediment surface of the ponds or fen was conducted as part of our BOREAS project. The isotopic composition of methane emitted by saturated anoxic sediment is dependent on the sediment composition and geochemistry, but will be influenced by in situ oxidation, in part, a function of rooted plant activity. The influence of oxidation mediated by rooted plant activities on the isotopic composition of methane is not well known and will depend on the plant type, sediment temperature, and numerous other variables. Information on this isotopic composition is important in both understanding the bio-geochemistry of the system and also in determining the regional and global inputs for the methane isotope budget. In determining the destruction of methane for balancing the atmospheric methane budget soil oxidation must be considered.

Iron isotopic composition of blood serum in anemia of chronic kidney disease.

PubMed

Anoshkina, Yulia; Costas-Rodríguez, Marta; Speeckaert, Marijn; Van Biesen, Wim; Delanghe, Joris; Vanhaecke, Frank

2017-05-24

Chronic kidney disease (CKD) is a general term for disorders that affect the structure and function of the kidneys. Iron deficiency (ID) and anemia occur in the vast majority of CKD patients, most of whom are elderly. However, establishing the cause of anemia in CKD, and therefore making an informed decision concerning the corresponding therapeutic treatment, is still a challenge. High-precision Fe isotopic analysis of blood serum samples of CKD patients with and without ID/anemia was performed via multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) for such a purpose. Patients with CKD and/or iron disorders showed a heavier serum Fe isotopic composition than controls. Many clinical parameters used for the diagnosis and follow-up of anemia correlated significantly with the serum Fe isotopic composition. In contrast, no relation was observed between the serum Fe isotopic composition and the estimated glomerular filtration rate as a measure of kidney function. Among the CKD patients, the serum Fe isotopic composition was substantially heavier in the occurrence of ID anemia, while erythropoietin-related anemia did not exert this effect. The Fe isotopic composition can thus be useful for distinguishing these different types of anemias in CKD patients, i.e. ID anemia vs. erythropoietin-related anemia.

The Amazon-Laurentian connection as viewed from the Middle Proterozoic rocks in the central Andes, western Bolivia and northern Chile

USGS Publications Warehouse

Tosdal, R.M.

1996-01-01

Middle Proterozoic rocks underlying the Andes in western Bolivia, western Argentina, and northern Chile and Early Proterozoic rocks of the Arequipa massif in southern Peru?? from the Arequipa-Antofalla craton. These rocks are discontinuously exposed beneath Mesozoic and Cenozoic rocks, but abundant crystalline clasts in Tertiary sedimentary rocks in the western altiplano allow indirect samples of the craton. Near Berenguela, western Bolivia, the Oligocene and Miocene Mauri Formation contains boulders of granodiorite augen gneiss (1171??20 Ma and 1158??12 Ma; U-Pb zircon), quartzose gneiss and granofels that are inferred to have arkosic protoliths (1100 Ma source region; U-Pb zircon), quartzofeldspathic and mafic orthogneisses that have amphibolite- and granulite-facies metamorphic mineral assemblages (???1080 Ma metamorphism; U-Pb zircon), and undeformed granitic rocks of Phanerozoic(?) age. The Middle Proterozoic crystalline rocks from Berenguela and elsewhere in western Bolivia and from the Middle Proterozoic Bele??n Schist in northern Chile generally have present-day low 206Pb/204Pb ( 15.57), and elevated 208Pb/204Pb (37.2 to 50.7) indicative of high time-averaged Th/U values. The Middle Proterozoic rocks in general have higher presentday 206Pb/204Pb values than those of the Early Proterozoic rocks of the Arequipa massif (206Pb/204Pb between 16.1 and 17.1) but lower than rocks of the southern Arequipa-Antofalla craton (206Pb/204Pb> 18.5), a difference inferred to reflect Grenvillian granulite metamorphism. The Pb isotopic compositions for the various Proterozoic rocks lie on common Pb isotopic growth curves, implying that Pb incorporated in rocks composing the Arequipa-Antofalla craton was extracted from a similar evolving Pb isotopic reservoir. Evidently, the craton has been a coherent terrane since the Middle Proterozoic. Moreover, the Pb isotopic compositions for the Arequipa-Antofalla craton overlap those of the Amazon craton, thereby supporting a link between these cratons and seemingly precluding part of the Arequipa-Antofalla craton from being a detached fragment of another craton such as eastern Laurentia, which has been characterized by a different U/Pb history. Pb isotopic compositions for the Arequipa-Antofalla craton are, furthermore, distinct from those of the Proterozoic basement in the Precordillera terrane, western Argentina, indicating a Pb isotopic and presumably a tectonic boundary between them. The Pb isotopic compositions for the Precordillera basement are similar to those of eastern Laurentia, and support other data indicating that these rocks are a detached fragment of North America. Finally, the distinct Pb isotopic evolution history of the Arequipa-Antofalla craton and eastern Laurentia require minor modification to tectonic models linking eastern North America-Scotland to the oroclinal bend in western South America.

Stable nitrogen and carbon isotope (δ 15N and δ 13C) variability in shallow tropical Pacific soft coral and black coral taxa and implications for paleoceanographic reconstructions

NASA Astrophysics Data System (ADS)

Williams, Branwen; Grottoli, Andréa G.

2010-09-01

Soft corals and black corals are useful proxy tools for paleoceanographic reconstructions. However, most work has focused on deep-water taxa and few studies have used these corals as proxy organisms in shallow water (<200 m). To facilitate the use of stable nitrogen and carbon isotope (δ 15N and δ 13C) records from shallow-water soft coral and black coral taxa for paleoceanographic reconstructions, quantification of the inherent variability in skeletal isotope values between sites, across depth, and among taxa is needed. Here, skeletal δ 15N and δ 13C values were measured in multiple colonies from eleven genera of soft corals and two genera of black corals from across a depth transect (5-105 m) at two sites in Palau located in the tropical western Pacific Ocean. Overall, no difference in skeletal δ 15N and δ 13C values between sites was present. Skeletal δ 15N values significantly increased and δ 13C values decreased with depth. This is consistent with changes in isotope values of suspended particulate organic matter (POM) across the photic zone, suggesting that the primary food source to these corals is suspended POM and that the stable isotopic composition of POM controls the skeletal isotopic composition of these corals. Thus, to compare the isotope records of corals collected across a depth range in the photic zone, first order depth corrections of -0.013‰ m -1 and +0.023‰ m -1 are recommended for δ 15N and δ 13C, respectively. Average depth-corrected δ 15N values were similar between black corals and soft corals, indicating that corals in these orders feed at a similar trophic level. In contrast, average depth-corrected δ 13C values of black corals were significantly lower than that of soft corals, potentially resulting from metabolic processes associated with differing skeletal compositions among the orders (i.e., gorgonin vs. chitin based). Thus, a correction of +1.0‰ is recommended for black corals when comparing their δ 13C-based proxy records to soft corals. After correcting for both the depth and order effects, variability in δ 15N values among corals within each genera was low (standard deviation (SD) of the mean <±0.5‰), with the exception of Acanthorgorgia. The calculated SD of <±0.5‰ provides a first order guideline for the amount of variability that could be expected in a δ 15N record, and suggests that these corals may be useful for δ 15N-based paleoceanographic reconstructions. Variability in δ 13C values among corals within genera was also low (standard deviation of the mean <±0.5‰) with the exception of Rhipidipathes and Villogorgia. Similar to δ 15N, records from the genera studied here with the exception of Rhipidipathes and Villogorgia may be useful for δ 13C-based paleoceanographic reconstructions. Overall, using the recommendations developed here, stable isotope records from multiple sites, depths and taxa of these corals can be more rigorously compared.

High precision calcium isotope analysis using 42Ca-48Ca double-spike TIMS technique

NASA Astrophysics Data System (ADS)

Feng, L.; Zhou, L.; Gao, S.; Tong, S. Y.; Zhou, M. L.

2014-12-01

Double spike techniques are widely used for determining calcium isotopic compositions of natural samples. The most important factor controlling precision of the double spike technique is the choice of appropriate spike isotope pair, the composition of double spikes and the ratio of spike to sample（CSp/CN）. We propose an optimal 42Ca-48Ca double spike protocol which yields the best internal precision for calcium isotopic composition determinations among all kinds of spike pairs and various spike compositions and ratios of spike to sample, as predicted by linear error propagation method. It is suggested to use spike composition of 42Ca/(42Ca+48Ca) = 0.44 mol/mol and CSp/(CN+ CSp)= 0.12mol/mol because it takes both advantages of the largest mass dispersion between 42Ca and 48Ca (14%) and lowest spike cost. Spiked samples were purified by pass through homemade micro-column filled with Ca special resin. K, Ti and other interference elements were completely separated, while 100% calcium was recovered with negligible blank. Data collection includes integration time, idle time, focus and peakcenter frequency, which were all carefully designed for the highest internal precision and lowest analysis time. All beams were automatically measured in a sequence by Triton TIMS so as to eliminate difference of analytical conditions between samples and standards, and also to increase the analytical throughputs. The typical internal precision of 100 duty cycles for one beam is 0.012‒0.015 ‰ (2δSEM), which agrees well with the predicted internal precision of 0.0124 ‰ (2δSEM). Our methods improve internal precisions by a factor of 2‒10 compared to previous methods of determination of calcium isotopic compositions by double spike TIMS. We analyzed NIST SRM 915a, NIST SRM 915b and Pacific Seawater as well as interspersed geological samples during two months. The obtained average δ44/40Ca (all relative to NIST SRM 915a) is 0.02 ± 0.02 ‰ (n=28), 0.72±0.04 ‰ (n=10) and 1.93±0.03 ‰ (n=21) for NIST SRM 915a, NIST SRM 915b and Pacific Seawater, respectively. The long-term reproducibility is 0.10‰ (2 δSD), which is comparable to the best external precision of 0.04 ‰ (2 δSD) of previous methods, but our sample throughputs are doubled with significant reduction in amount of spike used for single samples.

Modelling and intepreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2012-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, droplet size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

Modelling and interpreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2013-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed-phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters, including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, particle size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

Determination of lithium isotopes at natural abundance levels by atomic absorption spectrometry

USGS Publications Warehouse

Meier, A.L.

1982-01-01

The relationships of the absorption of 6Li and 7Li hollow cathode lamp emissions are used to determine lithium isotopic composition in the natural abundance range of geologic materials. Absorption was found to have a nonlinear dependence upon total lithium concentration and isotopic composition. A method using nonlinear equations to describe the relationship of the absorption of 6Li and 7Li lamp radiation is proposed as a means of calculating isotopic composition that is independent of total lithium concentration.

Palaeotemperature estimation in the Holsteinian Interglacial (MIS 11) based on oxygen isotopes of aquatic gastropods from eastern Poland

NASA Astrophysics Data System (ADS)

Szymanek, Marcin

2017-12-01

For quantitative estimation of past water temperature of four Holsteinian (MIS 11) palaeolakes from eastern Poland, the oxygen isotope palaeothermometer was applied to shells of the aquatic gastropods Viviparus diluvianus and Valvata piscinalis. The δ18O composition of their shells demonstrated the average growth-season water temperatures during the mesocratic stage of the interglacial (Ortel Królewski Lake), during its climatic optimum - the Carpinus-Abies Zone (Ossówka-Hrud, Roskosz and Szymanowo Lakes), and in the post-optimum (Szymanowo Lake). The calculation was based on δ18OShell values and the δ18OWater assumed for the Holsteinian from the modern oxygen isotope composition of precipitation and the expected amount of evaporative enrichment. The mean oxygen isotope palaeotemperatures of Ortel Królewski lake waters were in the range of 18.1-21.9°C and were uniform for the Taxus and Pinus-Larix zones. Ossówka-Hrud and Roskosz Lakes had mean temperatures of 17.4-21.0°C during the climatic optimum, whereas the temperature of Szymanowo lake waters was estimated at 20.6-21.7°C at that time. These values are concordant with the pollen-inferred July air temperatures noted during the Holsteinian in eastern Poland. Relatively high values of 25°C in the post-optimum noted at Szymanowo were connected with the presence of a shallow and warm isolated bay indicated by pollen and mollusc records.

Latitudinal change in precipitation and water vapor isotopes over Southern ocean

NASA Astrophysics Data System (ADS)

Rahul, P.

2015-12-01

The evaporation process over ocean is primary source of water vapor in the hydrological cycle. The Global Network of Isotopes in Precipitation (GNIP) dataset of rainwater and water vapor isotopes are predominantly based on continental observations, with very limited observation available from the oceanic area. Stable isotope ratios in precipitation provide valuable means to understand the process of evaporation and transport of water vapor. This is further extended in the study of past changes in climate from the isotopic composition of ice core. In this study we present latitudinal variability of water vapor and rainwater isotopic composition and compared it with factors like physical condition of sea surface water from near equator (1°S) to the polar front (56°S) during the summer time expedition of the year 2013. The water vapor and rainwater isotopes showed a sharp depletion in isotopes while progressively move southward from the tropical regions (i.e. >30°S), which follows the pattern recorded in the surface ocean water isotopic composition. From the tropics to the southern latitudes, the water vapor d18O varied between -11.8‰ to -14.7‰ while dD variation ranges between -77.7‰ to -122.2‰. Using the data we estimated the expected water vapor isotopic composition under kinetic as well as equilibrium process. Our observation suggests that the water vapor isotopic compositions are in equilibrium with the sea water in majority of cases. At one point of observation, where trajectory of air parcel originated from the continental region, we observed a large deviation from the existing trend of latitudinal variability. The deduced rainwater composition adopting equilibrium model showed a consistent pattern with observed values at the tropical region, while role of kinetic process become dominant on progressive shift towards the southern latitudes. We will draw comparison of our observation with other data available in the literature together with isotope model data during the presentation.

Stable Isotope Anatomy of Tropical Cyclone Ita, North-Eastern Australia, April 2014

PubMed Central

Munksgaard, Niels C.; Zwart, Costijn; Kurita, Naoyuki; Bass, Adrian; Nott, Jon; Bird, Michael I.

2015-01-01

The isotope signatures registered in speleothems during tropical cyclones (TC) provides information about the frequency and intensity of past TCs but the precise relationship between isotopic composition and the meteorology of TCs remain uncertain. Here we present continuous δ18O and δ2H data in rainfall and water vapour, as well as in discrete rainfall samples, during the passage of TC Ita and relate the evolution in isotopic compositions to local and synoptic scale meteorological observations. High-resolution data revealed a close relationship between isotopic compositions and cyclonic features such as spiral rainbands, periods of stratiform rainfall and the arrival of subtropical and tropical air masses with changing oceanic and continental moisture sources. The isotopic compositions in discrete rainfall samples were remarkably constant along the ~450 km overland path of the cyclone when taking into account the direction and distance to the eye of the cyclone at each sampling time. Near simultaneous variations in δ18O and δ2H values in rainfall and vapour and a near-equilibrium rainfall-vapour isotope fractionation indicates strong isotopic exchange between rainfall and surface inflow of vapour during the approach of the cyclone. In contrast, after the passage of spiral rainbands close to the eye of the cyclone, different moisture sources for rainfall and vapour are reflected in diverging d-excess values. High-resolution isotope studies of modern TCs refine the interpretation of stable isotope signatures found in speleothems and other paleo archives and should aim to further investigate the influence of cyclone intensity and longevity on the isotopic composition of associated rainfall. PMID:25742628

Intramolecular Isotopic Studies: Chemical Enhancements and Alternatives

NASA Astrophysics Data System (ADS)

Hayes, J. M.

2016-12-01

As mass spectroscopic and NMR-based methods now appropriately flourish, chemical techniques should not be forgotten. First, the methods developed by pioneering intramolecular analysts can be reapplied to new samples. Second, they can be extended. The synthesis of intramolecular isotopic standards is particularly important and straightforward. It requires only that a chemical reaction has no secondary products. An example is provided by the addition of carbon dioxide to a Grignard reagent. The reaction proceeds with an isotope effect. The isotopic composition of the carboxyl group in the acid which is produced is thus not equal to that of the starting carbon dioxide but the unconsumed CO2 can be recovered and analyzed. A simple titration can show that all the rest of the CO2 is in the product acid. The isotopic composition of the carboxyl group can then be calculated by difference. The product is an intramolecular isotopic standard, an organic molecule in which the isotopic composition of a specific carbon position is known accurately. Both analysts and reviewers can thus gain invaluable confidence in the accuracy of instrumental results. A second example: the haloform reaction quantitatively degrades methyl ketones, producing a carboxylic acid which can be decarboxylated to determine the isotopic composition of the parent carbonyl and a haloform (CHI3, for example) that can be combusted to determine the isotopic composition of the methyl group. Ketones thus analyzed can be combined with Grignard reagents to yield carbon skeletons in which the isotopic compositions of internal and terminal -CH2- and -CH3 groups are known accurately. In general, analysts accustomed to demanding quantitative reactions should remember the power of mass balances and recognize that many organic-chemical reactions, while not quantitative, lack side products and can be driven to the total consumption of at least one reactant.

Testing the chondrule-rich accretion model for planetary embryos using calcium isotopes

NASA Astrophysics Data System (ADS)

Amsellem, Elsa; Moynier, Frédéric; Pringle, Emily A.; Bouvier, Audrey; Chen, Heng; Day, James M. D.

2017-07-01

Understanding the composition of raw materials that formed the Earth is a crucial step towards understanding the formation of terrestrial planets and their bulk composition. Calcium is the fifth most abundant element in terrestrial planets and, therefore, is a key element with which to trace planetary composition. However, in order to use Ca isotopes as a tracer of Earth's accretion history, it is first necessary to understand the isotopic behavior of Ca during the earliest stages of planetary formation. Chondrites are some of the oldest materials of the Solar System, and the study of their isotopic composition enables understanding of how and in what conditions the Solar System formed. Here we present Ca isotope data for a suite of bulk chondrites as well as Allende (CV) chondrules. We show that most groups of carbonaceous chondrites (CV, CI, CR and CM) are significantly enriched in the lighter Ca isotopes (δ 44 / 40 Ca = + 0.1 to + 0.93 ‰) compared with bulk silicate Earth (δ 44 / 40 Ca = + 1.05 ± 0.04 ‰, Huang et al., 2010) or Mars, while enstatite chondrites are indistinguishable from Earth in Ca isotope composition (δ 44 / 40 Ca = + 0.91 to + 1.06 ‰). Chondrules from Allende are enriched in the heavier isotopes of Ca compared to the bulk and the matrix of the meteorite (δ 44 / 40 Ca = + 1.00 to + 1.21 ‰). This implies that Earth and Mars have Ca isotope compositions that are distinct from most carbonaceous chondrites but that may be like chondrules. This Ca isotopic similarity between Earth, Mars, and chondrules is permissive of recent dynamical models of planetary formation that propose a chondrule-rich accretion model for planetary embryos.

The carbon and nitrogen ecophysiologies of two endemic tropical orchids mirrors those of their temperate relatives and the local environment.

PubMed

Hynson, Nicole A

2016-11-01

Orchids are one of the most widely distributed plant families. However, current research on the ecophysiology of terrestrial orchids is biased towards temperate species. Thus, it is currently unknown whether tropical terrestrial orchids belong to similar trophic guilds as their temperate relatives. To examine the ecophysiologies of two tropical terrestrial orchids, I analysed the carbon and nitrogen stable isotope compositions and nitrogen concentrations of the Hawaiian endemics Anoectochilus sandvicensis and Liparis hawaiensis . I compared these values with those of surrounding vegetation and their temperate relatives. I found that A. sandvicensis was consistently enriched in the heavy isotope of nitrogen ( 15 N) and had higher nitrogen (N) concentrations than surrounding vegetation, and these values were even higher than those of its temperate relatives. Carbon stable isotope composition among populations of A. sandvicensis varied by island. These results point to local environment and evolutionary history determining the ecophysiology of this species. Whereas L.hawaiensis was also enriched in 15 N and had on average higher N concentrations than surrounding vegetation, these values were not significantly different from temperate relatives, indicating that evolutionary history may be a stronger predictor of this orchid species' ecophysiology than environment. I suggest that both Hawaiian species are potentially partially mycoheterotrophic.

The carbon and nitrogen ecophysiologies of two endemic tropical orchids mirrors those of their temperate relatives and the local environment

PubMed Central

2016-01-01

Orchids are one of the most widely distributed plant families. However, current research on the ecophysiology of terrestrial orchids is biased towards temperate species. Thus, it is currently unknown whether tropical terrestrial orchids belong to similar trophic guilds as their temperate relatives. To examine the ecophysiologies of two tropical terrestrial orchids, I analysed the carbon and nitrogen stable isotope compositions and nitrogen concentrations of the Hawaiian endemics Anoectochilus sandvicensis and Liparis hawaiensis. I compared these values with those of surrounding vegetation and their temperate relatives. I found that A. sandvicensis was consistently enriched in the heavy isotope of nitrogen (15N) and had higher nitrogen (N) concentrations than surrounding vegetation, and these values were even higher than those of its temperate relatives. Carbon stable isotope composition among populations of A. sandvicensis varied by island. These results point to local environment and evolutionary history determining the ecophysiology of this species. Whereas L.hawaiensis was also enriched in 15N and had on average higher N concentrations than surrounding vegetation, these values were not significantly different from temperate relatives, indicating that evolutionary history may be a stronger predictor of this orchid species' ecophysiology than environment. I suggest that both Hawaiian species are potentially partially mycoheterotrophic. PMID:28018622

Amazon capims (floating grassmats) - A source of C-13 enriched methane to the troposphere

NASA Technical Reports Server (NTRS)

Chanton, Jeffrey; Crill, Patrick; Bartlett, Karen; Martens, Christopher

1989-01-01

The C-13 isotopic composition of methane emitted to the troposphere from Amazon capims (floating grassmats) ranged from -36.9 to -48.0, per mil averaging -44.4 + or - 4.2 per mil. All pools of methane associated with the grassmats were enriched; methane withdrawn from plant stems ranged from -39 to -49 per mil while bubbles stirred from the root mat averaged -41.4 per mil. As the CH4 flux from these habitats makes up some 40 percent of the total flux from the Amazon floodplain, methane emissions from the region as a whole must be enriched in.

Lagrangian process attribution of isotopic variations in near-surface water vapour in a 30-year regional climate simulation over Europe

NASA Astrophysics Data System (ADS)

Dütsch, Marina; Pfahl, Stephan; Meyer, Miro; Wernli, Heini

2018-02-01

Stable water isotopes are naturally available tracers of moisture in the atmosphere. Due to isotopic fractionation, they record information about condensation and evaporation processes during the transport of air parcels, and therefore present a valuable means for studying the global water cycle. However, the meteorological processes driving isotopic variations are complex and not very well understood so far, in particular on short (hourly to daily) timescales. This study presents a Lagrangian method for attributing the isotopic composition of air parcels to meteorological processes, which provides new insight into the isotopic history of air parcels. It is based on the temporal evolution of the isotope ratios, the humidity, the temperature, and the location of the air parcels. Here these values are extracted along 7-day backward trajectories started every 6 hours from near the surface in a 30-year regional climate simulation over Europe with the isotope-enabled version of the model of the Consortium for Small-Scale Modelling (COSMOiso). The COSMOiso simulation has a horizontal resolution of 0.25° and is driven at the lateral boundaries by a T106 global climate simulation with the isotope-enabled version of the European Centre Hamburg model (ECHAMwiso). Both simulations are validated against measurements from the Global Network of Isotopes in Precipitation (GNIP), which shows that nesting COSMOiso within ECHAMwiso improves the representation of δ2H and deuterium excess in monthly accumulated precipitation. The method considers all isotopic changes that occur inside the COSMOiso model domain, which, on average, correspond to more than half of the mean and variability in both δ2H and deuterium excess at the air parcels' arrival points. Along every trajectory, the variations in the isotope values are quantitatively decomposed into eight process categories (evaporation from the ocean, evapotranspiration from land, mixing with moister air, mixing with drier air, liquid cloud formation, mixed phase cloud formation, ice cloud formation, and no process). The results show that for air parcels arriving over the ocean, evaporation from the ocean is the primary factor controlling δ2H and deuterium excess. Over land, evapotranspiration from land and mixing with moister air are similarly important. Liquid and mixed phase cloud formation contribute to the variability of δ2H and deuterium excess, especially over continental Europe. In summary, the presented method helps to better understand the linkage between the meteorological history of air parcels and their isotopic composition, and may support the interpretation of stable water isotope measurements in future.

Nitrogen stable isotope composition (δ15N) of vehicle-emitted NOx.

PubMed

Walters, Wendell W; Goodwin, Stanford R; Michalski, Greg

2015-02-17

The nitrogen stable isotope ratio of NOx (δ(15)N-NOx) has been proposed as a regional indicator for NOx source partitioning; however, knowledge of δ(15)N values from various NOx emission sources is limited. This study presents a detailed analysis of δ(15)N-NOx emitted from vehicle exhaust, the largest source of anthropogenic NOx. To accomplish this, NOx was collected from 26 different vehicles, including gasoline and diesel-powered engines, using a modification of a NOx collection method used by the United States Environmental Protection Agency, and δ(15)N-NOx was analyzed. The vehicles sampled in this study emitted δ(15)N-NOx values ranging from -19.1 to 9.8‰ that negatively correlated with the emitted NOx concentrations (8.5 to 286 ppm) and vehicle run time because of kinetic isotope fractionation effects associated with the catalytic reduction of NOx. A model for determining the mass-weighted δ(15)N-NOx from vehicle exhaust was constructed on the basis of average commute times, and the model estimates an average value of -2.5 ± 1.5‰, with slight regional variations. As technology improvements in catalytic converters reduce cold-start emissions in the future, it is likely to increase current δ(15)N-NOx values emitted from vehicles.

Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water

NASA Astrophysics Data System (ADS)

Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

2016-04-01

Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the oxygen isotope composition of ambient CO2. This non-destructive approach was tested through laboratory incubations of air-dried soils that were re-wetted with water of known isotopic composition. Performance was assessed by comparing estimates of the soil water oxygen isotope composition derived from open chamber flux measurements with those measured in the irrigation water and soil water extracted following incubations. The influence of soil pH and bovine carbonic anhydrase additions on these estimates was also investigated. Coherent values were found between the soil water composition estimates obtained from the dual steady state approach and those measured for irrigation waters. Estimates of carbonic anhydrase activity made using this approach also reflected well artificial increases to the concentration of carbonic anhydrase and indicated that this activity was sensitive to soil pH.

Multiple stable isotope fronts during non-isothermal fluid flow

NASA Astrophysics Data System (ADS)

Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

2018-02-01

Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may develop in kinetically limited systems, which propagates with the advection speed of the incoming fluid and is, therefore, traveling fastest. The results show that oxygen isotope signatures at thermal fronts recorded in rocks and veins that experienced isotope exchange with fluids can easily be misinterpreted, namely if bulk analytical techniques are applied. However, stable isotope microanalysis on precipitated minerals may - if later isotope exchange is kinetically limited - provide a valuable archive of the transient thermal and hydrological evolution of a system.

Water balance model for mean annual hydrogen and oxygen isotope distributions in surface waters of the contiguous United States

NASA Astrophysics Data System (ADS)

Bowen, Gabriel J.; Kennedy, Casey D.; Liu, Zhongfang; Stalker, Jeremy

2011-12-01

The stable H and O isotope composition of river and stream water records information on runoff sources and land-atmosphere water fluxes within the catchment and is a potentially powerful tool for network-based monitoring of ecohydrological systems. Process-based hydrological models, however, have thus far shown limited power to replicate observed large-scale variation in U.S. surface water isotope ratios. Here we develop a geographic information system-based model to predict long-term annual average surface water isotope ratios across the contiguous United States. We use elevation-explicit, gridded precipitation isotope maps as model input and data from a U.S. Geological Survey monitoring program for validation. We find that models incorporating monthly variation in precipitation-evapotranspiration (P-E) amounts account for the majority (>89%) of isotopic variation and have reduced regional bias relative to models that do not consider intra-annual P-E effects on catchment water balance. Residuals from the water balance model exhibit strong spatial patterning and correlations that suggest model residuals isolate additional hydrological signal. We use interpolated model residuals to generate optimized prediction maps for U.S. surface water δ2H and δ18O values. We show that the modeled surface water values represent a relatively accurate and unbiased proxy for drinking water isotope ratios across the United States, making these data products useful in ecological and criminal forensics applications that require estimates of the local environmental water isotope variation across large geographic regions.

Using multiple isotopes to understand the source of ingredients used in golden beverages

NASA Astrophysics Data System (ADS)

Wynn, J. G.

2011-12-01

Traditionally, beer contains 4 simple ingredients: water, barley, hops and yeast. Each of these ingredients used in the brewing process contributes some combination of a number of "traditional" stable isotopes (i.e., isotopes of H, C, O, N and S) to the final product. As an educational exercise in an "Analytical Techniques in Geology" course, a group of students analyzed the isotopic composition of the gas, liquid and solid phases of a variety of beer samples collected from throughout the world (including other beverages). The hydrogen and oxygen isotopic composition of the water followed closely the isotopic composition of local meteoric water at the source of the brewery, although there is a systematic offset from the global meteoric water line that may be due to the effects of CO2-H2O equilibration. The carbon isotopic composition of the CO2 reflected that of the solid residue (the source of carbon used as a fermentation substrate), but may potentially be modified by addition of gas-phase CO2 from an inorganic source. The carbon isotopic composition of the solid residue similarly tracks that of the fermentation substrate, and may indicate some alcohol fermented from added sugars in some cases. The nitrogen isotopic composition of the solid residue was relatively constant, and may track the source of nitrogen in the barley, hops and yeast. Each of the analytical methods used is a relatively standard technique used in geological applications, making this a "fun" exercise for those involved, and gives the students hands-on experience with a variety of analytes from a non-traditional sample material.

The ruthenium isotopic composition of the oceanic mantle

NASA Astrophysics Data System (ADS)

Bermingham, K. R.; Walker, R. J.

2017-09-01

The approximately chondritic relative, and comparatively high absolute mantle abundances of the highly siderophile elements (HSE), suggest that their concentrations in the bulk silicate Earth were primarily established during a final ∼0.5 to 1% of ;late accretion; to the mantle, following the cessation of core segregation. Consequently, the isotopic composition of the HSE Ru in the mantle reflects an amalgamation of the isotopic compositions of late accretionary contributions to the silicate portion of the Earth. Among cosmochemical materials, Ru is characterized by considerable mass-independent isotopic variability, making it a powerful genetic tracer of Earth's late accretionary building blocks. To define the Ru isotopic composition of the oceanic mantle, the largest portion of the accessible mantle, we report Ru isotopic data for materials from one Archean and seven Phanerozoic oceanic mantle domains. A sample from a continental lithospheric mantle domain is also examined. All samples have identical Ru isotopic compositions, within analytical uncertainties, indicating that Ru isotopes are well mixed in the oceanic mantle, defining a μ100Ru value of 1.2 ± 7.2 (2SD). The only known meteorites with the same Ru isotopic composition are enstatite chondrites and, when corrected for the effects of cosmic ray exposure, members of the Main Group and sLL subgroup of the IAB iron meteorite complex which have a collective CRE corrected μ100Ru value of 0.9 ± 3.0. This suggests that materials from the region(s) of the solar nebula sampled by these meteorites likely contributed the dominant portion of late accreted materials to Earth's mantle.

The influence of diet on the δ 13C of shell carbon in the pulmonate snail Helix aspersa

NASA Astrophysics Data System (ADS)

Stott, Lowell D.

2002-02-01

The influence of diet and atmospheric CO 2 on the carbon isotope composition of shell aragonite and shell-bound organic carbon in the pulmonate snail Helix aspersa raised in the laboratory was investigated. Three separate groups of snails were raised on romaine lettuce (C3 plant, δ 13C=-25.8‰), corn (C4 plant, δ 13C=-10.5‰), and sour orange ( 12C-enriched C3 plant, δ 13C=-39.1‰). The isotopic composition of body tissues closely tracked the isotopic composition of the snail diet as demonstrated previously. However, the isotopic composition of the acid insoluble organic matrix extracted from the aragonite shells does not track diet in all groups. In snails that were fed corn the isotopic composition of the organic matrix was more negative than the body by as much as 5‰ whereas the matrix was approximately 1‰ heavier than the body tissues in snails fed a diet of C3 plant material. These results indicate that isotopic composition of the organic matrix carbon cannot be used as an isotopic substrate for paleodietary reconstructions without first determining the source of the carbon and any associated fractionations. The isotopic composition of the shell aragonite is offset from the body tissues by 12.3‰ in each of the culture groups. This offset was not influenced by the consumption of carbonate and is not attributable to the diffusion of atmospheric CO 2 into the hemolymph. The carbon isotopic composition of shell aragonite is best explained in terms of equilibrium fractionations associated with exchange between metabolic CO 2 and HCO 3 in the hemolymph and the fractionation associated with carbonate precipitation. These results differ from previous studies, based primarily on samples collected in the field, that have suggested atmospheric carbon dioxide contributes significantly to the shell δ 13C. The culture results indicate that the δ 13C of aragonite is a good recorder of the isotopic composition of the snail body tissue, and therefore a better recorder of diet than is the insoluble shell organic carbon. Because the systematic fractionation of carbon isotopes within the snail is temperature dependent, the δ 13C of the shell could provide an independent technique for estimating paleotemperature changes.

Toward a better δDalkanes paleoclimate proxy; Partitioning of seasonal water sources and xylem-leaf deuterium enrichment according to plant growth form and phenology

NASA Astrophysics Data System (ADS)

Wispelaere, Lien; Bodé, Samuel; Herve-Fernández, Pedro; Hemp, Andreas; Verschuren, Dirk; Boeckx, Pascal

2016-04-01

The DeepCHALLA consortium is preparing an ICDP (International Continental Drilling Program) deep-drilling project on Lake Challa, a crater lake near Mt. Kilimanjaro in equatorial East Africa, where the climate is tropical semi-arid climate and characterized by two distinct rainy seasons. The main objective of this project is to acquire high-resolution and accurately dated proxy data of continental climate and ecosystem change near the Equator over 250,000 years. One of the paleoclimate proxies to be used is the hydrogen-isotopic composition of sedimentary n-alkanes (δDalkanes) derived from fossil plant leaf wax. However, this requires a better understanding of seasonal variability in the isotopic composition of precipitation, and of the fractionation of its hydrogen during incorporation in the plant waxes. In addition, recent studies have described the existence of "two water worlds", resulting in an additional deviation of the isotopic composition of the water taken up by plants. In this study, we measured the δD and δ18O of local precipitation, lake water, and xylem and leaf water from different plant species, seasons and sites with varying distances to Lake Challa. We use these data to set up a local meteoric water line (LMWL), and to assess spatial and temporal patterns of water utilization by local plants. Our data show a seasonal change in water-isotope partitioning with plants tapping water from isotopically lighter water sources during the dry seasons, as indicated by more negative xylem δD values and higher offsets from precipitation (i.e. greater distances from the LMWL), therefore supporting the "two water worlds" hypothesis. Surprisingly, trees appear to preferentially exploit isotopically more enriched sources of soil water, suggesting shallower water sources, than shrubs. Plants located at the lake shore use a mixture of precipitation and lake water, reflected in enriched xylem δD values and in the intersection of 2H and 18O with the LMWL. Leaf-water deuterium enrichment, averaged over all plant species, sites and seasons equals 23 ± 27‰. Several factors influence the isotopic enrichment between xylem and leaf water, but according to our results, the growth form and phenology of plant species are the primary factors, while the location (proximity to the lake) and season exert relatively minor effects.

The impact of pCO2 and climate on D/H and 13C/12C fractionation of higher-plant biomarkers: Implications for paleoclimate and paleoelevation reconstruction during global warm periods

NASA Astrophysics Data System (ADS)

Hren, M. T.; Tipple, B. J.; Pagani, M.

2012-12-01

Stable hydrogen isotope compositions (D/H) of plant biomarkers record the hydrogen isotopic composition of leaf water at the time of plant growth. However, the magnitude of the apparent hydrogen isotope fractionation between biomarkers and precipitation can vary due to soil- or leaf-water evaporation or differing water-use strategies. As a result, climate-induced changes in soil- or leaf-water evaporation rates and/or changes in plant assemblages during periods of global warming and high atmospheric CO2 could impact apparent carbon and hydrogen isotope fractionations. We measured hydrogen and carbon isotope ratios of long-carbon chain n-alkanes from modern and ~50 million year old fossil leaves preserved in paleo-Sierra Nevada riverine sediments to determine how climate and ecosystem differences during a period of extremely high pCO2 impact the magnitude and variability of D/H and 13C/12C ratios of leaf-waxes across a topographic gradient. δDalkanes (nC27 to nC31) of individual fossil and modern leaves decrease systematically across the topographic gradient and follow the change in the D/H of precipitation due to orographic lifting and continuous rainout. Using estimated values of Eocene δDprecip at the Pacific margin (-43 to -61‰), apparent fractionations (ɛalkane - precip) for Eocene angiosperm trees are similar to that seen for modern, humid environments (~ -106 to -124‰ ±10‰ 1σ), and more negative than observed in modern sun-exposed leaves in the Sierra Nevada (-96 to -102‰) or soils (-87 to -92‰). Single site variability in leaf-wax δD from individual fossil angiosperms can exceed 20‰, but is considerably smaller than observed for modern, mixed angiosperm/gymnosperm forests of the seasonally dry Sierra Nevada range. δ13Calkane values show little or no systematic variation across the range. However, carbon isotope discrimination in ancient and modern leaves is similar, suggesting strong climatic and weak pCO2 controls on D/H and 13C/12C fractionation. Site average δDalkane of multiple leaves closely mirrors bulk sediment δD values and suggests that the isotopic composition of bulk sediments provides a more robust record of local environmental and hydrologic conditions than analyses of biomarkers from individual leaves.

Isotopic composition of water vapor near the air-water interface

NASA Astrophysics Data System (ADS)

Zannoni, Daniele; Bergamasco, Andrea; Peschiutta, Mirco; Rampazzo, Giancarlo; Stenni, Barbara

2017-04-01

Evaporation is a key process in water cycle that links liquid water to the atmosphere. In the last fifty years stable isotopes of hydrogen and oxygen have been intensively used to describe climate processes related to evaporation and precipitation, ranging in different spatial and temporal scales. Evaporation introduces large isotopic effects in the phases involved. The well known Craig-Gordon model (Craig & Gordon, 1965) describes those isotopic effects involving several steps and different processes, moving from the air-water interface to the free atmosphere. However, very few works in literature have tested the vertical behavior of the Craig-Gordon model in natural conditions on both fresh and marine waters. In this work we present the results from four field experiments aimed to describe the vertical variability of δ18O and δD in the first few meters over a large water body (the coastal lagoon of Venice, northern Italy) and to test the Craig-Gordon model in such conditions. Each experiment involved cryotrapping of water vapor at different height over the water surface (0.1m, 2m and 4m) and the sampling of the liquid water at two depth (surface and 0.5m). During the experiments, water vapor was also sampled in the nearest mainland (˜2.5 km from gradient measurements) to determine the isotopic composition of background water vapor. Liquid samples were then analyzed with a Picarro L1102-i and Thermo-Fisher Delta Plus Advantage for water vapor and lagoon water, respectively. The last two experiments have also involved simultaneous measurements of relative humidity using commercially-available humidity probes at each height. This approach was used to determine a reference scale in order to compare observations to modeled estimates. Despite the coarse time resolution due to cryotrapping method (measurements are averaged over 1.5 hours), preliminary results show measurable differences in the isotopic composition of water vapor along the vertical gradient and good agreement between observations and predicted values from the model. Even if this work is an exploratory phase it shows an interesting potential to grow our understanding of the processes involved as well as a useful implementation for future studies focused on fractionation of water isotopes due to evaporation in natural conditions. References Craig, H., & Gordon, L. I. (1965). Deuterium and oxygen 18 variations in the ocean and the marine atmosphere.

Strontium and neodymium isotopes in hot springs on the East Pacific Rise and Guaymas Basin

NASA Technical Reports Server (NTRS)

Piepgras, D. J.; Wasserburg, G. J.

1985-01-01

Solutions collected from 21 deg N, East Pacific Rise (Epr) and Guaymas Basin, Gulf of California, are analyzed for Nd isotopic composition and Sm and Nd concentrations. The results indicate extensive but not complete isotopic exchange with Sr in the depleted oceanic crust and that Sr concentrations in these solutions are buffered. In contrast, the Nd data exhibit a wide range in isotopic composition and concentration between vents. Many samples show substantial contributions from MORB, but all have isotopic compositions below MORB, in spite of enrichments in Nd up to 100 times seawater. It is shown that the fluids must exchange Nd with a sedimentary reservoir having an isotopic composition less than Pacific seawater. Low-temperature reactions with metalliferous sediments on the flanks of the EPR may provide such a source. Using a simple box method, estimates of the hydrothermal fluxes of Nd are compared to fluxes which are necessary to maintain a radiogenic isotopic composition of about -3 in the Pacific against the influx of Antarctic waters. It is concluded that erosion from island arcs is the main source of radiogenic Nd in the Pacific.

Measurement of natural carbon isotopic composition of acetone in human urine.

PubMed

Yamada, Keita; Ohishi, Kazuki; Gilbert, Alexis; Akasaka, Mai; Yoshida, Naohiro; Yoshimura, Ryoko

2016-02-01

The natural carbon isotopic composition of acetone in urine was measured in healthy subjects using gas chromatography-combustion-isotope ratio mass spectrometry combined with headspace solid-phase microextraction (HS-SPME-GC-C-IRMS). Before applying the technique to a urine sample, we optimized the measurement conditions of HS-SPME-GC-C-IRMS using aqueous solutions of commercial acetone reagents. The optimization enabled us to determine the carbon isotopic compositions within ±0.2 ‰ of precision and ±0.3‰ of error using 0.05 or 0.2 mL of aqueous solutions with acetone concentrations of 0.3-121 mg/L. For several days, we monitored the carbon isotopic compositions and concentrations of acetone in urine from three subjects who lived a daily life with no restrictions. We also monitored one subject for 3 days including a fasting period of 24 h. These results suggest that changes in the availability of glucose in the liver are reflected in changes in the carbon isotopic compositions of urine acetone. Results demonstrate that carbon isotopic measurement of metabolites in human biological samples at natural abundance levels has great potential as a tool for detecting metabolic changes caused by changes in physiological states and disease.

Spatial and temporal patterns of nitrogen isotopic composition of ammonia at U.S. ammonia monitoring network sites

NASA Astrophysics Data System (ADS)

Felix, J. David; Elliott, Emily M.; Gay, David A.

2017-02-01

Ammonia (NH3) emissions and ammonium (NH4+) deposition can have harmful effects on the environment and human health but remain generally unregulated in the U.S. PM2.5 regulations require that an area not exceed an annual average PM2.5 value of 12 μg/m3 (averaged over three years), and since NH3 is a significant precursor to PM2.5 formation these are the closest indirect regulations of NH3 emissions in the U.S. If the U.S. elects to adopt NH3 emission regulations similar to those applied by the European Union, it will be imperative to first adequately quantify NH3 emission sources and transport, and also understand the factors causing varying emissions from each source. To further investigate NH3 emission sources and transport at a regional scale, NH3 was sampled monthly at a subset of nine Ammonia Monitoring Network (AMoN) sites and analyzed for nitrogen isotopic composition of NH3 (δ15N-NH3). The observed δ15N-NH3 values ranged from -42.4 to +7.1‰ with an average of -15.1 ± 9.7. The observed δ15N-NH3 values reported here provide insight into the spatial and temporal trends of the NH3 sources that contribute to ambient [NH3] in the U.S. In regions where agriculture is prevalent (i.e., U.S. Midwest), low and seasonally variable δ15N-NH3 values are observed and are associated with varying agricultural sources. In comparison, rural nonagricultural areas have higher and more seasonally consistent δ15N-NH3 values associated with a constant "natural" (e.g. soil, vegetation, bi-directional flux, ocean) NH3 source. With regards to temporal variation, the peak in U.S. spring agricultural activity (e.g. fertilizer application, livestock waste volatilization) is accompanied by a decrease in δ15N-NH3 values at a majority of the sites, whereas higher δ15N-NH3 values in other seasons could be due to shifting sources (e.g. coal-fired power plants) and/or fractionation scenarios. Fractionation processes that may mask NH3 source signatures are discussed and require further investigation to optimize the utility of the nitrogen isotopic composition to determine NH3 sources and dynamics.

Rare earth element transport in the western North Atlantic inferred from Nd isotopic observations

NASA Technical Reports Server (NTRS)

Piepgras, D. J.; Wasserburg, G. J.

1987-01-01

The relationship between the Nd isotopic composition in the Atlantic waters and the origin and circulation of the water masses was investigated. Samples were collected in the western North Atlantic between 7 and 54 deg N. The isotopic composition (Nd-143/Nd-144 ratios) showed extensive vertical structure at all locations. In regions where a thermocline was well-developed, large isotopic shifts were observed across the base of the thermocline, while regions without a thermocline were characterized by much more gradual shifts in isotopic composition with depth. The data reveal an excellent correlation between the Nd isotopic distribution in the western North Atlantic water column and the distribution of water masses identified from temperature and salinity measurements.

Sm-Nd in marine carbonates and phosphates - Implications for Nd isotopes in seawater and crustal ages

NASA Technical Reports Server (NTRS)

Shaw, H. F.; Wasserburg, G. J.

1985-01-01

The possibility of establishing a record of variations in the isotopic composition of Nd in seawater over geologic time is explored. To construct such a record, a phase must be identified which incorporated Nd with the same isotopic composition as seawater at the time of its formation, preserves that composition, and which is relatively common in sediments. To evaluate the suitability of carbonates and phosphates, the Rb, Sr, Sm, and Nd concentrations and the Nd and Sr isotopic composition of a variety of modern and ancient marine calcite, aragonite, and apatite samples have been measured and the results are presented and discussed.

Fingerprints of carbon, nitrogen, and silicon isotopes in small interstellar SiC grains from the Murchison meteorite

NASA Technical Reports Server (NTRS)

Hoppe, Peter; Geiss, Johannes; Buehler, Fritz; Neuenschwander, Juerg; Amari, Sachiko; Lewis, Roy S.

1993-01-01

We report ion microprobe determinations of the carbon, nitrogen, and silicon isotopic compositions of small SiC grains from the Murchison CM2 chondrite. Analyses were made on samples containing variable numbers of grains and on 14 individual grains. In some cases the multiple-grain sample compositions were probably dominated by only one or two grains. Total ranges observed are given. Only a few grains show values near the range limits. Both the total ranges of carbon and nitrogen isotopic compositions, and even the narrower ranges typical for the majority of the grains, are similar to those observed for larger SiC grains. Two rare components appear to be present in the smaller-size fraction, one characterized by C-12/C-13 about 12-16 and the other by very heavy nitrogen. The carbon and nitrogen isotopic compositions qualitatively may reflect hydrostatic H-burning via the CNO cycle and He-burning in red giants, as well as explosive H-burning in novae. The silicon isotopic compositions of most grains qualitatively show what is the signature of He-burning. The silicon isotopic composition of one grain, however, suggests a different process.

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

NASA Astrophysics Data System (ADS)

Liu, Nan; Stephan, Thomas; Boehnke, Patrick; Nittler, Larry R.; Meyer, Bradley S.; O’D. Alexander, Conel M.; Davis, Andrew M.; Trappitsch, Reto; Pellin, Michael J.

2018-03-01

We report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB (14N/15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains (14N/15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likely originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars’ pre-SN evolution rather than from an explosive neutron-capture process. In addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

DOE PAGES

Liu, Nan; Stephan, Thomas; Boehnke, Patrick; ...

2018-03-16

In this paper, we report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB ( 14N/ 15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains ( 14N/ 15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likelymore » originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars' pre-SN evolution rather than from an explosive neutron-capture process. Finally, in addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.« less

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

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

Liu, Nan; Stephan, Thomas; Boehnke, Patrick

In this paper, we report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB ( 14N/ 15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains ( 14N/ 15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likelymore » originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars' pre-SN evolution rather than from an explosive neutron-capture process. Finally, in addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.« less

Inverse methods for estimating primary input signals from time-averaged isotope profiles

NASA Astrophysics Data System (ADS)

Passey, Benjamin H.; Cerling, Thure E.; Schuster, Gerard T.; Robinson, Todd F.; Roeder, Beverly L.; Krueger, Stephen K.

2005-08-01

Mammalian teeth are invaluable archives of ancient seasonality because they record along their growth axes an isotopic record of temporal change in environment, plant diet, and animal behavior. A major problem with the intra-tooth method is that intra-tooth isotope profiles can be extremely time-averaged compared to the actual pattern of isotopic variation experienced by the animal during tooth formation. This time-averaging is a result of the temporal and spatial characteristics of amelogenesis (tooth enamel formation), and also results from laboratory sampling. This paper develops and evaluates an inverse method for reconstructing original input signals from time-averaged intra-tooth isotope profiles. The method requires that the temporal and spatial patterns of amelogenesis are known for the specific tooth and uses a minimum length solution of the linear system Am = d, where d is the measured isotopic profile, A is a matrix describing temporal and spatial averaging during amelogenesis and sampling, and m is the input vector that is sought. Accuracy is dependent on several factors, including the total measurement error and the isotopic structure of the measured profile. The method is shown to accurately reconstruct known input signals for synthetic tooth enamel profiles and the known input signal for a rabbit that underwent controlled dietary changes. Application to carbon isotope profiles of modern hippopotamus canines reveals detailed dietary histories that are not apparent from the measured data alone. Inverse methods show promise as an effective means of dealing with the time-averaging problem in studies of intra-tooth isotopic variation.

High Resolution Time Series Cave Ventilation Processes and the Effects on Cave Air Chemistry and Drip Waters: Speleoclimatology and Proxy Calibration

NASA Astrophysics Data System (ADS)

Kowalczk, A. J.; Froelich, P. N.; Gaffka, C.; Tremaine, D.

2008-12-01

Continuous high resolution (sub-hourly), long-term (Nov 2007-present) monitoring of cave air chemistry (Temperature, Relative Humidity, Barometric Pressure, Radon-222, CO2, Air flow, Wind speed and direction) in a shallow subtropical cave (Hollow Ridge) in N Florida reveals two major ventilation mechanisms: 1) ventilation driven by winds across the cave entrances, and 2) ventilation driven by density differences between atmospheric and cave air. The degree and type of ventilation strongly influence the 222Rn and CO2 of cave air, which in turn affects the timing and extent of calcite deposition in speleothems. The degree of ventilation is estimated using a cave air CO2-δ13CO2 Keeling Plot, or a simple radon deficiency model. Results show cave air has an atmospheric component ranging from 10-90%. During fall and winter, average CO2 (700 ppmv) and 222Rn (50-100 dpm/L) are lower than in spring and summer (CO2 = 1200 ppmv; 222Rn = 1000 dpm/L) due to increased winter ventilation. Decreased ventilation during the summer allows CO2 and 222Rn levels to rise. Winter daily ventilation is primarily a function of density gradients between cave air and atmospheric air, while summer daily ventilation is primarily a function of late morning NW-NE winds above the cave. Stable isotope analyses of drip water (fracture drip and pore flow drip) and aquifer water from Hollow Ridge agree with previous isotope studies of drip water at Florida Caverns State Park, 2 km to the NE. During summer, isotopic composition of pore flow drip water (δ18O -3.8 to -4.0 per mil; δD -17.3 to -20.2 per mil VSMOW) and aquifer water (δ18O -4.0 per mil; δD -18.0 to -21.1 per mil) are similar to average annual weighted isotopic composition of precipitation (δ18O -3.6 per mil) while fracture drip waters (δ18O -3 to -3.4 per mil; δD -11.9 to -14.3 per mil) likely reflect the isotopic composition of individual precipitation events. Pore flow drip waters δ18O are weakly correlated with drip rates (enriched δ18O during periods of higher drip rates) but show no correlation to precipitation amount. Knowledge of the type of drip flow is important when considering stalagmites for paleoclimate studies. A significant decrease in drip rate was observed from June (1034 drips/hour) through August 2008 (34 drips/hour). Higher water demands during summer months with increased evapotranspiration may be responsible for this decrease. A semi-diurnal drip rate cycle, negatively correlated with barometric pressure, is also observed throughout the period. This strong negative correlation is hypothesized to be controlled by atmospheric tidal oscillations. Observations into the fall and winter seasons should reveal seasonality, if any, and if there is an evapotranspiration effect present in the water cycle. High resolution studies of cave air chemistry and ventilation processes will enhance knowledge of the timing, extent, and isotopic and chemical composition of calcite deposition. When combined with drip water and precipitation isotope analyses, these studies will improve the understanding and interpretation of high- resolution (sub-annual) speleothem paleoclimate records.

Carbon, nitrogen, magnesium, silicon, and titanium isotopic compositions of single interstellar silicon carbide grains from the Murchison carbonaceous chondrite

NASA Technical Reports Server (NTRS)

Hoppe, Peter; Amari, Sachiko; Zinner, Ernst; Ireland, Trevor; Lewis, Roy S.

1994-01-01

Seven hundred and twenty SiC grains from the Murchison CM2 chondrite, ranging in size from 1 to 10 micrometers, were analyzed by ion microprobe mass spectrometry for their C-isotopic compositions. Subsets of the grains were also analyzed for N (450 grains), Si (183 grains), Mg (179 grains), and Ti (28 grains) isotopes. These results are compared with previous measurements on 41 larger SiC grains (up to 15 x 26 micrometers) from a different sample of Murchison analyzed by Virag et al. (1992) and Ireland, Zinner, & Amari (1991a). All grains of the present study are isotopically anomalous with C-12/C-13 ratios ranging from 0.022 to 28.4 x solar, N-14/N-15 ratios from 0.046 to 30 x solar, Si-29/Si-28 from 0.54 to 1.20 x solar, Si-30/Si-28 from 0.42 to 1.14 x solar, Ti-49/Ti-48 from 0.96 to 1.95 x solar, and Ti-50/Ti-48 from 0.94 to 1.39 x solar. Many grains have large Mg-26 excesses from the decay of Al-26 with inferred Al-26/Al-27 ratios ranging up to 0.61, or 12,200 x the ratio of 5 x 10(exp -5) inferred for the early solar system. Several groups can be distinguished among the SiC grains. Most of the grains have C-13 and N-14 excesses, and their Si isotopic compositions (mostly excesses in Si-29 and Si-30) plot close to a slope 1.34 line on a Delta Si-29/Si-28 versus Delta Si-30/Si-28 three-isotope plot. Grains with small C-12/C-13 ratios (less than 10) tend to have smaller or no N-14 excesses and high Al-26/Al-27 ratios (up to 0.01). Grains with C-12/C-13 greater than 150 fall into two groups: grains X have N-15 excesses and Si-29 and Si-30 deficits and the highest (0.1 to 0.6) Al-26/Al-27 ratios; grains Y have N-14 excesses and plot on a slope 0.35 line on a Si three-isotope plot. In addition, large SiC grains of the Virag et al. (1992) study fall into three-distinct clusters according to their C-, Si-, and Ti-isotopic compositions. The isotopic diversity of the grains and the clustering of their isotopic compositions imply distinct and multiple stellar sources. The C- and N-isotopic compositions of most grains are consistent with H-burning in the CNO cycle. These and s-process Kr, Xe, Ba, and Nd suggest asymptotic giant branch (AGB) or Wolf-Rayet stars as likely sources for the grains, but existing models of nucleosynthesis in these stellar sites fail to account in detail for all the observed isotopic compositions. Special problems are posed by grains with C-12/C-13 less than 10 and almost normal and heavy N-isotopic compositions. Also the Si- and Ti-isotopic compositions, with excesses in Si-29 and Si-30 relative to Si-28 and excesses in all Ti isotopes relative to Ti-48, do not precisely conform with the compositions predicted for slow neutron capture. Additional theoretical efforts are needed to achieve an understanding of the isotopic composition of the SiC grains and their stellar sources.

Rb-Sr and Sm-Nd Ages of Zagami DML and SR Isotopic Heterogeneity in Zagami

NASA Technical Reports Server (NTRS)

Nyquist, L.aurenceE.; Shih, C.-Y.; Reese, Y. D.

2010-01-01

Zagami contains lithologic heterogeneity suggesting that it did not form in a homogeneous, thick lava flow [1]. We have previously investigated the Sr and Nd isotopic systematics of Coarse-Grained (CG) and Fine-Grained (FG) lithologies described by [2]. Both appear to belong to Normal Zagami (NZ) [1,3], but their initial Sr-isotopic compositions differ [4,5]. Here we report new analyses of the Dark Mottled Lithology (DML, [3]) that show its age and initial Sr and Nd isotopic compositions to be identical within error limits with those of CG, but Sr initial isotopic compositions differ from those of FG.

Deciphering seasonal variations in the diet and drinking water of modern White-Tailed deer by in situ analysis of osteons in cortical bone

NASA Astrophysics Data System (ADS)

Larson, T. E.; Longstaffe, F. J.

2007-12-01

In situ carbon and oxygen isotope values for bioapatite were obtained from longitudinal slices of cortical bone from modern domesticated sheep and free-range White-Tailed deer. The analyses were obtained using an IR-laser coupled to a GC-IRMS interface. Ablation pits averaged 200 × 50 μm, making it possible to sample individual or small bundles of osteons. Cortical bone is remodeled along osteons throughout a mammal's life. Therefore, data at this scale can record seasonal variations in diet and drinking water during the adult stages of a mammal, whereas teeth provide may provide information about the juvenile years of a mammal. Average δ18O and δ13C values for the sheep from southwestern Ontario, Canada, were 14.0 and -16.1‰, respectively. No trend was observed in the isotopic composition of the sheep's osteons, consistent with its constant diet and water supply. The δ18O (14.2 to 16.6‰) and δ13C (-19.2 to -15.6‰) values of osteons from White-Tailed deer from nearby Pinery Provincial Park, however, varied systematically and were negatively correlated. Oxygen isotope values of the osteons correlated well with changes in the δ18O values of the main water source for these deer: winter average, -10.7‰; summer average, -8.6‰. The variation in δ13C values of the osteons reflects changes in diet; summer diet consisted mainly of leafy C3 vegetation (-28.4‰), whereas winter diet comprised bark (-25.6‰), C4 grasses (δ13C, -12.7‰), and corn stalks and husks (-11.3‰).

Enrichment and geochemical mobility of heavy metals in bottom sediment of the Hoedong reservoir, Korea and their source apportionment.

PubMed

Lee, Pyeong-Koo; Kang, Min-Ju; Yu, Soonyoung; Ko, Kyung-Seok; Ha, Kyoochul; Shin, Seong-Cheon; Park, Jung Han

2017-10-01

Physicochemical characteristics of bottom sediment in the Hoedong reservoir were studied to evaluate the effectiveness of the reservoir as traps for trace metals. Roadside soil, stream sediment and background soil were also studied for comparison. Sequential extractions were carried out, and lead isotopic compositions of each extraction were determined to apportion Pb sources. Besides, particle size distribution of roadside soil, and metal concentrations and Pb isotopes of each size group were determined to characterize metal contamination. In result, Zn and Cu were enriched in sediment through roadside soil. The data on metal partitioning implied that Zn posed potential hazards for water quality. Meanwhile, the noticeable reduction of the 206 Pb/ 207 Pb isotopic ratio in the acid-soluble fraction in the size group 200 μm - 2 mm of national roadside soil indicated that this size group was highly contaminated by automotive emission with precipitation of acid-soluble secondary minerals during evaporation. Based on the Pb isotopic ratios, the dry deposition of Asian dust (AD) and non-Asian dust (NAD) affected roadside soil, while the effects of AD and NAD on bottom sediment appeared to be low given the low metal concentrations in sediment. Metal concentrations and Pb isotopic compositions indicated that sediments were a mixture of background and roadside soil. Source apportionment calculations showed that the average proportion of traffic Pb in bottom and stream sediments was respectively 34 and 31% in non-residual fractions, and 26 and 28% in residual fraction. The residual fraction of sediments appeared to be as contaminated as the non-residual fractions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Carnivore stable carbon isotope niches reflect predator-prey size relationships in African savannas.

PubMed

Codron, Jacqueline; Avenant, Nico L; Wigley-Coetsee, Corli; Codron, Daryl

2018-03-01

Predator-prey size relationships are among the most important patterns underlying the structure and function of ecological communities. Indeed, these relationships have already been shown to be important for understanding patterns of macroevolution and differential extinction in the terrestrial vertebrate fossil record. Stable isotope analysis (SIA) is a powerful remote approach to examining animal diets and paleodiets. The approach is based on the principle that isotope compositions of consumer tissues reflect those of their prey. In systems where resource isotope compositions are distributed along a body size gradient, SIA could be used to reconstruct predator-prey size relationships. We analyzed stable carbon isotope distributions amongst mammalian herbivores in extant and Plio-Pleistocene African savanna assemblages, and show that the range of δ 13 C values among mammalian prey species (herbivores and rodents) increases with body mass (BM), because C 4 plant feeding (essentially grazing) is more common among larger taxa. Consequently, δ 13 C values of mammalian carnivores in these systems are related to species' BM, reflecting a higher average C 4 prey component in the diets of larger-bodied carnivores. This pattern likely emerges because only the largest carnivores in these systems have regular access to the C 4 prey base, whereas smaller carnivores do not. The δ 13 C-BM relationship observed in mammalian carnivores is a potentially powerful approach for reconstructing and parameterizing predator-prey size relationships in contemporary and fossil savanna assemblages, and for interpreting how various behavioral, ecological and environmental factors influence prey size selection. © 2017 International Society of Zoological Sciences, Institute of Zoology/Chinese Academy of Sciences and John Wiley & Sons Australia, Ltd.

Angiosperm n-alkane distribution patterns and the geologic record of C4 grassland evolution

NASA Astrophysics Data System (ADS)

Henderson, A.; Graham, H. V.; Patzkowsky, M.; Fox, D. L.; Freeman, K. H.

2012-12-01

n-Alkane average chain-length (ACL) patterns vary regionally with community composition and climate. To clarify the influence of phylogenetic and community patterns, we compiled and analyzed a global database of published n-alkane abundance for n-C27 to C35 homologs in modern plant specimens (n=205). ACL for waxes in C4 non-woody plants are longer than for woody plants, suggesting ACL can serve as an indicator of the three-dimensional structure of local vegetation. Further, these findings suggest compound-specific isotopic data for longer alkane homologs (C31, C33, C35) will proportionately represent non-woody vegetation and isotope measurements of C29 are more representative of woody vegetation. Thus, the combination of ACL and carbon isotope compositions should allow us to disentangle C3 woody, C3 non-woody, and C4 non-woody signals in terrestrial paleorecords. Application of this approach to the geologic record of Miocene C4 grassland expansion in the US Great Plains and the Siwaliks in Pakistan illustrate two very different transition scenarios. Alkane-specific isotopic data indicate C4 grasslands appeared 2.5 Ma in the Great Plains and 6.5 Ma in the Siwaliks, and ACL analysis indicates that this transition involved the replacement of woody vegetation in the US and the replacement of C3 grasses in Pakistan. Our analysis illustrates that, consistent with differences in the timing of C4 grassland, the drivers of change were likely not the same in these regions. Oxygen isotope records suggest that the more recent transition in the Great Plains was associated with climate cooling and possibly changes in disturbance regimes and that the transition in the Siwaliks was likely associated with warming and drying.

Use of radiation sources with mercury isotopes for real-time highly sensitive and selective benzene determination in air and natural gas by differential absorption spectrometry with the direct Zeeman effect.

PubMed

Revalde, Gita; Sholupov, Sergey; Ganeev, Alexander; Pogarev, Sergey; Ryzhov, Vladimir; Skudra, Atis

2015-08-05

A new analytical portable system is proposed for the direct determination of benzene vapor in the ambient air and natural gas, using differential absorption spectrometry with the direct Zeeman effect and innovative radiation sources: capillary mercury lamps with different isotopic compositions ((196)Hg, (198)Hg, (202)Hg, (204)Hg, and natural isotopic mixture). Resonance emission of mercury at a wavelength of 254 nm is used as probing radiation. The differential cross section of benzene absorption in dependence on wavelength is determined by scanning of magnetic field. It is found that the sensitivity of benzene detection is enhanced three times using lamp with the mercury isotope (204)Hg in comparison with lamp, filled with the natural isotopic mixture. It is experimentally demonstrated that, when benzene content is measured at the Occupational Exposure Limit (3.2 mg/m(3) for benzene) level, the interference from SO2, NO2, O3, H2S and toluene can be neglected if concentration of these gases does not exceed corresponding Occupational Exposure Limits. To exclude the mercury effect, filters that absorb mercury and let benzene pass in the gas duct are proposed. Basing on the results of our study, a portable spectrometer is designed with a multipath cell of 960 cm total path length and detection limit 0.5 mg/m(3) at 1 s averaging and 0.1 mg/m(3) at 30 s averaging. The applications of the designed spectrometer to measuring the benzene concentration in the atmospheric air from a moving vehicle and in natural gas are exemplified. Copyright © 2015 Elsevier B.V. All rights reserved.

Water utilization of the Cretaceous Mussentuchit Member local vertebrate fauna, Cedar Mountain Formation, Utah, USA: Using oxygen isotopic composition of phosphate

USGS Publications Warehouse

Suarez, C.A.; Gonzalez, Luis A.; Ludvigson, Greg A.; Cifelli, R.L.; Tremain, E.

2012-01-01

While the oxygen isotopic composition of pedogenic carbonate has successfully been used to address the effects of global climate change on the hydrologic cycle, detailed regional paleohydrologic studies are lacking. Since the hydrologic cycle can vary extensively on local or regional scales due to events such as such as mountain building, and since pedogenic carbonates (calcite) form in a narrow moisture regime, other proxies, such as vertebrate remains, must be used to decipher local versus regional variations in paleohydrology. In this study, the oxygen isotopic composition (?? 18O p) of phosphatic remains from a diverse set of vertebrate fossils (fish, turtles, crocodiles, dinosaurs, and micro-mammals) from the Mussentuchit Member (MM) of the Cedar Mountain Formation, Utah, USA (Aptian to Cenomanian) are analyzed in order to determine differences among the available water reservoirs and water utilization of each taxon. Calculated changes in water reservoir ?? 18O w over time are then used to determine the effects of the incursion of the Western Interior Seaway (WIS) and the Sevier Mountains on paleohydrology during the MM time. Calculation of ?? 18O w from the results of isotopic analysis of phosphate oxygen suggests that turtles and crocodiles serve as another proxy for meteoric water ?? 18O that can be used as a measure of average local precipitation ?? 18O w similar to pedogenic calcite. Pedogenic calcites can be slightly biased toward higher values, however, due to their formation during evaporative conditions. Turtles and crocodiles can be used in place of pedogenic calcite in environments that are not conducive to pedogenic carbonate formation. Remains of fish with rounded tooth morphology have ?? 18O p values that predict temperatures consistent with other estimates of mean annual temperature for this latitude and time. The ?? 18O p of ganoid scales and teeth with pointed morphology, however, indicates that these skeletal materials were precipitated from water that is 18O-enriched due to migration to either evaporatively enriched water, or 18O-enriched estuarine waters of the Western Interior Seaway (WIS). Another possibility that cannot be discounted and assuming all morphological remains are from the same taxon, is that the pointed teeth and ganoid scales precipitated at different temperatures than rounded teeth. Mammal and herbivorous dinosaur ?? 18O p suggests they primarily drank isotopically depleted river water. Co-existence of crocodiles, turtles, and mammals allows for calculation of relative humidity from site to site and these calculations suggest humidity averaged ~58% and ranged between ~42% and ~76%.The ?? 18O w values estimated from semi-aquatic taxa and pedogenic calcite suggest dominance of WIS-derived moisture during their growth. Herbivorous dinosaurs particularly indicate that altitude and catchment effects from the Sevier Mountains are seemingly important for river water ?? 18O w in the fall through early spring. These data suggest that temporal changes in the isotopic composition of the MM fauna are produced by the small-scale regressive-transgressive cycles of the WIS. ?? 2011.

Silicon biogeochemical processes in a large river (Cauvery, India)

NASA Astrophysics Data System (ADS)

Kameswari Rajasekaran, Mangalaa; Arnaud, Dapoigny; Jean, Riotte; Sarma Vedula, V. S. S.; Nittala, S. Sarma; Sankaran, Subramanian; Gundiga Puttojirao, Gurumurthy; Keshava, Balakrishna; Cardinal, Damien

2016-04-01

Silicon (Si), one of the key nutrients for diatom growth in ocean, is principally released during silicate weathering on continents and then exported by rivers. Phytoplankton composition is determined by the availability of Si relative to other nutrients, mainly N and P, which fluxes in estuarine and coastal systems are affected by eutrophication due to land use and industrialization. In order to understand the biogeochemical cycle of Si and its supply to the coastal ocean, we studied a tropical monsoonal river from Southern India (Cauvery) and compare it with other large and small rivers. Cauvery is the 7th largest river in India with a basin covering 85626 sq.km. The major part of the basin (˜66%) is covered by agriculture and inhabited by more than 30 million inhabitants. There are 96 dams built across the basin. As a consequence, 80% of the historical discharge is diverted, mainly for irrigation (Meunier et al. 2015). This makes the Cauvery River a good example of current anthropogenic pressure on silicon biogeochemical cycle. We measured amorphous silica contents (ASi) and isotopic composition of dissolved silicon (δ30Si-DSi) in the Cauvery estuary, including freshwater end-member and groundwater as well as along a 670 km transect along the river course. Other Indian rivers and estuaries have also been measured, including some less impacted by anthropogenic pressure. The average Cauvery δ30Si signature just upstream the estuary is 2.21±0.15 ‰ (n=3) which is almost 1‰ heavier than the groundwater isotopic composition (1.38±0.03). The δ30Si-DSi of Cauvery water is also almost 1‰ heavier than the world river supply to the ocean estimated so far and 0.4‰ heavier than other large Indian rivers like Ganges (Frings et al 2015) and Krishna. On the other hand, the smaller watersheds (Ponnaiyar, Vellar, and Penna) adjacent to Cauvery also display heavy δ30Si-DSi. Unlike the effect of silicate weathering, the heavy isotopic compositions in the river Cauvery may result from the successive dams along the main course which are expected to favor the retention of isotopically light Si isotopes in sediments via diatom uptake in reservoirs and/or, Si uptake by vegetation. Both processes likely result in heavier δ30Si-DSi downstream. In the estuary, the average δ30Si-DSi is 2.20±0.17 ‰ (n=11). There is a significant positive relationship between ASi contents and fucoxanthin (diatom marker pigment) (r=0.61, p<0.05, n=11) suggesting a significant control of diatoms on ASi. However a dominant mixing effect is observed in dissolved silicon with a strong positive relationship between 1/DSi and δ30Si-DSi (r=0.71, p<0.01, n=11). A comparative study with a west-flowing river, the Netravathi (southwest India) will be performed and presented during the session. We will also compare the Si isotopic signatures in Cauvery along the transect with focus on seasonal variability and on upstream vs. downstream large dams to strengthen interpretations.

Rainfall Type as a Dominant Control of the Isotopic Composition of Precipitation in the South Central United States

NASA Astrophysics Data System (ADS)

Sun, C.; Shanahan, T. M.; Partin, J. W.

2017-12-01

The processes that control the isotopic composition of precipitation in the mid-latitudes are understudied compared to the high and low latitudes, but are critical for interpreting paleo records using isotope proxies. To better understand these processes, we investigated changes of isotopic composition of rainwater in Central Texas using 20 months of event-based rainwater collection. We find that in both the event-based data and the monthly data from the Waco GNIP station, the dominant control on the isotopic composition of precipitation is the proportion that is derived from convective systems. This finding is consistent with previously reported data largely from tropical localities (Aggarwal et al., 2016), where large organized convective systems lead to high rainfall amounts and isotopically depleted precipitation. Although there are seasonal differences in the dominant rainfall types over the South Central US, with winter precipitation almost entirely stratiform, seasonality plays very little role in the net isotopic composition of precipitation because the total contribution during winter is small compared with spring, summer and fall. We also find that changes of source have little effect on the isotopic composition of rainfall, as the majority of the moisture is derived from the Gulf of Mexico with little influence of reevaporation or mixing. The majority of the warm season precipitation in the South Central US occurs in association with mesoscale convective systems (MCSs) and the development of these systems plays a critical role in the overall isotopic signature of precipitation. MCSs are characterized by a combination of intense, organized convection at their leading edges and trailing stratiform precipitation. Larger MCSs tend to contain higher proportions of stratiform rainfall and as a result, have isotopically depleted values. Proxy records from this region displaying more negative isotope values in the past should therefore be interpreted with caution as they could reflect either increases in cool versus warm season precipitation or changes in the intensity of warm season MCSs.

Silicon Isotopic Fractionation of CAI-like Vacuum Evaporation Residues

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

Knight, K; Kita, N; Mendybaev, R

2009-06-18

Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquidsmore » (Richter et al., 2002, 2007a). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, {alpha}{sub Si}, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that {alpha}{sub Si} = 0.98985 {+-} 0.00044 (2{sigma}) for {sup 29}Si/{sup 28}Si with no resolvable variation with temperature over the temperature range of the experiments, 1600-1900 C. This value is different from what has been reported for evaporation of liquid Mg{sub 2}SiO{sub 4} (Davis et al., 1990) and of a melt with CI chondritic proportions of the major elements (Wang et al., 2001). There appears to be some compositional control on {alpha}{sub Si}, whereas no compositional effects have been reported for {alpha}{sub Mg}. We use the values of {alpha}Si and {alpha}Mg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites whose chemical compositions and magnesium and silicon isotopic compositions have been previously measured.« less

Re-assessing the Molybdenum Isotope Composition of Pre-GOE Seawater: Evidence for Dynamic Ocean Redox

NASA Astrophysics Data System (ADS)

Ostrander, C. M.; Kendall, B.; Roy, M.; Romaniello, S. J.; Nunn, S. J.; Gordon, G. W.; Olson, S. L.; Lyons, T. W.; Zheng, W.; Anbar, A. D.

2016-12-01

Molybdenum (Mo) isotope compositions of Archean shales can provide important insights into ocean and atmosphere redox dynamics prior to the Great Oxidation Event (GOE). Unfortunately, the relatively limited Mo isotope database and small number of sample sets for Archean shales do not allow for in-depth reconstructions and specifically make it difficult to differentiate global from local effects. To accurately estimate the Mo isotope composition of Archean seawater and better investigate the systematics of local and global redox, more complete sample sets are needed. We carried out a Mo isotope analysis of the euxinic 2.65 Ga Roy Hill Shale sampled in two stratigraphically correlated cores, and revisited the well-studied euxinic 2.5 Ga Mt. McRae Shale in higher resolution. Our data show contrasting Mo isotope values in the 2.65 Ga Roy Hill Shale between near- and offshore depositional environments, with systematically heavier isotope values in the near-shore environment. High-resolution analysis of the Mt. McRae Shale yields oscillating Mo concentrations and isotope values at the cm- to dm-scale during the well-characterized "whiff of O2" interval, with the heaviest isotope values measured during euxinic deposition. Variations in the measured isotope values within each section are primarily associated with redox changes in the local depositional environment and amount of detrital content. Both non-quantitative removal of Mo associated with incorporation into non-euxinic sediments and large detrital Mo contributions shift some measured isotopic compositions toward lighter values. This is readily apparent in the near-shore Roy Hill Shale section and the Mt. McRae Shale, but may not fully explain variations observed in the offshore Roy Hill Shale deposit. Here, euxinic deposition is not accompanied by Mo enrichments or isotopic compositions as heavy as the near-shore equivalent, even after detrital correction. This disparity between the near- and offshore environment could signify spatial variation in the Mo isotope composition of 2.65 Ga seawater and highlights the need for multi-site and high-resolution studies in order to best assess paleoenvironmental conditions.

Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

NASA Technical Reports Server (NTRS)

Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.

2004-01-01

Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

Ultra-high-precision Nd-isotope measurements of geological materials by MC-ICPMS

PubMed Central

Saji, Nikitha Susan; Wielandt, Daniel; Paton, Chad; Bizzarro, Martin

2016-01-01

We report novel techniques allowing the measurement of Nd-isotope ratios with unprecedented accuracy and precision by multi-collector inductively coupled plasma mass spectrometry. Using the new protocol, we have measured the Nd-isotopic composition of rock and synthetic Nd standards as well as that of the Allende carbonaceous chondrite. Analyses of BCR-2, BHVO-2 and GSP-2 rock standards yield mass-independent compositions identical to the JNdi-1 Nd-reference standard, with an external reproducibility of 2.4, 1.6, 1.6 and 3.5 ppm respectively, on μ142Nd, μ145Nd, μ146Nd and μ150Nd (μ representing the ppm-deviation of the ratios from JNdi-1) using 148Nd/144Nd for internal normalization. This represents an improvement in precision by a factor of 2, 7 and 9 respectively for μ142Nd, μ145Nd and μ150Nd. Near-quantitative recovery from purification chemistry and sample-standard bracketing allow for the determination of mass-dependent Nd-isotopic composition of samples. Synthetic standards, namely La Jolla and AMES, record mass-dependent variability of up to 1.2 ε per atomic mass unit and mass-independent compositions resolvable by up to 3 ppm for μ142Nd and 8 ppm for μ150Nd, relative to JNdi-1. The mass-independent compositions are consistent with equilibrium mass fractionation during purification. The terrestrial rock standards define a uniform stable ε145Nd of −0.24 ± 0.19 (2SD) relative to JNdi-1, indistinguishable from the mean Allende ε145Nd of −0.19 ± 0.09. We consider this value to represent the mass-dependent Nd-isotope composition of Bulk Silicate Earth (BSE). The modest mass-dependent fractionation of JNdi-1 relative to BSE results in potential effects on mass-independent composition that cannot be resolved within the reproducibility of our analyses when correcting for natural and instrumental mass fractionation by kinetic law, making it a suitable reference standard for analysis of unknowns. Analysis of Allende (CV3) carbonaceous chondrite returns an average μ142Nd deficit of −30.1 ± 3.7 ppm in agreement with previous studies. The apparent deficit is, however, lowered to −23.8 ± 4.0 ppm while normalizing to 148Nd/144Nd instead of 146Nd/144Nd. We interpret this as the effect of a possible nucleosynthetic anomaly of −6.3 ± 0.5 ppm in μ146Nd. As 142Nd and 146Nd are both s-process-dominated nuclides, this hints at the possibility that terrestrial μ142Nd excess may not reflect 146Sm decay as widely accepted. PMID:27429505

Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

NASA Astrophysics Data System (ADS)

Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

2015-12-01

Chondrichthyan teeth (sharks, rays, and chimaeras) are mineralized in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are generally consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the hybodont shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

NASA Astrophysics Data System (ADS)

Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

2015-08-01

Chondrichthyan teeth (sharks, rays and chimaeras) are mineralised in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered as a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the primitive shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

The earliest Lunar Magma Ocean differentiation recorded in Fe isotopes

NASA Astrophysics Data System (ADS)

Wang, Kun; Jacobsen, Stein B.; Sedaghatpour, Fatemeh; Chen, Heng; Korotev, Randy L.

2015-11-01

Recent high-precision isotopic measurements show that the isotopic similarity of Earth and Moon is unique among all known planetary bodies in our Solar System. These observations provide fundamental constraints on the origin of Earth-Moon system, likely a catastrophic Giant Impact event. However, in contrast to the isotopic composition of many elements (e.g., O, Mg, Si, K, Ti, Cr, and W), the Fe isotopic compositions of all lunar samples are significantly different from those of the bulk silicate Earth. Such a global Fe isotopic difference between the Moon and Earth provides an important constraint on the lunar formation - such as the amount of Fe evaporation as a result of a Giant Impact origin of the Moon. Here, we show through high-precision Fe isotopic measurements of one of the oldest lunar rocks (4.51 ± 0.10 Gyr dunite 72 415), compared with Fe isotope results of other lunar samples from the Apollo program, and lunar meteorites, that the lunar dunite is enriched in light Fe isotopes, complementing the heavy Fe isotope enrichment in other lunar samples. Thus, the earliest olivine accumulation in the Lunar Magma Ocean may have been enriched in light Fe isotopes. This new observation allows the Fe isotopic composition of the bulk silicate Moon to be identical to that of the bulk silicate Earth, by balancing light Fe in the deep Moon with heavy Fe in the shallow Moon rather than the Moon having a heavier Fe isotope composition than Earth as a result of Giant Impact vaporization.

The role of stable isotopes in understanding rainfall interception processes: a review

EPA Science Inventory

The isotopic composition of water transmitted by the canopy as throughfall or stemflow reflects important hydrologic processes occurring in the canopy. A synthesis of the literature shows that complex spatiotemporal variations of isotopic composition are created by canopy interce...

Metal stable isotopes in weathering and hydrology: Chapter 10

USGS Publications Warehouse

Bullen, Thomas D.; Holland, Heinrich; Turekian, K.

2014-01-01

This chapter highlights some of the major developments in the understanding of the causes of metal stable isotope compositional variability in and isotope fractionation between natural materials and provides numerous examples of how that understanding is providing new insights into weathering and hydrology. At this stage, our knowledge of causes of stable isotope compositional variability among natural materials is greatest for the metals lithium, magnesium, calcium, and iron, the isotopes of which have already provided important information on weathering and hydrological processes. Stable isotope compositional variability for other metals such as strontium, copper, zinc, chromium, barium, molybdenum, mercury, cadmium, and nickel has been demonstrated but is only beginning to be applied to questions related to weathering and hydrology, and several research groups are currently exploring the potential. And then there are other metals such as titanium, vanadium, rhenium, and tungsten that have yet to be explored for variability of stable isotope composition in natural materials, but which may hold untold surprises in their utility. This impressive list of metals having either demonstrated or potential stable isotope signals that could be used to address important unsolved questions related to weathering and hydrology, constitutes a powerful toolbox that will be increasingly utilized in the coming decades.

Quality assurance and quality control in light stable isotope laboratories: A case study of Rio Grande, Texas, water samples

USGS Publications Warehouse

Coplen, T.B.; Qi, H.

2009-01-01

New isotope laboratories can achieve the goal of reporting the same isotopic composition within analytical uncertainty for the same material analysed decades apart by (1) writing their own acceptance testing procedures and putting them into their mass spectrometric or laser-based isotope-ratio equipment procurement contract, (2) requiring a manufacturer to demonstrate acceptable performance using all sample ports provided with the instrumentation, (3) for each medium to be analysed, prepare two local reference materials substantially different in isotopic composition to encompass the range in isotopic composition expected in the laboratory and calibrated them with isotopic reference materials available from the International Atomic Energy Agency (IAEA) or the US National Institute of Standards and Technology (NIST), (4) using the optimum storage containers (for water samples, sealing in glass ampoules that are sterilised after sealing is satisfactory), (5) interspersing among sample unknowns local laboratory isotopic reference materials daily (internationally distributed isotopic reference materials can be ordered at three-year intervals, and can be used for elemental analyser analyses and other analyses that consume less than 1 mg of material) - this process applies to H, C, N, O, and S isotope ratios, (6) calculating isotopic compositions of unknowns by normalising isotopic data to that of local reference materials, which have been calibrated to internationally distributed isotopic reference materials, (7) reporting results on scales normalised to internationally distributed isotopic reference materials (where they are available) and providing to sample submitters the isotopic compositions of internationally distributed isotopic reference materials of the same substance had they been analysed with unknowns, (8) providing an audit trail in the laboratory for analytical results - this trail commonly will be in electronic format and might include a laboratory information management system, (9) making at regular intervals a complete backup of laboratory analytical data (both of samples logged into the laboratory and of mass spectrometric analyses), being sure to store one copy of this backup offsite, and (10) participating in interlaboratory comparison exercises sponsored by the IAEA and other agencies at regular intervals. ?? Taylor & Francis.

Experimentally determined sulfur isotope fractionation between metal and silicate and implications for planetary differentiation

NASA Astrophysics Data System (ADS)

Labidi, J.; Shahar, A.; Le Losq, C.; Hillgren, V. J.; Mysen, B. O.; Farquhar, J.

2016-02-01

The Earth's mantle displays a subchondritic 34S/32S ratio. Sulfur is a moderately siderophile element (i.e. iron-loving), and its partitioning into the Earth's core may have left such a distinctive isotope composition on the terrestrial mantle. In order to constrain the sulfur isotope fractionation occurring during core-mantle differentiation, high-pressure and temperature experiments were conducted with synthetic mixtures of metal and silicate melts. With the purpose to identify the mechanism(s) responsible for the S isotope fractionations, we performed our experiments in different capsules - namely, graphite and boron nitride capsules - and thus at different fO2, with varying major element chemistry of the silicate and metal fractions. The S isotope fractionations Δ34Smetal-silicate of equilibrated metal alloys versus silicate melts is +0.2 ± 0.1‰ in a boron-free and aluminum-poor system quenched at 1-1.5 GPa and 1650 °C. The isotope fractionation increases linearly with increasing boron and aluminum content, up to +1.4 ± 0.2‰, and is observed to be independent of the silicon abundance as well as of the fO2 over ∼3.5 log units of variations explored here. The isotope fractionations are also independent of the graphite or nitride saturation of the metal. Only the melt structural changes associated with aluminum and boron concentration in silicate melts have been observed to affect the strength of sulfur bonding. These results establish that the structure of silicate melts has a direct influence on the S2- average bonding strengths. These results can be interpreted in the context of planetary differentiation. Indeed, the structural environments of silicate evolve strongly with pressure. For example, the aluminum, iron or silicon coordination numbers increase under the effect of pressure. Consequently, based on our observations, the sulfur-bonding environment is likely to be affected. In this scheme, we tentatively hypothesize that S isotope fractionations between the silicate mantle and metallic core of terrestrial planetary bodies would depend on the average pressure at which their core-mantle differentiation occurred.

Using Redwood Tree Ring Chronologies to Obtain the Long-View on California's Coastal Climate

NASA Astrophysics Data System (ADS)

Dawson, T. E.; Roden, J. S.; Voelker, S. L.; Johnstone, J. A.; Ambrose, A.

2014-12-01

Coast redwood (Sequoia sempervirens) occupies a long and narrow range at the land-sea interface from the southern Big Bur region to the California-Oregon boarder. Since mature trees can live in excess of 2000 years, using the interannual variability in the oxygen and carbon stable isotope composition of tree rings obtained from trees growing in different parts of the redwood range holds the potential for obtaining a long-term record of California's coastal climate, including the history of temperatures, low cloud / fog, rainfall and associated climatic drivers of their variation. We analyzed the oxygen and carbon stable isotope composition of tree ring cellulose from both tree cores and whole cross-sectional slabs and compared these data to several regional climate indicies and to published growth chronologies to obtain the long-view on California's coastal climate. Several highlights will be presented and discussed. These include: (1) redwoods faithfully record water sources they use in the oxygen stable isotope composition of their tree ring cellulose; (2) these is both strong watershed- and regional-scale coherence; (3) redwood tree ring carbon isotope composition shows its strongest correlations to tree water status, stand-scale humidity, and at the regional scale to what we term "summer precipitation" anomalies (lack of rain with presence of fog); also (4) that carbon stable isotope composition is very sensitive to within tree and stand microclimate while oxygen stable isotope composition seems to be sensitive to topographic site factors like slope position and proximity to riparian / gully habitats; (5) multivariate climatic analyses reveal that summertime drought recorded in the isotope excursions are most strongly linked to atmospheric circulation anomalies; and (6) that redwood tree rings and their isotope composition provide great potential for reconstructing high-resolution paleo-climate along the California coast.

A molecular stable carbon isotope study of organic matter in immature Miocene Monterey sediments, Pismo basin

NASA Astrophysics Data System (ADS)

Schouten, Stefan; Schoell, Martin; Rijpstra, W. Irene C.; Sinninghe Damsté, Jaap S.; de Leeuw, Jan W.

1997-05-01

The 300 m section of the Miocene Monterey Formation outcropping at Shell Beach (Pismo basin; ca. 15-11 Ma) is composed of calcareous phosphatic (15.1-14.5 Ma) and siliceous facies (14.5-11.0 Ma). An objective of this paper is to document lateral paleoenvironmental changes in the Miocene Moneterey Formation by comparing the Shell Beach (SB) profile with the Naples Beach (NB) section in the Santa Barbara-Ventura basin (Schouten et al., 1997) which is ˜80 km to the south. Eight samples (one sample representing, on average, a time period of ca. 2000 y) from this section were analyzed for variations of extractable biomarkers and their carbon isotopic signatures as indicators for paleoenvironmental change during the Miocene. Saturated hydrocarbons present include 28,30-dinorhopane, phytane, n-alkanes (C 17sbnd C 31), lycopane, and 17β,21β(H)-homohopane. The biomarkers released after desulfurization of the polar fractions predominantly consist of phytane, 2,6,10,14-tetramethyl-7-(3-methylpentyl)pentadecane, C 17sbnd C 31n-alkanes, regular 5α- and 5β-steranes, dinosteranes, and (22R)-17β,21β(H)-pentakishomohopane. Steranes have similar carbon isotopic compositions (-25 to -27‰) throughout the section and are isotopically similar at both sites, indicating laterally similar and vertically stable environmental conditions for algae living in the upper part of the photic zone. Free and S-bound n-alkanes at SB mainly originate from marine organisms and not from terrestrial sources as in the NB section. S-bound pentakishomohopane is ca. 1-4‰ depleted compared to the steranes and is thought to be derived from the deeper water dwelling cyanobacteria. These findings are consistent with stable carbon isotopic data obtained for these compounds from Middle Miocene Monterey sediments at Naples Beach and indicates similar environmental conditions in the depositional environments of the Santa Barbara-Ventura and the Pismo basin. S-bound highly branched isoprenoids have, at both sites, different isotopic compositions indicating the presence of different diatom species, special growth conditions, or different bloom periods in the Pismo basin. The carbon isotopic composition of 28,30-dinorhopane shifts to more depleted values up section, suggesting that the dinorhopane-synthesizing organism or organisms live on CO 2, which is isotopically influenced by methane production and oxidation. The C 31 hopane is enriched by 1-4‰ in 13C compared to other hopanes and steranes. Specific bacteria, possibly heterotrophs, may have been the organisms producing this compound.

The vanadium isotope compositions of subduction zone lavas

NASA Astrophysics Data System (ADS)

Tian, S.; Huang, F.

2017-12-01

Vanadium is a redox sensitive element with multiple oxidation states, and thus it has the potential to trace redox-related processes. With the advancement of analytical method for V isotopes, we are now able to recognize V isotope fractionation for igneous rocks. Subduction zones are critical zones on the Earth for the interaction between crust and mantle where undergo complex geological processes. However, V isotope data of subduction zone lavas are still rare except those reported in [1]. To investigate the V isotope variations of subduction zones and discuss the potential to apply V to trace mantle redox state. In this contribution, we report δ51V for three subduction zone lavas from Kamchatka, Lesser Antilles, and Aleutians which are characterized by well-documented magmatic evolutionary series. 47 arc lava samples have been analyzed and the δ51V data of them range from -0.91‰ to -0.53‰ (2sd = 0.10 ‰). Among these samples, primitive arc basalts with MgO > 6 wt. % have an average δ51V of -0.80 ± 0.15‰ (2sd, n = 20), broadly consistent with δ51V data of MORB [2, 3]. Within the single arc of Kamchatka, δ51V data of primitive basalts from the arc front to the back-arc is almost constant, suggesting limited influences of mantle melting and source heterogeneity on V isotopes. δ51V data of these samples show no correlation with Ba/Nb, suggesting that fluids have little impact on V isotopes. On the other hand, δ51V data of the more involved samples with MgO < 6 wt. % are negatively correlated with MgO contents, indicating that the 50V preferentially enters crystalline minerals, which produces heavier V isotope compositions of residual melts. Distinct to the observation showing 2‰ fractionation reported in [1], the magnitude of V isotope fractionation in arc lavas is much smaller (0.38‰) in this study. Future works are needed for better understanding the V isotope fractionation mechanisms of subduction zone lavas. [1]Prytulak et al., 2017, Geochem. Persp. Let. 3, 75-84. [2]Huang et al., 2016, Goldschmidt Abstracts. 1190. [3] Prytulak et al., 2013, EPSL. 365, 177-189.

Titanium stable isotope investigation of magmatic processes on the Earth and Moon

NASA Astrophysics Data System (ADS)

Millet, Marc-Alban; Dauphas, Nicolas; Greber, Nicolas D.; Burton, Kevin W.; Dale, Chris W.; Debret, Baptiste; Macpherson, Colin G.; Nowell, Geoffrey M.; Williams, Helen M.

2016-09-01

We present titanium stable isotope measurements of terrestrial magmatic samples and lunar mare basalts with the aims of constraining the composition of the lunar and terrestrial mantles and evaluating the potential of Ti stable isotopes for understanding magmatic processes. Relative to the OL-Ti isotope standard, the δ49Ti values of terrestrial samples vary from -0.05 to +0.55‰, whereas those of lunar mare basalts vary from -0.01 to +0.03‰ (the precisions of the double spike Ti isotope measurements are ca. ±0.02‰ at 95% confidence). The Ti stable isotope compositions of differentiated terrestrial magmas define a well-defined positive correlation with SiO2 content, which appears to result from the fractional crystallisation of Ti-bearing oxides with an inferred isotope fractionation factor of ΔTi49oxide-melt = - 0.23 ‰ ×106 /T2. Primitive terrestrial basalts show no resolvable Ti isotope variations and display similar values to mantle-derived samples (peridotite and serpentinites), indicating that partial melting does not fractionate Ti stable isotopes and that the Earth's mantle has a homogeneous δ49Ti composition of +0.005 ± 0.005 (95% c.i., n = 29). Eclogites also display similar Ti stable isotope compositions, suggesting that Ti is immobile during dehydration of subducted oceanic lithosphere. Lunar basalts have variable δ49Ti values; low-Ti mare basalts have δ49Ti values similar to that of the bulk silicate Earth (BSE) while high-Ti lunar basalts display small enrichment in the heavy Ti isotopes. This is best interpreted in terms of source heterogeneity resulting from Ti stable isotope fractionation associated with ilmenite-melt equilibrium during the generation of the mantle source of high-Ti lunar mare basalts. The similarity in δ49Ti between terrestrial samples and low-Ti lunar basalts provides strong evidence that the Earth and Moon have identical stable Ti isotope compositions.

Site-selective nitrogen isotopic ratio measurement of nitrous oxide using a TE-cooled CW-RT-QCL based spectrometer.

PubMed

Li, Jingsong; Zhang, Lizhu; Yu, Benli

2014-12-10

The feasibility of laser spectroscopic isotopic composition measurements of atmospheric N2O was demonstrated, although making them useful will require further improvements. The system relies on a thermoelectrically (TE) cooled continuous-wave (CW) room temperature (RT) quantum cascade laser source emitting wavelength of around 4.6μm, where strong fundamental absorption bands occur for the considered specie and its isotopomers. The analysis technique is based on wavelength modulation spectroscopy with second-harmonic detection and the combination of long-path absorption cell. Primary laboratory tests have been performed to estimate the achievable detection limits and the signal reproducibility levels in view of possible measurements of (15)N/(14)N and (18)O/(16)O isotope ratios. The experiment results showed that the site-selective (15)N/(14)N ratio can be measured with a precision of 3‰ with 90s averaging time using natural-abundance N2O sample of 12.7ppm. Copyright © 2014 Elsevier B.V. All rights reserved.

The post-Paleozoic chronology and mechanism of 13C depletion in primary marine organic matter

NASA Technical Reports Server (NTRS)

Popp, B. N.; Takigiku, R.; Hayes, J. M.; Louda, J. W.; Baker, E. W.

1989-01-01

Carbon-isotopic compositions of geoporphyrins have been measured from marine sediments of Mesozoic and Cenozoic age in order to elucidate the timing and extent of depletion of 13C in marine primary producers. These results indicate that the difference in isotopic composition of coeval marine carbonates and marine primary photosynthate was approximately 5 to 7 permil greater during the Mesozoic and early Cenozoic than at present. In contrast to the isotopic record of marine primary producers, isotopic compositions of terrestrial organic materials have remained approximately constant for this same interval of time. This difference in the isotopic records of marine and terrestrial organic matter is considered in terms of the mechanisms controlling the isotopic fractionation associated with photosynthetic fixation of carbon. We show that the decreased isotopic fractionation between marine carbonates and organic matter from the Early to mid-Cenozoic may record variations in the abundance of atmospheric CO2.

Isotopic compositions of cometary matter returned by Stardust.

PubMed

McKeegan, Kevin D; Aléon, Jerome; Bradley, John; Brownlee, Donald; Busemann, Henner; Butterworth, Anna; Chaussidon, Marc; Fallon, Stewart; Floss, Christine; Gilmour, Jamie; Gounelle, Matthieu; Graham, Giles; Guan, Yunbin; Heck, Philipp R; Hoppe, Peter; Hutcheon, Ian D; Huth, Joachim; Ishii, Hope; Ito, Motoo; Jacobsen, Stein B; Kearsley, Anton; Leshin, Laurie A; Liu, Ming-Chang; Lyon, Ian; Marhas, Kuljeet; Marty, Bernard; Matrajt, Graciela; Meibom, Anders; Messenger, Scott; Mostefaoui, Smail; Mukhopadhyay, Sujoy; Nakamura-Messenger, Keiko; Nittler, Larry; Palma, Russ; Pepin, Robert O; Papanastassiou, Dimitri A; Robert, François; Schlutter, Dennis; Snead, Christopher J; Stadermann, Frank J; Stroud, Rhonda; Tsou, Peter; Westphal, Andrew; Young, Edward D; Ziegler, Karen; Zimmermann, Laurent; Zinner, Ernst

2006-12-15

Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single (17)O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is (16)O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion.

Isotopic Analysis and Evolved Gases

NASA Technical Reports Server (NTRS)

Swindle, Timothy D.; Boynton, William V.; Chutjian, Ara; Hoffman, John H.; Jordan, Jim L.; Kargel, Jeffrey S.; McEntire, Richard W.; Nyquist, Larry

1996-01-01

Precise measurements of the chemical, elemental, and isotopic composition of planetary surface material and gases, and observed variations in these compositions, can contribute significantly to our knowledge of the source(s), ages, and evolution of solar system materials. The analyses discussed in this paper are mostly made by mass spectrometers or some other type of mass analyzer, and address three broad areas of interest: (1) atmospheric composition - isotopic, elemental, and molecular, (2) gases evolved from solids, and (3) solids. Current isotopic data on nine elements, mostly from in situ analysis, but also from meteorites and telescopic observations are summarized. Potential instruments for isotopic analysis of lunar, Martian, Venusian, Mercury, and Pluto surfaces, along with asteroid, cometary and icy satellites, surfaces are discussed.

Approaches to Plant Hydrogen and Oxygen Isoscapes Generation

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

West, Jason B.; Kreuzer-Martin, Helen W.; Ehleringer, James

2009-12-01

Plant hydrogen and oxygen isoscapes have been utilized to address important and somewhat disparate research goals. The isotopic composition of leaf water affects the isotopic composition of atmospheric CO2 and O2 and is a logical starting point for understanding the isotopic composition of plant organic compounds since photosynthesis occurs in the leaf water environment. Leaf water isoscapes have been produced largely as part of efforts to understand atmospheric gas isotopic composition. The isotopic composition of plant organic matter has also been targeted for its potential to serve as a proxy for past environmental conditions. Spatially distributed sampling and modeling ofmore » modern plant H & O isoscapes can improve our understanding of the controls of the isotope ratios of compounds such as cellulose or n-alkanes from plants and therefore their utility for paleoreconstructions. Spatially varying plant hydrogen and oxygen isotopes have promise for yielding geographic origin information for a variety of plant products, including objects of criminal forensic interest or food products. The future has rich opportunities for the continued development of mechanistic models, methodologies for the generation of hydrogen and oxygen isoscapes, and cross-disciplinary interactions as these tools for understanding are developed, shared, and utilized to answer large-scale questions.« less

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.

Mercury isotope fractionation during ore retorting in the Almadén mining district, Spain

USGS Publications Warehouse

Gray, John E.; Pribil, Michael J.; Higueras, Pablo L.

2013-01-01

Almadén, Spain, is the world's largest mercury (Hg) mining district, which has produced over 250,000 metric tons of Hg representing about 30% of the historical Hg produced worldwide. The objective of this study was to measure Hg isotopic compositions of cinnabar ore, mine waste calcine (retorted ore), elemental Hg (Hg0(L)), and elemental Hg gas (Hg0(g)), to evaluate potential Hg isotopic fractionation. Almadén cinnabar ore δ202Hg varied from − 0.92 to 0.15‰ (mean of − 0.56‰, σ = 0.35‰, n = 7), whereas calcine was isotopically heavier and δ202Hg ranged from − 0.03‰ to 1.01‰ (mean of 0.43‰, σ = 0.44‰, n = 8). The average δ202Hg enrichment of 0.99‰ between cinnabar ore and calcines generated during ore retorting indicated Hg isotopic mass dependent fractionation (MDF). Mass independent fractionation (MIF) was not observed in any of the samples in this study. Laboratory retorting experiments of cinnabar also were carried out to evaluate Hg isotopic fractionation of products generated during retorting such as calcine, Hg0(L), and Hg0(g). Calcine and Hg0(L) generated during these retorting experiments showed an enrichment in δ202Hg of as much as 1.90‰ and 0.67‰, respectively, compared to the original cinnabar ore. The δ202Hg for Hg0(g) generated during the retorting experiments was as much as 1.16‰ isotopically lighter compared to cinnabar, thus, when cinnabar ore was roasted, the resultant calcines formed were isotopically heavier, whereas the Hg0(g) generated was isotopically lighter in Hg isotopes.

The evolution of 13C and 18O isotope composition of DIC in a calcite depositing film of water with isotope exchange between the DIC and a CO2 containing atmosphere, and simultaneous evaporation of the water. Implication to climate proxies from stalagmites: A theoretical model

NASA Astrophysics Data System (ADS)

Dreybrodt, Wolfgang; Romanov, Douchko

2016-12-01

The most widely applied climate proxies in speleothems are the isotope compositions of carbon and oxygen expressed by δ13C and δ18O values. However, mechanisms, which are not related to climate changes, overlay the climate signal. One is the temporal increase of both, δ13C and δ18O values by kinetic processes during precipitation of calcite. Isotope exchange between DIC in the water and the CO2 in the surrounding cave atmosphere can also change isotope composition. Here we present a theoretical model of the temporal isotope evolution of DIC in a thin water layer during precipitation of calcite and simultaneous isotope exchange with the cave atmosphere, and simultaneous evaporation of water. The exchange of oxygen isotopes in the DIC with those in the water is also considered.

The Suess-Urey mission (return of solar matter to Earth).

PubMed

Rapp, D; Naderi, F; Neugebauer, M; Sevilla, D; Sweetnam, D; Burnett, D; Wiens, R; Smith, N; Clark, B; McComas, D; Stansbery, E

1996-01-01

The Suess-Urey (S-U) mission has been proposed as a NASA Discovery mission to return samples of matter from the Sun to the Earth for isotopic and chemical analyses in terrestrial laboratories to provide a major improvement in our knowledge of the average chemical and isotopic composition of the solar system. The S-U spacecraft and sample return capsule will be placed in a halo orbit around the L1 Sun-Earth libration point for two years to collect solar wind ions which implant into large passive collectors made of ultra-pure materials. Constant Spacecraft-Sun-Earth geometries enable simple spin stabilized attitude control, simple passive thermal control, and a fixed medium gain antenna. Low data requirements and the safety of a Sun-pointed spinner, result in extremely low mission operations costs.

Triple oxygen isotope composition of tropospheric carbon dioxide and terrestrial carbonates

NASA Astrophysics Data System (ADS)

Hofmann, M. E.; Horváth, B.; Pack, A.

2011-12-01

The triple oxygen isotope composition of tropospheric CO2 is a potential new tracer in urban air studies and for biosphere-atmosphere interactions [1]. In this study, we are analyzing CO2 from different provenances in order to trace the influx of anthropogenic CO2 to urban air and to test predictions on the stratosphere-troposphere exchange flux. Since July 2010, we are monitoring the triple oxygen isotope composition of CO2 in urban air in a two-week interval. For this purpose, carbon dioxide was extracted from ~450L of ambient air on the campus of the University of Göttingen using a Russian Doll type cryogenic trap [2]. The CO2 was analyzed by CO2-CeO2 equilibration at 685°C and subsequent IR laser fluorination of CeO2 and CF-irmMS [3]. All triple oxygen isotope data are reported as Δ17OTFL values relative to the terrestrial fractionation line (TFL) with a slope βTFL=0.5251 and an intercept γTFL=-0.014%. On average, the Δ17OTFL value of ambient CO2 was -0.11±0.05% (SD) with a seasonal cycle of 0.04±0.01%. Lower Δ17O values were observed during wintertime. In order to test the potential of Δ17O as a tracer for anthropogenic CO2, we analyzed CO2 from different combustion processes. Our results showed that the Δ17O anomaly of tropospheric O2 [4] is passed on fully, or partially to the combustion CO2 [5]. We estimate that elevated anthropogenic emission during wintertime could be responsible for a decrease in Δ17O of urban air CO2 of -0.02±0.01%. In order to predict the triple oxygen isotope composition of tropospheric CO2 on a global scale, we revised the box model calculation from Hoag et al. [1]. For the exponent β for CO2-water equilibrium, we assume that βCO2-water=0.522±0.001 [6]. Furthermore, we took into account that the Δ17OTFL value of CO2 released from soils is affected by kinetic fractionation. Thus, we obtained a Δ17OTFL value for global tropospheric CO2 of -0.13%. The model calculation agrees well with the Δ17OTFL value determined for ambient air CO2. The triple oxygen isotope composition of terrestrial carbonates should provide additional information on the formation process of biogenic and abiotic carbonates. In order to determine the triple oxygen isotope composition on carbonates, phosphoric acid decomposition of carbonates was carried out. Subsequently, the liberated CO2 was also analyzed by the CO2-CeO2 equilibration method [3]. The Δ17OTFL of CO2 released from Solnhofen limestone was -0.11±0.09% (SE, t0.95, n=6). We are currently determining the exponent β for phosphoric acid decomposition. [1] Hoag, K.J., et al., Geophys. Res. Lett., 2005. 32: p. 1-5. [2] Brenninkmeijer, C.A.M. and T. Röckmann, Anal. Chem., 1996. 68(17): p. 3050-3053. [3] Hofmann, M. and A. Pack, Anal. Chem., 2010. 82: p. 4357-4361. [4] Barkan, E. and B. Luz, Rapid Commun. Mass Spec., 2005. 19(24): p. 3737-3742. [5] Horváth, B., M.E.G. Hofmann, and A. Pack, 2011. XI Isotope Workshop. Budapest. [6] Hofmann, M., et al., 2011. EGU. Vienna.

Heterogeneity of the Caribbean plateau mantle source: Sr, O and He isotopic compositions of olivine and clinopyroxene from Gorgona Island

NASA Astrophysics Data System (ADS)

Révillon, S.; Chauvel, C.; Arndt, N. T.; Pik, R.; Martineau, F.; Fourcade, S.; Marty, B.

2002-12-01

The composition of the mantle plumes that created large oceanic plateaus such as Ontong Java or the Caribbean is still poorly known. Geochemical and isotopic studies on accreted portions of the Caribbean plateau have shown that the plume source was heterogeneous and contained isotopically depleted and relatively enriched portions. A distinctive feature of samples from the Caribbean plateau is their unusual Sr isotopic compositions, which, at a given Nd isotopic ratio, are far higher than in samples from other oceanic plateaus. Sr, O and He isotopic compositions of whole rocks and magmatic minerals (clinopyroxene or olivine) separated from komatiites, gabbros and peridotites from Gorgona Island in Colombia were determined to investigate the origin of these anomalously radiogenic compositions. Sequentially leached clinopyroxenes have Sr isotopic compositions in the range 87Sr/ 86Sr=0.70271-0.70352, systematically lower than those of leached and unleached whole rocks. Oxygen isotopic ratios of clinopyroxene vary within the range δ 18O=5.18-5.35‰, similar to that recorded in oceanic island basalts. He isotopic ratios are high ( R/ Ra=8-19). The lower 87Sr/ 86Sr ratios of most of the clinopyroxenes shift the field of the Caribbean plateau in Nd-Sr isotope diagrams toward more 'normal' values, i.e. a position closer to the field defined by mid-ocean ridge basalts and oceanic-island basalts. Three clinopyroxenes have slightly higher 87Sr/ 86Sr ratios that cannot be explained by an assimilation model. The high 87Sr/ 86Sr and variations of 143Nd/ 144Nd are interpreted as a source characteristic. Trace-element ratios, however, are controlled mainly by fractionation during partial melting. We combine these isotopic data in a heterogeneous plume source model that accounts for the diversity of isotopic signatures recorded on Gorgona Island and throughout the Caribbean plateau. The heterogeneities are related to old recycled oceanic lithosphere in the plume source; the high 3He/ 4He ratios may indicate that the source material once resided in the lower mantle.

Nd Isotope and U-Th-Pb Age Mapping of Single Monazite Grains by Laser Ablation Split Stream Analysis

NASA Astrophysics Data System (ADS)

Fisher, C. M.; Hanchar, J. M.; Miller, C. F.; Phillips, S.; Vervoort, J. D.; Martin, W.

2015-12-01

Monazite is a common accessory mineral that occurs in medium to high grade metamorphic and Ca-poor felsic igneous rocks, and often controls the LREE budget (including Sm and Nd) of the host rock in which it crystallizes. Moreover, it contains appreciable U and Th, making it an ideal mineral for determining U-Th-Pb ages and Sm-Nd isotopic compositions, both of which are readily determined using in situ techniques with very high spatial resolution like LA-MC-ICPMS. Here, we present the results of laser ablation split stream analyses (LASS), which allows for simultaneous determination of the age and initial Nd isotopic composition in a single analysis. Analyses were done using a 20mm laser spot that allowed for detailed Nd isotope mapping of monazite grains (~30 analyses per ~250mm sized grain). Combined with LREE ratios (e.g., Sm/Nd, Ce/Gd, and Eu anomalies) these results yield important petrogenetic constraints on the evolution of peraluminous granites from the Old Woman-Piute batholith in southeastern California. Our findings also allow an improved understanding of the causes of isotope heterogeneity in granitic rocks. U-Th-Pb age mapping across the crystals reveals a single Cretaceous age for all grains with precision and accuracy typical of laser ablation analyses (~2%). In contrast, the concurrent Nd isotope mapping yields homogeneous initial Nd isotope compositions for some grains and large initial intra-grain variations of up to 8 epsilon units in others. The grains that yield homogeneous Nd isotope compositions have REE ratios suggesting that they crystallized in a fractionally crystallizing magma. Conversely, other grains, which also record fractional crystallization of both feldspar and LREE rich minerals, demonstrate a change in the Nd isotope composition of the magma during crystallization of monazite. Comparison of inter- and intra-grain Nd isotope compositions reveals further details on the potential mechanisms responsible for isotope heterogeneity present in single rock samples. This method highlights the potential of single grain isotope mapping of LREE phases such as monazite, allanite, and titanite for understanding both igneous and metamorphic petrogenesis.

Measurement and Modeling of Site-specific Nitrogen and Oxygen Isotopic Composition of Atmospheric Nitrous Oxide at Mace Head, Ireland

NASA Astrophysics Data System (ADS)

McClellan, M. J.; Saikawa, E.; Prinn, R. G.; Ono, S.

2015-12-01

Global mixing ratios of atmospheric nitrous oxide (N2O), a potent greenhouse gas, have increased nearly linearly from the beginning of the modern industrial period to today, with the current global average in excess of 325 ppb. This increase can be largely attributed to anthropogenic activity above the level of N2O emissions from natural biotic sources. The effect of N2O on Earth's climate is twofold: in the troposphere, N2O is radiatively active and chemically inert, while it serves as a reactive source of ozone-destroying nitrogen oxides in the stratosphere. The marked altitudinal divide in its reactivity means that all stages in the N2O life cycle—emission, transport, and destruction—must be examined to understand the overall effect of N2O on Earth's climate. However, the understanding of the total impact of N2O is incomplete, as there remain significant uncertainties in the global budget of this gas. Due to unique isotopic substitutions (15N and 18O) made by different N2O sources and stratospheric chemical reactions, the measurement of N2O isotopic ratios in ambient air can help identify the distribution and magnitude of distinct source types. We present the first year of site-specific nitrogen and oxygen isotopic composition data from the MIT Stheno-tunable infrared direct absorption spectroscopy (TILDAS) instrument at Mace Head, Ireland. Aided by the Stheno preconcentration system, Stheno-TILDAS can achieve measurement precisions of 0.10‰ or greater for all isotopic ratios (δ15N and δ18O) in ambient N2O. We further compare these data to the results from Model for Ozone and Related Tracers version 4 (MOZART-4) simulations, including N2O isotopic fractionation processes and MERRA/GEOS-5 reanalysis meteorological fields. These results will form the basis of future Bayesian inverse modeling simulations that will constrain global N2O source, circulation, and sink dynamics better.

Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

NASA Technical Reports Server (NTRS)

Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

1983-01-01

In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

Fluid inclusion and sulphur isotope evidence for syntectonic mineralisation at the Elura mine, southeastern Australia

NASA Astrophysics Data System (ADS)

Seccombe, P. K.

1990-10-01

Fluid inclusion and sulphur isotope data for the discordant, metasediment-hosted massive sulphide deposit at Elura are consistent with a syntectonic origin of the orebodies. Thermometric and laser Raman microprobe analyses indicate that two-phase, primary fluid inclusions are low salinity and H2O-CO2-CH4 types. Inclusion fluids from quartz in ore yield homogenisation temperatures (Th) ranging from 298 ° to 354 °C (mean 320 °C). They are likely to have been trapped close to the solvus of the H2O-CO2-(CH4-NaCl) system and thus should give temperatures of the mineralising fluid. An additional, low Th population of later fluid inclusions is recognised in quartz from ore and syntectonic extension veins in the adjacent wallrock. Th's for these low CO2bearing inclusions range from 150 to 231 °C (mean 190 °C), and should be considerably lower than true trapping temperatures. Sulphur isotopic composition (δ34S) of pyrite, sphalerite, pyrrhotite and galena ranges from 4.7 to 12.6% and indicates a sulphur source from underlying Cobar Supergroup metasediments. An average temperature of 275 °C from the sphalerite-galena sulphur isotopic thermometer suggests isotopic re-equilibration below peak metamorphic temperatures.

Effects of thermal maturation and thermochemical sulfate reduction on compound-specific sulfur isotopic compositions of organosulfur compounds in Phosphoria oils from the Bighorn Basin, USA

USGS Publications Warehouse

Ellis, Geoffrey S.; Said-Ahamed, Ward; Lillis, Paul G.; Shawar, Lubna; Amrani, Alon

2017-01-01

Compound-specific sulfur isotope analysis was applied to a suite of 18 crude oils generated from the Permian Phosphoria Formation in the Bighorn Basin, western USA. These oils were generated at various levels of thermal maturity and some experienced thermochemical sulfate reduction (TSR). This is the first study to examine the effects of thermal maturation on stable sulfur isotopic compositions of individual organosulfur compounds (OSCs) in crude oil. A general trend of 34S enrichment in all of the studied compounds with increasing thermal maturity was observed, with the δ34S values of alkyl-benzothiophenes (BTs) tending to be enriched in 34S relative to those of the alkyl-dibenzothiophenes (DBTs) in lower-maturity oils. As thermal maturity increases, δ34S values of both BTs and DBTs become progressively heavier, but the difference in the average δ34S value of the BTs and DBTs (Δ34S BT-DBT) decreases. Differences in the isotopic response to thermal stress exhibited by these two compound classes are considered to be the result of relative differences in their thermal stabilities. TSR-altered Bighorn Basin oils have OSCs that are generally enriched in 34S relative to non-TSR-altered oils, with the BTs being enriched in 34S relative to the DBTs, similar to the findings of previous studies. However, several oils that were previously interpreted to have been exposed to minor TSR have Δ34S BT-DBT values that do not support this interpretation. The δ34S values of the BTs and DBTs in some of these oils suggest that they did not experience TSR, but were derived from a more thermally mature source. The heaviest δ34S values observed in the OSCs are enriched in 34S by up to 10‰ relative to that of Permian anhydrite in the Bighorn Basin, suggesting that there may be an alternate or additional source of sulfate in some parts of the basin. These results indicate that the sulfur isotopic composition of OSCs in oil provides a sensitive indicator for the extent of TSR, which cannot be determined from other bulk geochemical parameters. Moreover, when combined with additional geochemical and geologic evidence, the sulfur isotopic composition of OSCs in oils can help to identify the source of sulfate for TSR alteration in petroleum reservoirs.

Osmium Isotope Compositions of Komatiite Sources Through Time

NASA Astrophysics Data System (ADS)

Walker, R. J.

2001-12-01

Extending Os isotopic measurements to ancient plume sources may help to constrain how and when the well-documented isotopic heterogeneities in modern systems were created. Komatiites and picrites associated with plume-related volcanism are valuable tracers of the Os isotopic composition of plumes because of their typically high Os concentrations and relatively low Re/Os. Re-Os data are now available for a variety of Phanerozoic, Proterozoic and Archean komatiites and picrites. As with modern plumes, the sources of Archean and Proterozoic komatiites exhibit a large range of initial 187Os/188Os ratios. Most komatiites are dominated by sources with chondritic Os isotopic compositions (e.g. Song La; Norseman-Wiluna; Pyke Hill; Alexo), though some (e.g. Gorgona) derive from heterogeneous sources. Of note, however, two ca. 2.7 Ga systems, Kostomuksha (Russia) and Belingwe (Zimbabwe), have initial ratios enriched by 2-3% relative to the contemporary convecting upper mantle. These results suggest that if the 187Os enrichment was due to the incorporation of minor amounts of recycled crust into the mantle source of the rocks, the crust formed very early in Earth history. Thus, the Os results could reflect derivation of melt from hybrid mantle whose composition was modified by the addition of mafic crustal material that would most likely have formed between 4.2 and 4.5 Ga. Alternately, the mantle sources of these komatiites may have derived a portion of their Os from the putative 187Os - and 186Os -enriched outer core. For this hypothesis to be applicable to Archean rocks, an inner core of sufficient mass would have to have crystallized sufficiently early in Earth history to generate an outer core with 187Os enriched by at least 3% relative to the chondritic average. Using the Pt-Re-Os partition coefficients espoused by our earlier work, and assuming linear growth of the inner core started at 4.5 Ga and continued to present, would yield an outer core at 2.7 Ga with a gamma Os value of only +1.2 and a 186Os/188Os enrichment relative to the contemporary upper mantle of only +13 ppm. Greater isotopic enrichments could have been achieved by 2.7 Ga if either the inner core comprised >2.8% of the mass of the core by 2.7 Ga, or if Re and Os solid metal-liquid metal D's for core crystallization were greater that those applied in the initial calculation.

The preliminary result of the δ65Cu and δ34S values of major ore minerals in the Erdenetiin-Ovoo Cu-Mo porphyry deposit, Northern Mongolia

NASA Astrophysics Data System (ADS)

KIM, Y.; Lee, I.; Oyungerel, S.; Jargal, L.; Tsedenbal, T.; Ryu, J. S.

2016-12-01

The copper isotope (δ65Cu) and sulfur isotope (δ34S) compositions of major ore minerals from the Erdenetiin-Ovoo Cu-Mo porphyry deposit were measured to trace sources of copper and sulfur, and to evaluate the precipitation environment of ore minerals. The major ore minerals are pyrite, chalcopyrite, molybdenite and chalcocite developed in the QSP (Quartz-Sericite-Pyrite) alteration zone. The sulfide minerals such as sphalerite and covellite, and carbonate ore minerals like malachite, azurite are also identified. The copper isotope ratios (65Cu/63Cu) of copper ore minerals (chalcopyrite, chalcocite, malachite, azurite, covellite and chrysocolla) were analyzed by the MC-ICPMS in KBSI located in Ochang, South Korea. The measured δ65Cu values relative to NIST 976 range from -1.01 ‰ to 5.76 ‰. The average δ65Cu values of sulfide minerals such as chalcopyrite (1.03 ‰), chalcocite (0.62 ‰) and covellite (0.51 ‰) seem to be relatively lower than those of carbonate and silicate Cu minerals such as malachite (0.24 ‰), azurite (2.17 ‰) and chrysocolla (5.76 ‰). The sulfur isotope ratios (34S/32S) of major sulfide minerals were measured by EA-CF-IRMS (Elemental Analyzer - Continuous Flow - Isotope Ratio Mass Spectrometer) in NCIRF, Seoul National University. The average δ34SV-CDT value is -1.1 ‰ indicating the magmatic signature of sulfur. There is the difference of δ34S values between sulfide minerals. While the δ34S values of pyrite, chalcopyrite and molybdenite range from -0.9 to 0.8 ‰, the δ34S values of chalcocite range from -2.6 ‰ to -1.4 ‰. These lower values might be attributed to the sulfur isotope fractionation during its precipitation.

Isotopic compositions of the elements 2013 (IUPAC Technical Report)

USGS Publications Warehouse

Meija, Juris; Coplen, Tyler B.; Berglund, Michael; Brand, Willi A.; De Bièvre, Paul; Gröning, Manfred; Holden, Norman E.; Irrgeher, Johanna; Loss, Robert D.; Walczyk, Thomas; Prohaska, Thomas

2016-01-01

The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) of the International Union of Pure and Applied Chemistry (iupac.org) has revised the Table of Isotopic Compositions of the Elements (TICE). The update involved a critical evaluation of the recent published literature. The new TICE 2013 includes evaluated data from the “best measurement” of the isotopic abundances in a single sample, along with a set of representative isotopic abundances and uncertainties that accommodate known variations in normal terrestrial materials.

Compositional evolution of the upper continental crust through time, as constrained by ancient glacial diamictites

NASA Astrophysics Data System (ADS)

Gaschnig, Richard M.; Rudnick, Roberta L.; McDonough, William F.; Kaufman, Alan J.; Valley, John W.; Hu, Zhaochu; Gao, Shan; Beck, Michelle L.

2016-08-01

The composition of the fine-grained matrix of glacial diamictites from the Mesoarchean, Paleoproterozoic, Neoproterozoic, and Paleozoic, collected from four modern continents, reflects the secular evolution of the average composition of the upper continental crust (UCC). The effects of localized provenance are present in some cases, but distinctive geochemical signatures exist in diamictites of the same age from different localities, suggesting that these are global signatures. Archean UCC, dominated by greenstone basalts and to a lesser extent komatiites, was more mafic, based on major elements and transition metal trace elements. Temporal changes in oxygen isotope ratios, rare earth elements, and high field strength elements indicate that the UCC became more differentiated and that tonalite-trondhjemite-granodiorite suites became less important with time, findings consistent with previous studies. We also document the concentrations of siderophile and chalcophile elements (Ga, Ge, Cd, In, Sn, Sb, W, Tl, Bi) and lithophile Be in the UCC through time, and use the data for the younger diamictites to construct a new estimate of average UCC along with associated uncertainties.

Uncoupling between soil and xylem water isotopic composition: how to discriminate mobile and tightly-bound water?

NASA Astrophysics Data System (ADS)

Martín Gómez, Paula; Aguilera, Mònica; Pemán, Jesús; Gil Pelegrín, Eustaquio; Ferrio, Juan Pedro

2014-05-01

As a general rule, no isotopic fractionation occurs during water uptake and water transport, thus, xylem water reflects source water. However, this correspondence does not always happen. Isotopic enrichment of xylem water has been found in several cases and has been either associated to 'stem processes' like cuticular evaporation 1 and xylem-phloem communication under water stress 2,3 or to 'soil processes' such as species-specific use of contrasting water sources retained at different water potential forces in soil. In this regard, it has been demonstrated that mobile and tightly-bound water may show different isotopic signature 4,5. However, standard cryogenic distillation does not allow to separate different water pools within soil samples. Here, we carried out a study in a mixed adult forest (Pinus sylvestris, Quercus subpyrenaica and Buxus sempervirens) growing in a relatively deep loamy soil in the Pre-Pyrenees. During one year, we sampled xylem from twigs and soil at different depths (10, 30 and 50 cm). We also sampled xylem from trunk and bigger branches to assess whether xylem water was enriched in the distal parts of the tree. We found average deviations in the isotopic signature from xylem to soil of 4o 2o and 2.4o in δ18O and 18.3o 7.3o and 8.9o in δ2H, for P.sylvestris, Q.subpyrenaica and B.sempervirens respectively. Xylem water was always enriched compared to soil. In contrast, we did not find clear differences in isotopic composition between xylem samples along the tree. Declining the hypothesis that 'stem processes' would cause these uncoupling between soil and xylem isotopic values, we tested the possibility to separate mobile and tightly-bound water by centrifugation. Even though we could separate two water fractions in soils close to saturation, we could not recover a mobile fraction in drier soils. In this regard, we welcome suggestions on alternatives to separate different soil fractions in order to find the correspondence between soil and xylem water. References 1. Dawson, T. E. & Ehleringer, J. R. Isotopic enrichment of water in the 'woody' tissues of plants: Implications for plant water source, water uptake, and other studies which use the stable isotopic composition of cellulose. (1993). 2. Cernusak, L. a, Farquhar, G. D. & Pate, J. S. Environmental and physiological controls over oxygen and carbon isotope composition of Tasmanian blue gum, Eucalyptus globulus. Tree Physiol. 25, 129-46 (2005). 3. Bertrand, G. et al. Determination of spatiotemporal variability of tree water uptake using stable isotopes (δ 18 O, δ 2 H) in an alluvial system supplied by a high-altitude watershed, Pfyn forest, Switzerland. Ecohydrology (2012). doi:10.1002/eco.1347 4. Tang, K. & Feng, X. The effect of soil hydrology on the oxygen and hydrogen isotopic compositions of plants ' source water. 185, (2001). 5. Brooks, J. R., Barnard, H. R., Coulombe, R. & McDonnell, J. J. Ecohydrologic separation of water between trees and streams in a Mediterranean climate. Nat. Geosci. 3, 100-104 (2009). Acknowledgements This study was funded by RESILFOR project (AGL 2012-40039-C02-02) and FPU fellowship from the Spanish Ministry of Science and Innovation (FPU12/00648). We thank Instituto de Formación Agroambiental de Jaca and Unidad de Salud de los Bosques de Aragón for their support on field work and we feel very grateful to Miguel Ángel Lázaro for climbing the studied trees, José María Alcaire for one year of rain collection and Pilar Sopeña and Ma Josep Pau for laboratory analysis. Helpful comments by Jordi Voltas on statistical analysis have improved the quality of the work.

Open system models of isotopic evolution in Earth's silicate reservoirs: Implications for crustal growth and mantle heterogeneity

NASA Astrophysics Data System (ADS)

Kumari, Seema; Paul, Debajyoti; Stracke, Andreas

2016-12-01

An open system evolutionary model of the Earth, comprising continental crust (CC), upper and lower mantle (UM, LM), and an additional isolated reservoir (IR) has been developed to study the isotopic evolution of the silicate Earth. The model is solved numerically at 1 Myr time steps over 4.55 Gyr of Earth history to reproduce both the present-day concentrations and isotope ratios of key radioactive decay systems (Rb-Sr, Sm-Nd, and U-Th-Pb) in these terrestrial reservoirs. Various crustal growth scenarios - continuous versus episodic and early versus late crustal growth - and their effect on the evolution of Sr-Nd-Pb isotope systematics in the silicate reservoirs have been evaluated. Modeling results where the present-day UM is ∼60% of the total mantle mass and a lower mantle that is non-primitive reproduce the estimated geochemical composition and isotope ratios in Earth's silicate reservoirs. The isotopic evolution of the silicate Earth is strongly affected by the mode of crustal growth; only an exponential crustal growth pattern with crustal growth since the early Archean satisfactorily explains the chemical and isotopic evolution of the crust-mantle system and accounts for the so-called Pb paradoxes. Assuming that the OIB source is located in the deeper mantle, our model could, however, not reproduce its target ɛNd of +4.6 for the UM, which has been estimated from the average isotope ratios of 32 individual ocean island localities. Hence, either mantle plumes sample the LM in a non-representative way, or the simplified model set-up does not capture the full complexity of Earth's lower mantle (Nd isotope) evolution. Compared to the results obtained for a 4.55 Ga Earth, a model assuming a protracted U-Pb evolution of silicate Earth by ca. 100 Myr reproduces a slightly better fit for the Pb isotope ratios in Earth's silicate reservoirs. One notable feature of successful models is the early depletion of incompatible elements (as well as rapid decrease in Th/U) in the UM within the initial 500 Myr, as a result of early formation of CC, which supports other evidence in favor of the presence of Hadean continental crust. Therefore, a chondritic Th/U ratio (4 ± 0.2) in the UM until 2 Gyr appears rather unlikely. We find that the κ conundrum - the observation that measured Th/U ratios and those deduced from 208Pb-206Pb isotope systematics differ - is a natural outcome of an open system evolution in which preferential recycling of U for the past 2 Gyr has played a dominant role. Overall, our simulations strongly favor exponential crustal growth, starting in the early Hadean, the transient preservation of compositionally distinct mantle reservoirs over billion year time periods, and a generally less incompatible element depleted, but non-primitive composition of the lower mantle.

Trace Element and Cu Isotopic Tracers of Subsurface Flow and Transport in Wastewater Irrigated Soils

NASA Astrophysics Data System (ADS)

Carte, J.; Fantle, M. S.

2017-12-01

An understanding of subsurface flow paths is critical for quantifying the fate of contaminants in wastewater irrigation systems. This study investigates the subsurface flow of wastewater by quantifying the distribution of trace contaminants in wastewater irrigated soils. Soil samples were collected from the upper 1m of two wetlands at Penn State University's wastewater irrigation site, at which all effluent from the University's wastewater treatment plant has been sprayed since 1983. Major and trace element and Cu isotopic composition were determined for these samples, in addition to wastewater effluent and bedrock samples. The upper 20 cm of each wetland shows an enrichment of Bi, Cd, Cr, Cu, Mo, Ni, Pb, and Zn concentrations relative to deep (>1m) soils at the site by a factor of 1.7-3.5. Each wetland also has a subsurface clay rich horizon with Bi, Cu, Li, Ni, Pb, and Zn concentrations enriched by a factor of 1.4 to 5 relative to deep soils. These subsurface horizons directly underlie intervals that could facilitate preferential effluent flow: a gravel layer in one wetland, and a silty loam with visible mottling, an indication of dynamic water saturation, in the other. Trace metal concentrations in other horizons from both wetlands fall in the range of the deep soils. Significant variability in Cu isotopic composition is present in soils from both wetlands, with δ65Cu values ranging from 0.74‰ to 5.09‰. Soil δ65Cu correlates well with Cu concentrations, with lighter δ65Cu associated with higher concentrations. The Cu isotopic composition of the zones of metal enrichment are comparable to the ostensible average wastewater effluent δ65Cu value (0.61‰), while other horizons have considerably heavier δ65Cu values. We hypothesize that wastewater is the source of the metal enrichments, as each of the enriched elements are present as contaminants in wastewater, and the enrichments are located in clay-rich horizons conducive to trace metal immobilization due to adsorption. This hypothesis will be further tested by modeling with the reactive transport code CrunchTope. This study provides evidence that trace element and isotopic composition of soils can be useful tracers of subsurface hydrologic pathways and elemental fate and transport.

Relationship between the trajectory of mid-latitude cyclones in the eastern Pacific Ocean and the isotopic composition of snowfall in the Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Vasquez, K. T.; Sickman, J. O.; Heard, A.; Lucero, D.

2013-12-01

Diatoms, preserved in lake sediments, provide a potential archive of snowfall variability in the Sierra Nevada through their sensitivity to changes in water chemistry (a proxy for runoff volume) and by recording the isotopic composition of snow-melt (potentially a proxy for sources of atmospheric moisture). In the Sierra Nevada, we hypothesize that the oxygen isotopic composition of diatom silica is principally controlled by snow and that the isotopic composition of snow varies as a function of the tracks of mid-latitude cyclonic storms in the eastern Pacific Ocean. Snow samples from discrete storms were collected from December 2012 to March 2013 at 2042 meters a.s.l. in Sequoia National Park. The δ18O and δ2H values of the snow samples were measured using a temperature-conversion elemental analyzer coupled to a Delta V isotope ratio mass spectrometer. The isotopic measurements were then coupled to 3, 5 and 7-day air mass back trajectories using the NOAA HYSPLIT model. The measured δ18O values ranged from -17.6 to -7.8 per mil and the δ2H ranged from -119.8 to -73.3 per mil. Both δ18O and δ2H were inversely related to the latitude of the storm origin (R^2 values of 0.67 and 0.57, respectively). Winter storms from the Gulf of Alaska were the most isotopically depleted while storms originating in the subtropical/tropical Pacific were the most isotopically enriched, reflecting the overall latitudinal pattern of ocean-water isotope composition in the Pacific Ocean. Our results suggest that the isotopic composition of Sierra Nevada snowfall is influenced by storm track trajectory and this relationship could be useful in interpreting the climatic significance of δ18O of diatom silica preserved in lake cores.

Overview and Brief History of the Boron Isotope Proxy for Past Seawater pH

NASA Astrophysics Data System (ADS)

Hoenisch, B.; Hemming, G.

2007-05-01

In 1992 Hemming and Hanson (GCA, vol. 56, p. 537-543) showed that a variety of modern marine carbonates revealed a boron isotopic composition close to the isotopic composition of dissolved borate at modern seawater pH, suggesting this was the boron species preferentially adsorbed and incorporated into marine carbonates. With a constant offset between the trigonal and tetrahedrally coordinated boron species and a pH-dependent variation in their fractions, it appeared that this system would be sensitive to pH changes in the natural range of seawater. Accordingly, it was suggested that the boron isotope composition of marine carbonates is a proxy for past seawater pH. Subsequent culture studies with living planktic foraminifers and corals, as well as synthetic precipitation experiments confirmed that the boron isotopic composition follows the isotopic composition of borate across a wide range of seawater pH. In order to use the proxy with confidence, however, all other controls apart from pH need to be thoroughly understood. Recent laboratory and sediment experiments have demonstrated that vital effects and partial shell dissolution have the potential to modify the primary seawater pH signal recorded in the boron isotopic composition of planktic foraminifers. However it has also been shown that careful sample selection allows for avoiding these potential complications. A record of reconstructed surface seawater pH and estimated aqueous PCO2 shows a remarkable match between boron isotope based atmospheric pCO2 estimates and the Vostok ice core CO2 record. This convincingly demonstrates that boron isotopes in planktic foraminifers allow quantitative estimates of atmospheric pCO2 in the past, and confirms that glacial surface ocean pH was ~0.2 units higher compared to interglacial periods. We are going to review and discuss the achievements generated in Gil Hanson's lab over the past 15 years in the light of recent empirical measurements of the boron isotope fractionation between boric acid and borate in seawater.

Calibrating NIST SRM 683 as A New International Reference Standard for Zn Isotopes

NASA Astrophysics Data System (ADS)

Yang, Y.; Zhang, X.; Yu, H.; Huang, F.

2017-12-01

Zinc isotopes have been widely applied in the cosmochemical, geochemical, and environmental studies (Moynier et al. 2017). Obtaining precise Zn isotopic data for inter-laboratory comparison is a prerequisite to these applications. Currently, the JMC3-0749L is the primary reference standard for Zn isotopes (Albarède 2004), but it is not commercially available now. Thus, it is necessary to calibrate a new international primary reference standard for Zn isotopic analysis. Chen et al. (2016) showed that NIST SRM 683 (a pure Zn metal nugget of 140 grams) has a δ66ZnJMC of 0.12‰, which is falling within the range of natural Zn isotopic compositions, and it may a good candidate for the next generation of international reference standard (Chen et al. 2016). In order to further examine whether NIST SRM 683 has a homogeneous Zn isotopic composition, we measured more NIST SRM 683 by double-spike methods using MC-ICPMS (Conway et al. 2013). The metal nuggets of NIST SRM 683 were intensively sampled by micro-drilling. Zinc isotope analyses for two nuggets show that they have δ66Zn of 0.14 ± 0.02‰ (2SD, N = 32) and 0.13 ± 0.02‰ (2SD, N = 33), respectively. These values are similar to those of two Zn metal nuggets (0.11 ± 0.02‰ vs. 0.12 ± 0.02‰) reported previously by Chen et al. (2016). We fully dissolved one nugget, producing pure Zn solution with identical Zn isotopic composition with the drilling samples. All results strongly support that NIST SRM 683 is homogeneous in Zn isotopic compositions which could be an ideal candidate for the next reference for Zn isotopes. Tests on more metal nuggets will be performed in a few months for further confirming the Zn isotope compositions and homogeneity. Reference: Albarède et al., 2004. 'The stable isotope geochemistry of copper and zinc', Reviews in Mineralogy and Geochemistry, 55: 409-27. Chen et al., 2016. 'Zinc Isotopic Compositions of NIST SRM 683 and Whole-Rock Reference Materials', Geostandards and Geoanalytical Research, 40: 417-32. Conway et al., 2013. 'A new method for precise determination of iron, zinc and cadmium stable isotope ratios in seawater by double-spike mass spectrometry', Analytica chimica acta, 793: 44-52. Moynier et al., 2017. 'The isotope geochemistry of zinc and copper', Reviews in Mineralogy and Geochemistry, 82: 543-600.

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

Conroy, Jessica L; Cobb, Kim M; Noone, David

The objective of this field campaign was to investigate climatic controls on the stable isotopic composition of water vapor, precipitation, and seawater in the western tropical Pacific. Simultaneous measurements of the stable isotopic composition of vapor and precipitation from April 28 to May 8, 2013, at the Manus Tropical Western Pacific Atmospheric Radiation Measurement site, provided several key insights into the nature of the climate signal archived in precipitation and vapor isotope ratios. We observed a large shift from lower to higher isotopic values in vapor and precipitation because of the passage of a mesoscale convective system west of themore » site and a transition from a regional stormy period into a more quiescent period. During the quiescent period, the stable isotopic composition of vapor and precipitation indicated the predominance of oceanic evaporation in determining the isotopic composition of boundary-layer vapor and local precipitation. There was not a consistent relationship between intra-event precipitation amount at the site and the stable isotopic composition of precipitation, thus challenging simplified assumptions about the isotopic “amount effect” in the tropics on the time scale of individual storms. However, some storms did show an amount effect, and deuterium excess values in precipitation had a significant relationship with several meteorological variables, including precipitation, temperature, relative humidity, and cloud base height across all measured storms. The direction of these relationships points to condensation controls on precipitation deuterium excess values on intra-event time scales. The relationship between simultaneous measurements of vapor and precipitation isotope ratios during precipitation events indicates the ratio of precipitation-to-vapor isotope ratios can diagnose precipitation originating from a vapor source unique from boundary-layer vapor and rain re-evaporation.« less

Origin of heavy Fe isotope compositions in high-silica igneous rocks: A rhyolite perspective

NASA Astrophysics Data System (ADS)

Du, De-Hong; Wang, Xiao-Lei; Yang, Tao; Chen, Xin; Li, Jun-Yong; Li, Weiqiang

2017-12-01

The origin of heavy Fe isotope compositions in high-silica (>70 wt% SiO2) igneous rocks remains a highly controversial topic. Considering that fluid exsolution in eruptive rocks is more straight-forward to constrain than in plutonic rocks, this study addresses the problem of Fe isotope fractionation in high-silica igneous rocks by measuring Fe isotope compositions of representative rhyolitic samples from the Neoproterozoic volcanic-sedimentary basins in southern China and the Triassic Tu Le Basin in northern Vietnam. The samples show remarkably varied δ56FeIRMM014 values ranging from 0.05 ± 0.05‰ to 0.55 ± 0.05‰, which is among the highest values reported from felsic rocks. The extensional tectonic setting and short melt residence time in magma chambers for the studied rhyolites rule out Soret diffusion and thermal migration processes as causes of the high δ56Fe values. Effects of volcanic degassing and fluid exsolution on bulk rock δ56Fe values for the rhyolites are also assessed using bulk rock geochemical indicators and Rayleigh fractionation models, and these processes are found to be insufficient to produce resolvable changes in Fe isotope compositions of the residual melt. The most probable mechanism accounting for heavy Fe isotope compositions in the high-silica rhyolites is narrowed down to fractional crystallization processes in the magma before rhyolite eruption. Removal of isotopically light Fe-bearing minerals (i.e. ulvöspinel-rich titanomagnetite, ilmenite and biotite) is proposed as the main cause of Fe isotope variation in silicic melts during magmatic evolution. This study implies that crystal fractionation is the dominant mechanism that controls Fe isotope fractionation in eruptive rocks and Fe isotopes could be used to study magmatic differentiation of high-silica magmas.

High-precision 87Sr/86Sr analyses in wines and their use as a geological fingerprint for tracing geographic provenance.

PubMed

Marchionni, Sara; Braschi, Eleonora; Tommasini, Simone; Bollati, Andrea; Cifelli, Francesca; Mulinacci, Nadia; Mattei, Massimo; Conticelli, Sandro

2013-07-17

The radiogenic isotopic compositions of inorganic heavy elements such as Sr, Nd, and Pb of the food chain may constitute a reliable geographic fingerprint, their isotopic ratios being inherited by the geological substratum of the territory of production. The Sr isotope composition of geomaterials (i.e., rocks and soils) is largely variable, and it depends upon the age of the rocks and their nature (e.g., genesis, composition). In this study we developed a high-precision analytical procedure for determining Sr isotopes in wines at comparable uncertainty levels of geological data. With the aim of verifying the possibility of using Sr isotope in wine as a reliable tracer for geographic provenance, we performed Sr isotope analyses of 45 bottled wines from four different geographical localities of the Italian peninsula. Their Sr isotope composition has been compared with that of rocks from the substrata (i.e., rocks) of their vineyards. In addition wines from the same winemaker but different vintage years have been analyzed to verify the constancy with time of the (87)Sr/(86)Sr. Sr isotope compositions have been determined by solid source thermal ionization mass spectrometry following purification of Sr in a clean laboratory. (87)Sr/(86)Sr of the analyzed wines is correlated with the isotopic values of the geological substratum of the vineyards, showing little or no variation within the same vineyard and among different vintages. Large (87)Sr/(86)Sr variation is observed among wines from the different geographical areas, reinforcing the link with the geological substratum of the production territory. This makes Sr isotopes a robust geochemical tool for tracing the geographic authenticity and provenance of wine.

Geochemical Monitoring Of The Gas Hydrate Production By CO2/CH4 Exchange In The Ignik Sikumi Gas Hydrate Production Test Well, Alaska North Slope

NASA Astrophysics Data System (ADS)

Lorenson, T. D.; Collett, T. S.; Ignik Sikumi, S.

2012-12-01

Hydrocarbon gases, nitrogen, carbon dioxide and water were collected from production streams at the Ignik Sikumi gas hydrate production test well (TD, 791.6 m), drilled on the Alaska North Slope. The well was drilled to test the feasibility of producing methane by carbon dioxide injection that replaces methane in the solid gas hydrate. The Ignik Sikumi well penetrated a stratigraphically-bounded prospect within the Eileen gas hydrate accumulation. Regionally, the Eileen gas hydrate accumulation overlies the more deeply buried Prudhoe Bay, Milne Point, and Kuparuk River oil fields and is restricted to the up-dip portion of a series of nearshore deltaic sandstone reservoirs in the Sagavanirktok Formation. Hydrate-bearing sandstones penetrated by Ignik Sikumi well occur in three primary horizons; an upper zone, ("E" sand, 579.7 - 597.4 m) containing 17.7 meters of gas hydrate-bearing sands, a middle zone ("D" sand, 628.2 - 648.6 m) with 20.4 m of gas hydrate-bearing sands and a lower zone ("C" sand, 678.8 - 710.8 m), containing 32 m of gas hydrate-bearing sands with neutron porosity log-interpreted average gas hydrate saturations of 58, 76 and 81% respectively. A known volume mixture of 77% nitrogen and 23% carbon dioxide was injected into an isolated section of the upper part of the "C" sand to start the test. Production flow-back part of the test occurred in three stages each followed by a period of shut-in: (1) unassisted flowback; (2) pumping above native methane gas hydrate stability conditions; and (3) pumping below the native methane gas hydrate stability conditions. Methane production occurred immediately after commencing unassisted flowback. Methane concentration increased from 0 to 40% while nitrogen and carbon dioxide concentrations decreased to 48 and 12% respectively. Pumping above the hydrate stability phase boundary produced gas with a methane concentration climbing above 80% while the carbon dioxide and nitrogen concentrations fell to 2 and 18% respectively. Pumping below the gas hydrate stability phase boundary occurred in two periods with the composition of the produced gases continually increasing in methane reaching an excess of 96%, along with carbon dioxide decreasing to <1% and nitrogen to ~3%. The isotopic composition of all the gases was monitored. Methane carbon and hydrogen isotopic compositions remained stable throughout the test, while the carbon dioxide carbon became isotopically heavier. Nitrogen isotopic composition remained stable or became slightly isotopically depleted at the later phase of the test. These results imply that the produced methane was not isotopically fractionated, whereas carbon dioxide was fractionated becoming isotopically heavier at the end of each production phase. In addition, water samples were analyzed during the production phase documenting an increase in salinity.

Effect Of Substrates On The Fractionation Of Hydrogen Isotopes During Lipid-Biosynthesis By Haloarcula marismortui

NASA Astrophysics Data System (ADS)

Dirghangi, S. S.; Pagani, M.

2010-12-01

Lipids form an important class of proxies for paleoclimatological research, and hydrogen isotope ratios of lipids are being increasingly used for understanding changes in the hydrological system. Proper understanding of hydrogen isotope fractionation during lipid biosynthesis is therefore important and attention has been directed toward understanding the magnitude of hydrogen isotope fractionation that occurs during lipid biosynthesis in various organisms. Hydrogen isotope ratios of lipids depend on the hydrogen isotopic composition of the ambient water, hydrogen isotopic composition of NADPH used during biosynthesis, growth conditions, pathways of lipid biosynthesis, and substrates in the case of heterotrophic organisms. Recently it has been observed that NADPH contributes a significant part of the hydrogen in fatty acids synthesized by bacteria during heterotrophic growth (Zhang et al, 2009). As NADPH is formed by reduction of NADP+ during metabolism of substrates, different metabolic pathways form NADPH with different D/H ratios, which in turn results in variation in D/H ratios of lipids (Zhang et al, 2009). Therefore, substrates play a significant role in hydrogen isotopic compositions of lipids. For this study, we are investigating the effects of substrates on hydrogen isotope fractionation during biosynthesis of isoprenoidal lipids by heterotrophically growing halophilic archaea. Haloarcula marismortui is a halophilic archaea which synthesizes Archaeol (a diether lipid) and other isoprenoidal lipids. We have grown Haloarcula marismortui in pure cultures on three different substrates and are in the process of evaluating isotopic variability of Archaeol and other lipids associated with substrate and the D/H composition of ambient water. Our results will be helpful for a better understanding of hydrogen isotope fractionations during lipid synthesis by archaea. Also, halophilic archaea are the only source of archaeol in hypersaline environments. Therefore, our results will also indicate whether archaeol can be used as a proxy of ambient water hydrogen isotopic compositions in hypersaline environments.

A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis

NASA Technical Reports Server (NTRS)

Boehme, Susan E.

1993-01-01

A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.

Anatexis, hybridization and the modification of ancient crust: Mesozoic plutonism in the Old Woman Mountains area, California

USGS Publications Warehouse

Miller, C.F.; Wooden, J.L.

1994-01-01

A compositionally expanded array of granitic (s.l.) magmas intruded the > 2 Ga crust of the Old Woman Mountains area between 160 and 70 Ma. These magmas were emplaced near the eastern (inland) edge of the Jurassic/Cretaceous arcs of western North America, in an area where magma flux, especially during the Jurassic, was considerably lower than to the west. The Jurassic intrusives and over half of the Cretaceous intrusives are predominantly metaluminous and variable in composition; a major Cretaceous suite comprises only peraluminous monzogranite. Only the Jurassic intrusions show clear evidence for the presence of mafic liquids. All units, including the most mafic rocks, reveal isotopic evidence for a significant crustal component. However, none of the Mesozoic intrusives matches in isotopic composition either average pre-intrusion crust or any major unit of the exposed crust. Elemental inconsistencies also preclude closed system derivation from exposed crust. Emplacement of these magmas, which doubled the volume of the mid- to upper crust, did not dramatically change its elemental composition. It did, however, affect its Nd and especially Sr isotopic composition and modify some of the distinctive aspects of the elemental chemistry. We propose that Jurassic magmatism was open-system, with a major influx of mantle-derived mafic magma interacting strongly with the ancient crust. Mesozoic crustal thickening may have led to closed-system crustal melting by the Late Cretaceous, but the deep crust had been profoundly modified by earlier Mesozoic hybridization so that crustal melts did not simply reflect the original crustal composition. The clear evidence for a crustal component in magmas of the Old Woman Mountains area may not indicate any fundamental differences from the processes at work elsewhere in this or other magmatic arcs where the role of pre-existing crust is less certain. Rather, a compositionally distinctive, very old crust may simply have yielded a more readily identifiable crustal fingerprint. The same processes that were involved here-mafic magma influx, hybridization, and remelting of hybridized crust-are likely to be typical of arc settings. ?? 1994.

New technique for study on isotopic fractionation between sea water and foraminiferal growing processes

NASA Astrophysics Data System (ADS)

Cang, Shuxi; Shackleton, N. J.

1990-12-01

The stable isotopic δ18O and δ13C composition of foraminiferal shell calcite varies as a function of many factors including temperature and salinity. In order to understand and interpret the variations in the isotopic composition of foraminiferal shell calcite, research has been recently focused on the role of the “vital effects”. Our examination of the lamella structure of several recent planktonic foraminifera indicates that the secretion of sequential lamellae results in multiple lamillae on earlier chambers and a single lamella on the final chamber. We used a very simple procedure to separate the individual whole test of foraminifera into several chambers and measured the isotopic composition of each growth stage chamber. The results indicate that the stable isotopic composition (carbon and oxygen), particularly that of the last two chambers, of the foraminiferal test varies as a function of the individual growing process.

Hafnium isotope stratigraphy of ferromanganese crusts

PubMed

Lee; Halliday; Hein; Burton; Christensen; Gunther

1999-08-13

A Cenozoic record of hafnium isotopic compositions of central Pacific deep water has been obtained from two ferromanganese crusts. The crusts are separated by more than 3000 kilometers but display similar secular variations. Significant fluctuations in hafnium isotopic composition occurred in the Eocene and Oligocene, possibly related to direct advection from the Indian and Atlantic oceans. Hafnium isotopic compositions have remained approximately uniform for the past 20 million years, probably reflecting increased isolation of the central Pacific. The mechanisms responsible for the increase in (87)Sr/(86)Sr in seawater through the Cenozoic apparently had no effect on central Pacific deep-water hafnium.

Importance of depth and intensity of convection on the isotopic composition of water vapor as seen from IASI and TES δD observations

NASA Astrophysics Data System (ADS)

Lacour, Jean-Lionel; Risi, Camille; Worden, John; Clerbaux, Cathy; Coheur, Pierre-François

2018-01-01

We use tropical observations of the water vapor isotopic composition, derived from IASI and TES spaceborne measurements, to show that the isotopic composition of water vapor in the free troposphere is sensitive to both the depth and the intensity of convection. We find that for any given precipitation intensity, vapor associated with deep convection is isotopically depleted relative to vapor associated with shallow convection. The intensity of precipitation also plays a role as for any given depth of convection, the relative enrichment of water vapor decreases as the intensity of precipitation increases. Shallow convection, via the uplifting of enriched boundary layer air into the free troposphere and the convective detrainment, enriches the free troposphere. In contrast, deep convection is associated with processes that deplete the water vapor in the free troposphere, such as rain re-evaporation. The results of this study allow for a better identification of the parameters controlling the isotopic composition of the free troposphere and indicate that the isotopic composition of water vapor can be used to evaluate the relative contributions of shallow and deep convection in global models.

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

Spatial patterns of throughfall isotopic composition at the event and seasonal timescales

NASA Astrophysics Data System (ADS)

Allen, Scott T.; Keim, Richard F.; McDonnell, Jeffrey J.

2015-03-01

Spatial variability of throughfall isotopic composition in forests is indicative of complex processes occurring in the canopy and remains insufficiently understood to properly characterize precipitation inputs to the catchment water balance. Here we investigate variability of throughfall isotopic composition with the objectives: (1) to quantify the spatial variability in event-scale samples, (2) to determine if there are persistent controls over the variability and how these affect variability of seasonally accumulated throughfall, and (3) to analyze the distribution of measured throughfall isotopic composition associated with varying sampling regimes. We measured throughfall over two, three-month periods in western Oregon, USA under a Douglas-fir canopy. The mean spatial range of δ18O for each event was 1.6‰ and 1.2‰ through Fall 2009 (11 events) and Spring 2010 (7 events), respectively. However, the spatial pattern of isotopic composition was not temporally stable causing season-total throughfall to be less variable than event throughfall (1.0‰; range of cumulative δ18O for Fall 2009). Isotopic composition was not spatially autocorrelated and not explained by location relative to tree stems. Sampling error analysis for both field measurements and Monte-Carlo simulated datasets representing different sampling schemes revealed the standard deviation of differences from the true mean as high as 0.45‰ (δ18O) and 1.29‰ (d-excess). The magnitude of this isotopic variation suggests that small sample sizes are a source of substantial experimental error.

What controls silicon isotope fractionation during dissolution of diatom opal?

NASA Astrophysics Data System (ADS)

Wetzel, F.; de Souza, G. F.; Reynolds, B. C.

2014-04-01

The silicon isotope composition of opal frustules from photosynthesising diatoms is a promising tool for studying past changes in the marine silicon cycle, and indirectly that of carbon. Dissolution of this opal may be accompanied by silicon isotope fractionation that could disturb the pristine silicon isotope composition of diatom opal acquired in the surface ocean. It has previously been shown that dissolution of fresh and sediment trap diatom opal in seawater does fractionate silicon isotopes. However, as the mechanism of silicon isotope fractionation remained elusive, it is uncertain whether opal dissolution in general is associated with silicon isotope fractionation considering that opal chemistry and surface properties are spatially and temporally (i.e. opal of different age) diverse. In this study we dissolved sediment core diatom opal in 5 mM NaOH and found that this process is not associated with significant silicon isotope fractionation. Since no variability of the isotope effect was observed over a wide range of dissolution rates, we can rule out the suggestion that back-reactions had a significant influence on the net isotope effect. Similarly, we did not observe an impact of temperature, specific surface area, or degree of undersaturation on silicon isotope partitioning during dissolution, such that these can most likely also be ruled out as controlling factors. We discuss the potential impacts of the chemical composition of the dissolution medium and age of diatom opal on silicon isotope fractionation during dissolution. It appears most likely that the controlling mechanism of silicon isotope fractionation during dissolution is related to the reactivity, or potentially, aluminium content of the opal. Such a dependency would imply that silicon isotope fractionation during dissolution of diatom opal is spatially and temporally variable. However, since the isotope effects during dissolution are small, the silicon isotope composition of diatom opal appears to be robust against dissolution in the deep sea sedimentary environment.

Nitrogen isotopic composition of nitrate in the South China Sea: A clue to the origin of nitrogen

NASA Astrophysics Data System (ADS)

Yang, Z.; Chen, J.; Chen, M.; Ran, L.; Li, H.; Zhu, Y.; Wang, C.; Ji, Z.; Zhang, J.; Zhang, D.

2016-02-01

Nitrogen isotopic composition of water column nitrate was measured in the South China Sea to clarify the sources of nitrogen. The δ15NNO3 value in deep water (5.4±0.2‰) was higher than the average deep oceanic δ15NNO3 ( 5‰), and a weak δ15NNO3 maximum (5.9±0.2‰) was observed at 500 m depth, matching the salinity minimum. These indicated the intrusion of the North Pacific Water which carried nitrate with a high δ15NNO3 and showed a similar δ15NNO3 distribution profile with the South China Sea. The high N* (1.74±0.23 μmol/L) combined with the low δ15NNO3 (4.7±0.2‰) at 100 m depth indicated that N2 fixation (and possibly Atmospheric Deposition) introduces new N to the surface ocean. The distribution of δ15N values of nitrate, sinking particles and surface sediment suggest that laterally-advected sediments may be a source of nitrogen to the deep ocean.

Marine sulfur cycle constrained from isotope analysis of different forms of sulfur in the 3.2 Ga black shale (DXCL-DP) from Pilbara, Australia

NASA Astrophysics Data System (ADS)

Kobayashi, Y.; Yamaguchi, K. E.; Sakamoto, R.; Naraoka, H.; Kiyokawa, S.; Ikehara, M.; Ito, T.

2012-12-01

Co-evolution of early life and surface environment has been one of the most important events on Earth. Rise of atmospheric oxygen, or as known as GOE (Great Oxidation Event: e.g., Holland, 1994), has been widely believed to have occurred at around 2.4 billion years ago. But geological and geochemical evidence suggest possibility of much earlier (by hundreds of millions of years) existence of oxic atmosphere and oceans. In order to further investigate the mystery of biological and environmental evolution, we conducted continental drilling in northwestern Pilbara, Western. Australia, to obtain 3.2 billion-years-old least-metamorphosed drillcore black shale samples (DXCL-DP:Dixon Island - Cleaverville Drilling Project; Yamaguchi et al., 2009). Preliminary stable isotope analyses using these samples suggested that photosynthetic organisms produced organic matter (Hosoi et al., 2011), nitrogen fixing bacteria were intermittently active (Yamada et al., 2011), and sulfate-reducing bacteria were active in environment with a limited supply of sulfate (Sakamoto et al., 2011) in the 3.2 Ga ocean. Bulk S isotope compositions could only provide limited information on the biogeochemical cycling of sedimentary S, because it is normally present as different facies (acid-volatile sulfur: AVS, pyrite: FeS2, sulfate, organic sulfur: Sorg, and elemental sulfur: S0) that depend on physicochemical and biological conditions. Therefore, abundance and isotope ratios of these species possess very useful information on oceanic and diagenetic conditions such as redox state and microbiological activity. In order to constrain biogeochemical cycling of S in the 3.2 Ga ocean, we conducted sequential extraction analysis using the DXCL-DP black shales to obtain different S-bearing species and S isotopic analysis. Average S contents for each form of S-bearing species were: ΣS = 2.56 wt.%, AVS = 0.02 wt.%, pyrite = 1.61 wt.%, and sulfate = 0.57 wt%. Relationship between amounts of pyrite-S and organic C suggest presence of syngenetic pyrite (formed in water column) as well as diagenetic pyrite. Average S isotope compositions are: pyrite = 12.3±6.3 ‰, sulfate = 17.3 ± 7.1 ‰, and difference between them are up to as high as 16.8 ‰. These results show that depositional environment was probably close to the modern Black Sea, where sulfate-reducing bacteria are active in anaerobic water mass in semi-closed deep basin, with a limited supply of sulfate from the oxic surface ocean.

Characteristics of Martian Crustal Materials and Implications for Magmatic Assimilation: Preliminary Re-Os Isotope and Highly Siderophile Element Abundance Data for Nakhlites and Tissint

NASA Astrophysics Data System (ADS)

Mari, N.; Riches, A. J. V.; Hallis, L. J.; Lee, M. R.

2017-07-01

This project, for the first time, aims to integrate nakhlite Os-isotope compositions and HSE abundance data with S-isotope compositions for sample fractions for which textural information is constrained prior to destructive analyses.

Isotopic Composition of Barium in Single Presolar Silicon Carbide Grains

NASA Technical Reports Server (NTRS)

Savina, M. R.; Tripa, C. E.; Pellin, M. J.; Davis, A. M.; Clayton, R. N.; Lewis, R. S.; Amari, S.

2002-01-01

We have measured Ba isotope distributions in individual presolar SiC grains. We find that the Ba isotopic composition in mainstream SiC grains is consistent with models of nucleosynthesis in low to intermediate mass asymptotic giant branch (AGB) stars. Additional information is contained in the original extended abstract.

Soil drying effects on the carbon isotope composition of soil respiration

EPA Science Inventory

Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opp...

Stable isotopes of carbon and nitrogen as markers of dietary variation among sociocultural subgroups of Inuit in Greenland.

PubMed

Bjerregaard, Peter; Larsen, Christina V L; Dahl-Petersen, Inger K; Buchardt, Bjørn

2017-09-10

We assessed the use of stable isotopes of carbon and nitrogen as biomarkers for traditional versus store-bought food among the Inuit. Furthermore, we compared the isotope patterns among sociocultural population groups. As a part of a country-wide health survey in Greenland during 2005-2010, we analyzed the isotope composition of toenails from 1025 adult Inuit and meat of common species hunted for food. Information on diet and sociocultural variables was collected by interviews. Weighted by sex and place of residence to the total population of Inuit in Greenland, the average δ 13 C value in toenails was -20.2‰ and the δ 15 N value was 12.0‰ which are higher than in a general Danish omnivorous population. Both isotopes were significantly associated with other biomarkers of marine food and with results of a Food Frequency Questionnaire (FFQ). The percentage of marine food in the diet was estimated at 21% from the mean δ 13 C value, 25% from the mean δ 15 N value, and 23% from the FFQ. Nail samples for analysis of stable isotopes of carbon and nitrogen were convenient to collect during a large population health survey among the Inuit. Isotope enrichment levels showed statistically significant associations with other biomarkers for consumption of marine food and with results of an FFQ and were used to estimate the percentage of marine food in the diet. Isotope levels were significantly associated with a novel score of sociocultural transition. © 2017 Wiley Periodicals, Inc.

Iron isotope behavior during fluid/rock interaction in K-feldspar alteration zone - A model for pyrite in gold deposits from the Jiaodong Peninsula, East China

NASA Astrophysics Data System (ADS)

Zhu, Zhi-Yong; Jiang, Shao-Yong; Mathur, Ryan; Cook, Nigel J.; Yang, Tao; Wang, Meng; Ma, Liang; Ciobanu, Cristiana L.

2018-02-01

Mechanisms for Fe isotope fractionation in hydrothermal mineral deposits and in zones of associated K-feldspar alteration remain poorly constrained. We have analyzed a suite of bulk samples consisting of granite displaying K-feldspar alteration, Precambrian metamorphic rocks, and pyrite from gold deposits of the Jiaodong Peninsula, East China, by multi-collector inductively-coupled plasma mass spectrometry. Pyrites from disseminated (J-type) ores show a δ56Fe variation from +0.01 to +0.64‰, overlapping with the signature of the host granites (+0.08 to +0.39‰). In contrast, pyrites from quartz veins (L-type ores) show a wide range of Fe-isotopic composition from -0.78 to +0.79‰. Negative values are never seen in the J-type pyrites. The Fe isotope signature of the host granite with K-feldspar alteration is significantly heavier than that of the bulk silicate Earth. The Fe isotopic compositions of Precambrian metamorphic rocks across the district display a narrow range between -0.16‰ and +0.19‰, which is similar to most terrestrial rocks. Concentrations of major and trace elements in bulk samples were also determined, so as to evaluate any correlation between Fe isotope composition and degree of alteration. We note that during progressive K-feldspar alteration to rocks containing >70 wt% SiO2, >75 ppm Rb, and <1.2 wt% total Fe2O3, the Fe isotope composition of the granite changes systematically. The Fe isotope signature becomes heavier as the degree of alteration increases. The extremely light Fe isotopic compositions in L-type gold deposits may be explained by Rayleigh fractionation during pyrite precipitation in an open fracture system. We note that the sulfur isotopic compositions of pyrite in the two types of ores are also different. Pyrite from J-type ores has a systematically 3.5‰-higher δ34S value (11.2‰) than those of pyrite from the L-type ores (7.7‰). There is, however, no correlation between Fe and S isotope signatures. The isotopic fractionation of sulfur is used to constrain a change in the fO2 of the hydrothermal fluids from which pyrite precipitated. This work demonstrates that the Fe isotope composition of pyrite displays a significant response to the process of pyrite precipitation in hydrothermal systems, and that systematic fractionation of iron isotopes occurs during fluid/rock reaction in the K-feldspar alteration zone of the Linglong granite. The implications of the results are that processes of mineralization and associated fluid-rock interaction, which are ubiquitously observed in porphyry-style Cu-Au-Mo and other hydrothermal deposits, may be readily traceable using Fe isotopes.

Transboundary atmospheric lead pollution.

PubMed

Erel, Yigal; Axelrod, Tamar; Veron, Alain; Mahrer, Yitzak; Katsafados, Petros; Dayan, Uri

2002-08-01

A high-temporal resolution collection technique was applied to refine aerosol sampling in Jerusalem, Israel. Using stable lead isotopes, lead concentrations, synoptic data, and atmospheric modeling, we demonstrate that lead detected in the atmosphere of Jerusalem is not only anthropogenic lead of local origin but also lead emitted in other countries. Fifty-seven percent of the collected samples contained a nontrivial fraction of foreign atmospheric lead and had 206Pb/207Pb values which deviated from the local petrol-lead value (206Pb/207Pb = 1.113) by more than two standard deviations (0.016). Foreign 206Pb/207Pb values were recorded in Jerusalem on several occasions. The synoptic conditions on these dates and reported values of the isotopic composition of lead emitted in various countries around Israel suggest that the foreign lead was transported to Jerusalem from Egypt, Turkey, and East Europe. The average concentration of foreign atmospheric lead in Jerusalem was 23 +/- 17 ng/m3, similar to the average concentration of local atmospheric lead, 21 +/- 18 ng/ m3. Hence, the load of foreign atmospheric lead is similar to the load of local atmospheric lead in Jerusalem.

Inductively coupled plasma-mass spectrometric method for the determination of dissolved trace elements in natural water

USGS Publications Warehouse

Garbarino, J.R.; Taylor, Howard E.

1996-01-01

An inductively coupled plasma-mass spectrometry method was developed for the determination of dissolved Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sr, Tl, U, V, and Zn in natural waters. Detection limits are generally in the 50-100 picogram per milliliter (pg/mL) range, with the exception of As which is in the 1 microgram per liter (ug/L) range. Interferences associated with spectral overlap from concomitant isotopes or molecular ions and sample matrix composition have been identified. Procedures for interference correction and reduction related to isotope selection, instrumental operating conditions, and mathematical data processing techniques are described. Internal standards are used to minimize instrumental drift. The average analytical precision attainable for 5 times the detection limit is about 16 percent. The accuracy of the method was tested using a series of U.S. Geological Survey Standard Reference Water Standards (SWRS), National Research Council Canada Riverine Water Standard, and National Institute of Standards and Technology (NIST) Trace Elements in Water Standards. Average accuracies range from 90 to 110 percent of the published mean values.

Sr isotopic variations in Upper Proterozoic carbonates from Svalbard and East Greenland.

PubMed

Derry, L A; Keto, L S; Jacobsen, S B; Knoll, A H; Swett, K

1989-01-01

We report initial 87Sr/86Sr values from an Upper Proterozoic carbonate succession from Svalbard and East Greenland. This succession, now tectonically separated into three sequences, is thick, relatively continuous, and well preserved. The relative ages of the samples from within the basin are well constrained by litho-, bio-, and chemostratigraphic techniques. The data from this study and related data from the literature are used to construct a curve of 87Sr/86Sr for Upper Proterozoic seawater. The new data reported in this study substantially improve the isotopic record of Sr in seawater for the period between 650 and 800 Ma. The data indicate that delta 87Sr values of seawater were variable but low (delta 87Sr approximately -500 to -250) between 900 and 650 Ma, and rose rapidly to approximately +30 by 600 Ma. The range of variation of delta 87Sr in seawater during the Riphean-Vendian exceeds the entire range of delta 87Sr in seawater during the Phanerozoic. While variation in the average isotopic composition of Sr delivered to the oceans by rivers can account for some of the observed range, changes in the ratio of submarine hydrothermal flux to river water (continental) flux are responsible for the large variation in seawater Sr isotopic composition. Changes in the continental flux of Sr to the oceans can be related to tectonic factors. Large changes in the hydrothermal flux to river water flux ratio indicated by the data could have significant consequences for the chemistry of the ocean-atmosphere system.

Uptake and mobility of uranium in black oaks: implications for biomonitoring depleted uranium-contaminated groundwater.

PubMed

Edmands, J D; Brabander, D J; Coleman, D S

2001-08-01

In a preliminary study, the uptake and the mobility of uranium (U) by black oak trees (Quercus velutina) were assessed by measuring the isotopic composition of tree rings in two mature oak trees in a heavy metal contaminated bog in Concord, MA. The bog is adjacent to a nuclear industrial facility that has been processing depleted uranium (DU) since 1959. Over the past 40 years, DU has been leaking from an onsite holding basin and cooling pond down gradient to the bog where the oaks are located. Because DU has no source outside the nuclear industry, contamination from the industrial facility is readily discernable from uptake of natural U by measuring isotopic compositions. Isotope ratio analysis confirms the occurrence of DU in bark, sapwood and heartwood tree rings dating back to 1937, pre-dating the introduction of DU at the site by at least 20 years. Isotope dilution analysis indicates high concentrations of U (>3 ppb) in sapwood that drop rapidly to relatively constant concentrations (0.3-0.4 ppb) in heartwood. These data indicate that once incorporated into tree cells, U is mobile, possibly by diffusion through the tree wood. Concentrations of U in sapwood are approximately equal to average U concentrations in groundwater onsite over the past 10 years, suggesting that oak trees can be used as present-day bioindicators of U-contaminated groundwater. We suggest that regional sampling of oak bark and sapwood is a reasonable, inexpensive alternative to drilling wells to monitor shallow groundwater U contamination.

Site-specific 13C content by quantitative isotopic 13C nuclear magnetic resonance spectrometry: a pilot inter-laboratory study.

PubMed

Chaintreau, Alain; Fieber, Wolfgang; Sommer, Horst; Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro; Pagelot, Alain; Moskau, Detlef; Moreno, Aitor; Schleucher, Jürgen; Reniero, Fabiano; Holland, Margaret; Guillou, Claude; Silvestre, Virginie; Akoka, Serge; Remaud, Gérald S

2013-07-25

Isotopic (13)C NMR spectrometry, which is able to measure intra-molecular (13)C composition, is of emerging demand because of the new information provided by the (13)C site-specific content of a given molecule. A systematic evaluation of instrumental behaviour is of importance to envisage isotopic (13)C NMR as a routine tool. This paper describes the first collaborative study of intra-molecular (13)C composition by NMR. The main goals of the ring test were to establish intra- and inter-variability of the spectrometer response. Eight instruments with different configuration were retained for the exercise on the basis of a qualification test. Reproducibility at the natural abundance of isotopic (13)C NMR was then assessed on vanillin from three different origins associated with specific δ (13)Ci profiles. The standard deviation was, on average, between 0.9 and 1.2‰ for intra-variability. The highest standard deviation for inter-variability was 2.1‰. This is significantly higher than the internal precision but could be considered good in respect of a first ring test on a new analytical method. The standard deviation of δ (13)Ci in vanillin was not homogeneous over the eight carbons, with no trend either for the carbon position or for the configuration of the spectrometer. However, since the repeatability for each instrument was satisfactory, correction factors for each carbon in vanillin could be calculated to harmonize the results. Copyright © 2013 Elsevier B.V. All rights reserved.

Continental sedimentary processes decouple Nd and Hf isotopes

NASA Astrophysics Data System (ADS)

Garçon, Marion; Chauvel, Catherine; France-Lanord, Christian; Huyghe, Pascale; Lavé, Jérôme

2013-11-01

The neodymium and hafnium isotopic compositions of most crustal and mantle rocks correlate to form the "Terrestrial Array". However, it is now well established that whereas coarse detrital sediments follow this trend, fine-grained oceanic sediments have high Hf ratios relative to their Nd isotopic ratios. It remains uncertain whether this "decoupling" of the two isotopic systems only occurs in the oceanic environment or if it is induced by sedimentary processes in continental settings. In this study, the hafnium and neodymium isotopic compositions of sediments in large rivers is expressly used to constrain the behavior of the two isotopic systems during erosion and sediment transport from continent to ocean. We report major and trace element concentrations together with Nd and Hf isotopic compositions of bedloads, suspended loads and river banks from the Ganges River and its tributaries draining the Himalayan Range i.e. the Karnali, the Narayani, the Kosi and the Marsyandi Rivers. The sample set includes sediments sampled within the Himalayan Range in Nepal, at the Himalayan mountain front, and also downstream on the floodplain and at the outflow of the Ganges in Bangladesh. Results show that hydrodynamic sorting of minerals explains the entire Hf isotopic range, i.e. more than 10 εHf units, observed in the river sediments but does not affect the Nd isotopic composition. Bedloads and bank sediments have systematically lower εHf values than suspended loads sampled at the same location. Coarse-grained sediments lie below or on the Terrestrial Array in an εHf vs. εNd diagram. In contrast, fine-grained sediments, including most of the suspended loads, deviate from the Terrestrial Array toward higher εHf relative to their εNd, as is the case for oceanic terrigenous clays. The observed Nd-Hf decoupling is explained by mineralogical sorting processes that enrich bottom sediments in coarse and dense minerals, including unradiogenic zircons, while surface sediments are enriched in fine material with radiogenic Hf signatures. The data also show that Nd-Hf isotopic decoupling increases with sediment transport in the floodplain to reach its maximum at the river mouth. This implies that the Nd-Hf isotopic decoupling observed in worldwide oceanic clays and river sediments is likely to have the same origin. Finally, we estimated the Nd-Hf isotopic composition of the present-day mantle if oceanic sediments had never been subducted and conclude that the addition of oceanic sediments with their anomalous Nd-Hf isotopic compositions has slowly shifted the composition of the Earth's mantle towards more radiogenic Hf values through time.

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study

NASA Astrophysics Data System (ADS)

Lauwens, Sara; Costas-Rodríguez, Marta; van Vlierberghe, Hans; Vanhaecke, Frank

2016-07-01

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient’s condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about -0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ65Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure.

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study

PubMed Central

Lauwens, Sara; Costas-Rodríguez, Marta; Van Vlierberghe, Hans; Vanhaecke, Frank

2016-01-01

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient’s condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about −0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ65Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure. PMID:27468898

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study.

PubMed

Lauwens, Sara; Costas-Rodríguez, Marta; Van Vlierberghe, Hans; Vanhaecke, Frank

2016-07-29

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient's condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about -0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ(65)Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure.

Deep Mantle Origin for the DUPAL Anomaly?

NASA Astrophysics Data System (ADS)

Ingle, S.; Weis, D.

2002-12-01

Twenty years after the discovery of the Dupal Anomaly, its origin remains a geochemical and geophysical enigma. This anomaly is associated with the Southern Hemisphere oceanic mantle and is recognized by basalts with geochemical characteristics such as low 206Pb/204Pb and high 87Sr/86Sr. Both mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) are affected, despite originating from melting at different depths and of different mantle sources. We compile geochemical data for both MORB and OIB from the three major oceans to help constrain the physical distribution and chemical composition of the Dupal Anomaly. There is a clear decrease in 206Pb/204Pb and an increase in 87Sr/86Sr with more southerly latitude for Indian MORB and OIB; these correlations are less obvious in the Atlantic and non-existent in the Pacific. The average* 143Nd/144Nd for Pacific and Atlantic OIB is 0.5129, but is lower for Indian OIB (0.5128). Interestingly, Pacific, Atlantic and Indian OIB all have 176Hf/177Hf averages of 0.2830. Indian MORB also record this phenomenon of low Nd with normal Hf isotopic compositions (Chauvel and Blichert-Toft, EPSL, 2001). Hf isotopes appear, therefore, to be a valid isotopic proxy for measuring the presence and magnitude of the Dupal Anomaly at specific locations. Wen (EPSL, 2001) reported a low-velocity layer at the D'' boundary beneath the Indian Ocean from which the Dupal Anomaly may originate. This hypothesis may be consistent with our compilations demonstrating that the long-lived Dupal Anomaly does not appear to be either mixing efficiently into the upper mantle or spreading to other ocean basins through time. We suggest that the Dupal source could be continually tapped by upwelling Indian Ocean mantle plumes. Plumes would then emplace pockets of Dupal material into the upper mantle and other ascending plumes might further disperse this material into the shallow asthenosphere. This could explain both the presence of the Dupal signature in MORB and OIB and the geochemical similarities between some Indian Ocean mantle plumes, such as Kerguelen, and the Dupal signature. * To avoid sampling biases, data for each ocean island (or group) are averaged and these values are used to calculate the average for each ocean.

Evaluating Crustal Contamination Effects on the Lithophile Trace Element Budget of Shergottites

NASA Technical Reports Server (NTRS)

Brandon, A. D.; Ferdous, J.; Peslier, A. H.

2017-01-01

The origin of the incompatible trace element (ITE) enriched compositions of shergottites has been a point of contention for decades [1-2]. Two scenarios have been proposed, the first is that enriched shergottite compositions reflect an ITE-enriched mantle source, whereas in the second, the ITE enrichment reflects crustal contamination of mantle-derived parent magmas. Evidence supporting the first scenario is that the ITE-enriched shergottite compositions are consistent with the outcomes of magma ocean crystallization [3], and that Os-Nd isotope relationships for shergottites cannot be explained by realistic crustal contamination models [4]. In contrast, Cl and S isotopes are consistent with shergottite magmas interacting with Mars crust [5,6], and ITE-enriched olivine-hosted melt inclusions and interstitial glass are found in depleted shergottite Yamato 980459 [7]. These findings indicate that some level of crustal interaction occurred but the question of whether ITE-enrichments in some bulk shergottites reflect crustal contamination remains open. Recently, a Mars crustal breccia meteorite has been found, NWA 7034 and its paired stones, that is our best analogue to an average of Mars ancient crust [8-10]. This allows for better constraints on crustal contamination of shergottite magmas. We modeled magma-crust mixing and assimilation-fractional crystallization (AFC) using ITE-depleted shergottite compositions and bulk NWA 7034 and its clasts as end-members. The results of these models indicate that crustal contamination can only explain the ITE-enriched compositions of some bulk shergottites under unusual circumstances. It is thus likely that the shergottite range of compositions reflects primarily mantle sources.

Clumped Isotope Composition of Cold-Water Corals: A Role for Vital Effects?

NASA Astrophysics Data System (ADS)

Spooner, P.; Guo, W.; Robinson, L. F.

2014-12-01

Measurements on a set of cold-water corals (mainly Desmophyllum dianthus) have suggested that their clumped isotope composition could serve as a promising proxy for reconstructing paleocean temperatures. Such measurements have also offered support for certain isotope models of coral calcification. However, there are differences in the clumped isotope compositions between warm-water and cold-water corals, suggesting that different kinds of corals could have differences in their biocalcification processes. In order to understand the systematics of clumped isotope variations in cold-water corals more fully, we present clumped isotope data from a range of cold-water coral species from the tropical Atlantic and the Southern Ocean.Our samples were either collected live or recently dead (14C ages < 1,000 yrs) with associated temperature data. They include a total of 11 solitary corals and 1 colonial coral from the Atlantic, and 8 solitary corals from the Southern Ocean. The data indicate that coral clumped isotope systematics may be more complicated than previously thought. For example, for the genus Caryophyllia we observe significant variations in clumped isotope compositions for corals which grew at the same temperature with an apparent negative correlation between Δ47 and δ18O, different to patterns previously observed in Desmophyllum. These results indicate that existing isotope models of biocalcification may not apply equally well to all corals. Clumped isotope vital effects may be present in certain cold-water corals as they are in warm-water corals, complicating the use of this paleoclimate proxy.

An ion microprobe study of individual zircon phenocrysts from voluminous post-caldera rhyolites of the Yellowstone caldera

NASA Astrophysics Data System (ADS)

Watts, K. E.; Bindeman, I. N.; Schmitt, A. K.

2010-12-01

Following the formation of the Yellowstone caldera from the 640 ka supereruption of the Lava Creek Tuff (LCT), a voluminous episode of post-caldera volcanism filled the caldera with >600 km3 of low-δ18O rhyolite. Such low-δ18O signatures require remelting of 100s of km3 of hydrothermally altered (18O-depleted) rock in the shallow crust. We present a high resolution oxygen isotope and geochronology (U-Th and U-Pb) study of individual zircon crystals from seven of these voluminous post-caldera rhyolites in order to elucidate their genesis. Oxygen isotope and geochronology analyses of zircon were performed with an ion microprobe that enabled us to doubly fingerprint 25-30 µm diameter spots. Host groundmass glasses and coexisting quartz were analyzed in bulk for oxygen isotopes by laser fluorination. We find that zircons from the youngest (200-80 ka) post-caldera rhyolites have oxygen isotopic compositions that are in equilibrium with low-δ18O host groundmass glasses and quartz and are unzoned in oxygen and U-Th age. This finding is in contrast to prior work on older (500-250 ka) post-caldera rhyolites, which exhibit isotopic disequilibria and age zoning, including the presence of clearly inherited zircon cores. Average U-Th crystallization ages and δ18O zircon values for Pitchstone Plateau flow (81±7 ka, 2.8±0.2‰), West Yellowstone flow (118±8 ka, 2.8±0.1‰), Elephant Back flow (175±22 ka, 2.7±0.2‰) and Tuff of Bluff Point (176±20 ka, 2.7±0.1‰) are overlapping or nearly overlapping in age and identical in oxygen isotope composition within uncertainty (2 SE). New U-Pb geochronology and oxygen isotope data for the North Biscuit Basin flow establish that it has an age (188±33 ka) and δ18O signature (2.8±0.2‰) that is distinctive of the youngest post-caldera rhyolites. Conversely, the South Biscuit Basin flow has a heterogeneous zircon population with ages that range from 550-250 ka. In this unit, older and larger (200-400 µm) zircons have more disparity in δ18O signatures (-0.2-3.6‰) while the younger and smaller (<100-200 µm) zircons have δ18O signatures (2.6±0.3‰) that are identical to the youngest post-caldera rhyolites. Our results are consistent with derivation of the youngest post-caldera rhyolites from a common magma reservoir that was assembled from heterogeneous pockets of low-δ18O melt. The magma was homogenized prior to eruption, erasing evidence of batch assembly in all but the oldest South Biscuit Basin unit. An important new finding of this study is that the newly defined post-LCT East Biscuit Basin flow is the oldest (U-Pb age of 761±66 ka) and most primitive (70 wt% SiO2) rhyolite to erupt from within the Yellowstone caldera. Unlike the youngest post-caldera rhyolites, the average δ18O composition of East Biscuit Basin zircons (4.4±0.3‰) is significantly higher and out of equilibrium with the host groundmass glass (δ18O=1.0‰). Its formation requires remelting of hydrothermally altered LCT and pre-LCT subcaldera rocks that retain oxygen isotopic evidence of inherited zircon phenocrysts.

Petrology and geochemistry of the Tasse mantle xenoliths of the Canadian Cordillera: A record of Archean to Quaternary mantle growth, metasomatism, removal, and melting

NASA Astrophysics Data System (ADS)

Polat, Ali; Frei, Robert; Longstaffe, Fred J.; Thorkelson, Derek J.; Friedman, Eyal

2018-07-01

Mantle xenoliths hosted by the Quaternary Tasse alkaline basalts in the Canadian Cordillera, southeastern British Columbia, are mostly spinel lherzolite originating from subcontinental lithospheric mantle. The xenoliths contain abundant feldspar veins, melt pockets and spongy clinopyroxene, recording extensive alkaline metasomatism and partial melting. Feldspar occurs as veins and interstitial crystal in melt pockets. Melt pockets occur mainly at triple junctions, along grain boundaries, and consist mainly of olivine, cpx, opx and spinel surrounded by interstitial feldspar. The Nd, Sr and Pb isotopic compositions of the xenoliths indicate that their sources are characterized by variable mixtures of depleted MORB mantle and EM1 and EM2 mantle components. Large variations in εNd values (-8.2 to +9.6) and Nd depleted mantle model ages (TDM = 66 to 3380 Ma) are consistent with multiple sources and melt extraction events, and long-term (>3300 Ma) isolation of some source regions from the convecting mantle. Samples with Archean and Paleoproterozoic Nd model ages are interpreted as either have been derived from relict Laurentian mantle pieces beneath the Cordillera or have been eroded from the root of the Laurentian craton to the east and transported to the base of the Cordilleran lithosphere by edge-driven convection currents. The oxygen isotope compositions of the xenoliths (average δ18O = +5.1 ± 0.5‰) are similar to those of depleted mantle. The average δ18O values of olivine (+5.0 ± 0.2‰), opx (+5.9 ± 0.6‰), cpx (+6.0 ± 0.6‰) and spinel (+4.5 ± 0.2‰) are similar to mantle values. Large fractionations for olivine-opx, olivine-cpx and opx-cpx pairs, however, reflect disequilibrium stemming from metasomatism and partial melting. Whole-rock trace element, Nd, Sr, Pb and O isotope compositions of the xenoliths and host alkaline basalts indicate different mantle sources for these two suites of rocks. The xenoliths were derived from shallow lithospheric sources, whereas the alkaline basalts originated from a deeper asthenospheric mantle source.

Anthropogenic imprints on nitrogen and oxygen isotopic composition of precipitation nitrate in a nitrogen-polluted city in southern China

NASA Astrophysics Data System (ADS)

Fang, Y. T.; Koba, K.; Wang, X. M.; Wen, D. Z.; Li, J.; Takebayashi, Y.; Liu, X. Y.; Yoh, M.

2010-09-01

Nitric acid (HNO3) or nitrate (NO3-) is the dominant sink for reactive nitrogen oxides (NOx = NO + NO2) in the atmosphere. In many Chinese cities, HNO3 is becoming a significant contributor to acid deposition. In the present study, we used the denitrifier method to measure nitrogen (N) and oxygen (O) isotopic composition of NO3- in 113 precipitation samples collected from Guangzhou City in southern China over a two-year period (2008 and 2009). We attempted to better understand the spatial and seasonal variability of atmospheric NOx sources and the NO3- formation pathways in this N-polluted city in the Pearl River Delta region. The δ15N values of NO3- (versus air N2) ranged from -4.9 to +10.1‰, and averaged +3.9‰ in 2008 and +3.3‰ in 2009. Positive δ15N values were observed throughout the year, indicating the anthropogenic contribution of NOx emissions, particularly from coal combustion. Different seasonal patterns of δ15N-NO3- were observed between 2008 and 2009, which might reflect different human activities associated with the global financial crisis and the intensive preparations for the 16th Asian Games. Nitrate δ18O values (versus Vienna Standard Mean Ocean Water) varied from +33.4 to +86.5‰ (average +65.0‰ and +67.0‰ in 2008 and 2009, respectively), a range being lower than those reported for high altitude and polar areas. Several δ18O values were observed lower than the expected minimum of 50‰ at our study site. This was likely caused by the reaction of NO with peroxy radicals; peroxy radicals can compete with O3 to convert NO to NO2, thereby donate O atoms with much lower δ18O value than that of O3 to atmospheric NO3-. Our results highlight that the influence of human activities on atmospheric chemistry can be recorded by the N and O isotopic composition of atmospheric NO3- in a N-polluted city.

Anthropogenic imprints on nitrogen and oxygen isotopic composition of precipitation nitrate in a nitrogen-polluted city in southern China

NASA Astrophysics Data System (ADS)

Fang, Y. T.; Koba, K.; Wang, X. M.; Wen, D. Z.; Li, J.; Takebayashi, Y.; Liu, X. Y.; Yoh, M.

2011-02-01

Nitric acid (HNO3) or nitrate (NO3-) is the dominant sink for reactive nitrogen oxides (NOx = NO + NO2) in the atmosphere. In many Chinese cities, HNO3 is becoming a significant contributor to acid deposition. In the present study, we measured nitrogen (N) and oxygen (O) isotopic composition of NO3- in 113 precipitation samples collected from Guangzhou City in southern China over a two-year period (2008 and 2009). We attempted to better understand the spatial and seasonal variability of atmospheric NOx sources and the NO3- formation pathways in this N-polluted city in the Pearl River Delta region. The δ15N values of NO3- (versus air N2) ranged from -4.9 to +10.1‰, and averaged +3.9‰ in 2008 and +3.3‰ in 2009. Positive δ15N values were observed throughout the year, indicating the anthropogenic contribution of NOx emissions, particularly from coal combustion. Different seasonal patterns of δ15N-NO3- were observed between 2008 and 2009, which might reflect different human activities associated with the global financial crisis and the intensive preparations for the 16th Asian Games. Nitrate δ18O values (versus Vienna Standard Mean Ocean Water) varied from +33.4 to +86.5‰ (average +65.0‰ and +67.0‰ in 2008 and 2009, respectively), a range being lower than those reported for high latitude and polar areas. Sixteen percent of δ18O values was observed lower than the expected minimum of +55‰ at our study site. This was likely caused by the reaction of NO with peroxy radicals; peroxy radicals can compete with O3 to convert NO to NO2, thereby donate O atoms with much lower δ18O value than that of O3 to atmospheric NO3-. Our results highlight that the influence of human activities on atmospheric chemistry can be recorded by the N and O isotopic composition of atmospheric NO3- in a N-polluted city.

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.

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.

FE and MG Isotopic Analyses of Isotopically Unusual Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Messenger, S.; Ito, M.; Rahman, Z.

2011-01-01

Interstellar and circumstellar silicate grains are thought to be Mg-rich and Fe-poor, based on astronomical observations and equilibrium condensation models of silicate dust formation in stellar outflows. On the other hand, presolar silicates isolated from meteorites have surprisingly high Fe contents and few Mg-rich grains are observed. The high Fe contents in meteoritic presolar silicates may indicate they formed by a non-equilibrium condensation process. Alternatively, the Fe in the stardust grains could have been acquired during parent body alteration. The origin of Fe in presolar silicates may be deduced from its isotopic composition. Thus far, Fe isotopic measurements of presolar silicates are limited to the Fe-54/Fe-56 ratios of 14 grains. Only two slight anomalies (albeit solar within error) were observed. However, these measurements suffered from contamination of Fe from the adjacent meteorite matrix, which diluted any isotopic anomalies. We have isolated four presolar silicates having unusual O isotopic compositions by focused ion beam (FIB) milling and obtained their undiluted Mg and Fe isotopic compositions. These compositions help to identify the grains stellar sources and to determine the source of Fe in the grains.