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.

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

Lead isotope studies of the Guerrero composite terrane, west-central Mexico: implications for ore genesis

NASA Astrophysics Data System (ADS)

Potra, Adriana; Macfarlane, Andrew W.

2014-01-01

New thermal ionization mass spectrometry and multi-collector inductively coupled plasma mass spectrometry Pb isotope analyses of three Cenozoic ores from the La Verde porphyry copper deposit located in the Zihuatanejo-Huetamo subterrane of the Guerrero composite terrane are presented and the metal sources are evaluated. Lead isotope ratios of 3 Cenozoic ores from the El Malacate and La Esmeralda porphyry copper deposits located in the Zihuatanejo-Huetamo subterrane and of 14 ores from the Zimapan and La Negra skarn deposits from the adjoining Sierra Madre terrane are also presented to look for systematic differences in the lead isotope trends and ore metal sources among the proposed exotic tectonostratigraphic terranes of southern Mexico. Comparison among the isotopic signatures of ores from the Sierra Madre terrane and distinct subterranes of the Guerrero terrane supports the idea that there is no direct correlation between the distinct suspect terranes of Mexico and the isotopic signatures of the associated Cenozoic ores. Rather, these Pb isotope patterns are interpreted to reflect increasing crustal contribution to mantle-derived magmas as the arc advanced eastward onto a progressively thicker continental crust. The lead isotope trend observed in Cenozoic ores is not recognized in the ores from Mesozoic volcanogenic massive sulfide and sedimentary exhalative deposits. The Mesozoic ores formed prior to the amalgamation of the Guerrero composite terrane to the continental margin, which took place during the Late Cretaceous, in intraoceanic island arc and intracontinental marginal basin settings, while the Tertiary deposits formed after this event in a continental arc setting. Lead isotope ratios of the Mesozoic and Cenozoic ores appear to reflect these differences in tectonic setting of ore formation. Most Pb isotope values of ores from the La Verde deposit (206Pb/204Pb = 18.674-18.719) are less radiogenic than those of the host igneous rocks, but plot within the field defined by the Huetamo Sequence, suggesting that these ores may also contain metals from the sedimentary rocks. The Pb isotope ratios of ore samples from the Zimapan deposit (206Pb/204Pb = 18.771-18.848) are substantially higher than the whole-rock Pb isotope compositions of the basement rocks. The similarity of ore Pb to igneous rock Pb in the Zimapan district (206Pb/204Pb = 18.800-18.968) may indicate that the proximal source of ore metals in the hydrothermal system was the igneous activity.

Modeling secular changes in seawater chemistry accurately requires inclusion of environmental controls on low-temperature, off-axis, hydrothermal fluxes

NASA Astrophysics Data System (ADS)

Coogan, L. A.; Dosso, S. E.; Higgins, J. A.

2014-12-01

There are sharp rises in the Sr- and Li-isotopic composition of seawater at the Eocene-Oligocene boundary that are generally thought to be associated with Himalayan uplift and associated climatic changes and continental weathering variability. In modeling such data the norm is to hold the chemical fluxes associated with off-axis hydrothermal circulation through the oceanic crust constant while varying the river fluxes (and/or isotopic ratios). There is, however, no a priori reason to assume the chemical fluxes (or isotopic compositions) associated with off-axis hydrothermal systems should stay constant. Instead, changing environmental conditions (e.g. seawater composition and bottom water temperature) will lead to changes in these fluxes. An alternative model to explain the sharp rise in the Sr- and Li-isotopic composition of seawater at the Eocene-Oligocene boundary is cooling of the deep ocean. Decreased reaction rates in the oceanic crust, due to decreasing temperature, can be shown to lead to a decrease in the flux of unradiogenic Sr into the ocean. The magnitude matches, within uncertainty, that required to explain the increase in seawater Sr-isotopic composition [Coogan and Dosso, in review]. The story for Li is more uncertain. Two factors may lead to smaller effective fractionation factors between seawater and the (large) Li sink in the oceanic crust when bottom water is warmer: (i) higher temperature will decrease the isotopic fractionation factor; (ii) the more extensive fluid-rock reaction in the ocean crust when bottom water is warmer will make Li uptake by the oceanic crust more efficient. All other things being equal this will lead to a lower Li content of seawater. In turn, a lower Li content in seawater will mean that for a given Li-uptake rate by the crust the effective fractionation factor is smaller, due to Rayleigh distillation of Li-isotopes during fluid-rock reaction in the oceanic crust. In combination these factors predict a significant (many per mil), but poorly constrained, increase in the Li-isotopic composition of the ocean due to cooling bottom water. Models of many geochemical species, including carbon [Coogan and Gillis, 2013], should include environmentally dependent fluxes from off-axis hydrothermal systems.

Lead isotopic fingerprinting of aerosols to characterize the sources of atmospheric lead in an industrial city of India

NASA Astrophysics Data System (ADS)

Sen, Indra S.; Bizimis, Michael; Tripathi, Sachchida Nand; Paul, Debajyoti

2016-03-01

Anthropogenic Pb in the environment is primarily sourced from combustion of fossil fuel and high-temperature industries such as smelters. Identifying the sources and pathways of anthropogenic Pb in the environment is important because Pb toxicity is known to have adverse effects on human health. Pb pollution sources for America, Europe, and China are well documented. However, sources of atmospheric Pb are unknown in India, particularly after leaded gasoline was phased out in 2000. India has a developing economy with a rapidly emerging automobile and high temperature industry, and anthropogenic Pb emission is expected to rise in the next decade. In this study, we report on the Pb-isotope compositions and trace metal ratios of airborne particulates collected in Kanpur, a large city in northern part of India. The study shows that the PM10 aerosols had elevated concentration of Cd, Pb, Zn, As, and Cu in the Kanpur area, however their concentrations are well below the United States Environmental Protection Agency chronic exposure limit. Lead isotopic and trace metal data reveal industrial emission as the plausible source of anthropogenic Pb in the atmosphere in Kanpur. However, Pb isotopic compositions of potential source end-members are required to fully evaluate Pb contamination in India over time. This is the first study that characterizes the isotopic composition of atmospheric Pb in an Indian city after leaded gasoline was phased out by 2000.

Lead mobilization during tectonic reactivation of the western Baltic Shield

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

Romer, R.L.; Wright, J.E.

Lead isotope data from sulfide deposits of the western part of the Baltic Shield define mixing lines in the [sup 206]Pb/[sup 204]Pb-[sup 207]Pb/[sup 204]Pb diagram. Lead from two types of sulfide deposits have been investigated: (1) Exhalative and volcanogenic deposits that are syngenetic with their host rocks; and (2) vein deposits. The syngenetic deposits locally show a very wide range of lead isotopic compositions that reflect a variable addition of highly radiogenic lead, while the vein deposits, although they have radiogenic lead isotopic compositions, exhibit only limited isotopic variations. In different provinces of the shield, both types of deposits fallmore » on the same lead mixing array. The slope of the lead mixing lines varies as a function of the age of basement rocks and the age of the tectonic event which produced the lead mobilization and therefore relates the source rock age with the age of lead mobilization. Calculated mixing ages fall into several short time periods that correspond either to orogenic events or to major phases of continental rifting. The orogenic events are the ca 360--430 Ma Caledonian, ca 900--1100 Ma Sveconorwegian, and the ca 1800--1900 Ma Svecofennian orogenic cycles. The rifting events correspond to the formation of the ca 280 Ma Oslo rift and the Ordovician (ca 450 Ma) graben system in the area of the present Gulf of Bothnia. Each mixing age indicates that lead was mobilized, probably as a consequence of mild thermal disturbances, and that the crust was permeable to lead migration. The data show that the geographic distribution of sulfide deposits with highly radiogenic lead isotopic compositions coincides with old graben systems, orogenic belts, and orogenic forelands on the Baltic Shield. The ages of vein deposits and their geographic distribution demonstrate multiple tectonic reactivation of the interior of the Baltic Shield in response to orogenic events at its margin. 68 refs., 6 refs., 4 tabs.« less

Lead isotopic composition of trinitite melt glass: evidence for the presence of Canadian industrial lead in the first atomic weapon test.

PubMed

Bellucci, Jeremy J; Simonetti, Antonio; Wallace, Christine; Koeman, Elizabeth C; Burns, Peter C

2013-08-06

The Pb isotopic compositions for 51 spots of melt glass in 11 samples of trinitite have been determined by laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Trinitite glass yields a large range of Pb isotopic compositions (i.e., (206)Pb/(204)Pb = 17.08-19.04), which reflect mixing between industrial Pb from materials used in the Trinity test and natural geologic components. Areas within trinitite melt glass containing high concentrations of both Cu and Pb, which are derived from the bomb and blast site-related components, were used for delineating the Pb isotopic composition corresponding to the anthropogenic Pb component. Comparison between the isotopic composition estimated here for the industrial Pb used in the Trinity test and those from known Pb deposits worldwide indicates close agreement with ore from the Buchans mine (Newfoundland, Canada). The Buchans mine was active during the time of the Trinity test and was operated by the American Smelting and Refining Company, which could have provided the Pb used in the test. The industrial Pb used in the Trinity test materials is not documented in the literature (or declassified) but could have been present in bricks, solder, pigs, or some other anthropogenic component related to the experiment.

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.

Statistical clumped isotope signatures

PubMed Central

Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.

2016-01-01

High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

High-precision Pb isotopic measurements of teeth and environmental samples from Sofia (Bulgaria): insights for regional lead sources and possible pathways to the human body

NASA Astrophysics Data System (ADS)

Kamenov, George D.

2008-08-01

High-precision Pb isotopic measurements on teeth and possible sources in a given area can provide important insights for the lead (Pb) sources and pathways in the human body. Pb isotopic analyses on soils from the area of Sofia, Bulgaria show that Pb is contributed by three end-members represented by two natural sources and leaded gasoline. Sequential leaching experiments reveal that the alumosilicate fraction of the soils is mainly controlled by natural Pb derived from two mountain massifs bordering the city. Around 1/3 to a half of the Pb in the soil leachates, however, can be explained by contamination from leaded gasoline. Contemporary teeth from Sofia residents show very similar Pb isotopic compositions to the soil leachates, also indicating that around 1/3 to a half of the Pb can be explained by derivation from leaded gasoline. The remarkable isotopic similarities between the teeth and the most labile fractions of the local soils suggest that the lead can be derived from the latter. Pb incorporation in the human body via soil-plant-human or soil-plant-animal-human chains is unlikely due to the fact that no significant farming occurs in the city area. The isotopic compositions of the local soil labile fractions can be used as approximation of the bioaccessible lead for humans. Considering all possible scenarios it appears that soil and/or soil-born dust inhalation and/or ingestion is the most probable pathway for incorporation of local soil lead in the local population. The high-precision Pb isotope data presented in this work indicate that apparently the local soil is what plays major role in the human Pb exposure.

Stable lead isotopes reveal a natural source of high lead concentrations to gasoline-contaminated groundwater

USGS Publications Warehouse

Landmeyer, J.E.; Bradley, P.M.; Bullen, T.D.

2003-01-01

Concentrations of total lead as high as 1,600 ??g/L were detected in gasoline-contaminated and uncontaminated groundwater at three gasoline-release sites in South Carolina. Total lead concentrations were highest in turbid groundwater samples from gasoline-contaminated and uncontaminated wells, whereas lower turbidity groundwater samples (collected using low-flow methods) had lower total lead concentrations. Dissolved lead concentrations in all wells sampled, however, were less than 15 ??g total lead/L, the current United States Environmental Protection Agency (US EPA) maximum contaminant level (MCL). Because many total lead concentrations exceeded the MCL, the source of lead to the groundwater system at two of the three sites was investigated using a stable lead isotope ratio approach. Plots of the stable isotope ratios of lead (Pb) in groundwater as 207Pb/206Pb versus 208Pb/206Pb, and 208Pb/204Pb versus 206Pb/204Pb were similar to ratios characteristic of lead-based minerals in local rocks of the southeastern US, and were not similar to the stable lead isotopes ratios characteristic of distant lead ore deposits such as Broken Hill, Australia, used to produce tetraethyl lead in gasoline products prior to its phase-out and ban in the United States. Moreover, the isotopic composition of dissolved lead was equivalent to the isotopic composition of total lead in turbid samples collected from the same well, suggesting that the majority of the lead detected in the groundwater samples was associated with sediment particulates of indigenous aquifer material, rather than lead associated with spilled leaded gasoline. The results of this investigation indicate that (1) lead detected at some gasoline-release sites may be derived from the local aquifer material, rather than the gasoline release, and consequently may affect site-specific remediation goals; (2) non-low flow groundwater sampling methods, such as a disposable bailer, may result in turbid groundwater samples and high total lead concentrations, and; (3) stable lead isotopes can be used to clarify the source of lead detected above permissible levels in gasoline-contaminated groundwater systems.

DISSOLUTION AND ANALYSIS OF YELLOWCAKE COMPONENTS FOR FINGERPRINTING UOC SOURCES

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

Hexel, Cole R; Bostick, Debra A; Kennedy, Angel K

2012-01-01

There are a number of chemical and physical parameters that might be used to help elucidate the ore body from which uranium ore concentrate (UOC) was derived. It is the variation in the concentration and isotopic composition of these components that can provide information as to the identity of the ore body from which the UOC was mined and the type of subsequent processing that has been undertaken. Oak Ridge National Laboratory (ORNL) in collaboration with Lawrence Livermore and Los Alamos National Laboratories is surveying ore characteristics of yellowcake samples from known geologic origin. The data sets are being incorporatedmore » into a national database to help in sourcing interdicted material, as well as aid in safeguards and nonproliferation activities. Geologic age and attributes from chemical processing are site-specific. Isotopic abundances of lead, neodymium, and strontium provide insight into the provenance of geologic location of ore material. Variations in lead isotopes are due to the radioactive decay of uranium in the ore. Likewise, neodymium isotopic abundances are skewed due to the radiogenic decay of samarium. Rubidium decay similarly alters the isotopic signature of strontium isotopic composition in ores. This paper will discuss the chemical processing of yellowcake performed at ORNL. Variations in lead, neodymium, and strontium isotopic abundances are being analyzed in UOC from two geologic sources. Chemical separation and instrumental protocols will be summarized. The data will be correlated with chemical signatures (such as elemental composition, uranium, carbon, and nitrogen isotopic content) to demonstrate the utility of principal component and cluster analyses to aid in the determination of UOC provenance.« less

Lead isotopes in the western North Atlantic: Transient tracers of pollutant lead inputs

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

Veron, A.J.; Church, T.M.; Flegal, A.R.

1998-08-01

In the early 1980s, Patterson and colleagues demonstrated that most lead in oceanic surface waters had an anthropogenic origin. Their discovery occurred during the phasing out of leaded gasoline in North America initiated in the previous decade. The corresponding decrease in anthropogenic lead emissions, verified by Pb/{sup 210}Pb ratios, accounted for the systematic decline in lead concentrations in surface waters of the western Sargasso Sea. Subsequent changes in anthropogenic lead inputs to the western Sargasso Sea surface waters have been documented by measurements of lead concentrations, isotopic compositions ({sup 206}Pb/{sup 207}Pb, {sup 208}Pb/{sup 206}Pb), and Pb/{sup 210}Pb ratios in precipitationmore » and seawater for the period of 1981 to 1994. These data indicate the easterly trade winds are now the primary source of atmospheric lead in Bermuda, and they confirm that the decline of lead concentrations in the North Atlantic is associated with the phasing out of leaded gasoline in North America and western Europe over the past decade. Moreover, temporal variations in the relative contribution of industrial lead inputs from the two sides of the North Atlantic over that period can be quantified based on differences in their isotopic composition. The transient character of those isotopic signatures also allows calculations of pollutant lead penetration rates into the mixed layer and upper thermocline of the western Sargasso Sea.« less

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.

Calcium and Titanium Isotope Fractionation in CAIS: Tracers of Condensation and Inheritance in the Early Solar Protoplanetary Disk

NASA Technical Reports Server (NTRS)

Simon, J. I.; Jordan, M. K.; Tappa, M. J.; Kohl, I. E.; Young, E. D.

2016-01-01

The chemical and isotopic compositions of calcium-aluminum-rich inclusions (CAIs) can be used to understand the conditions present in the protoplantary disk where they formed. The isotopic compositions of these early-formed nebular materials are largely controlled by chemical volatility. The isotopic effects of evaporation/sublimation, which are well explained by both theory and experimental work, lead to enrichments of the heavy isotopes that are often exhibited by the moderately refractory elements Mg and Si. Less well understood are the isotopic effects of condensation, which limits our ability to determine whether a CAI is a primary condensate and/or retains any evidence of its primordial formation history.

Lead-203 as a label for radioimaging

DOEpatents

Srivastava, Suresh C.; Meinken, George E.

1990-01-01

A radiopharmaceutical composition comprising a radioactive isotope of lead (Pb-203) in combination with a pharmaceutical or an antibody or antibody fragment and a bifunctional chelating agent. These compositions are especially useful in the imaging and diagnosis of tumors and tumor metastases.

Lead-203 as a label for radioimaging

DOEpatents

Srivastava, Suresh C.; Meinken, George E.

1990-02-06

A radiopharmaceutical composition comprising a radioactive isotope of lead (Pb-203) in combination with a pharmaceutical or an antibody or antibody fragment and a bifunctional chelating agent. These compositions are especially useful in the imaging and diagnosis of tumors and tumor metastases.

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 spatio-temporal pattern identification in urban microenvironments using moss bags and the Kohonen self-organizing maps

NASA Astrophysics Data System (ADS)

Deljanin, Isidora; Antanasijević, Davor; Vuković, Gordana; Urošević, Mira Aničić; Tomašević, Milica; Perić-Grujić, Aleksandra; Ristić, Mirjana

2015-09-01

The first investigation of the use of the Kohonen self-organizing map (SOM) which includes lead concentration and its isotopic composition in moss bags to assess the spatial and temporal patterns of lead in the urban microenvironments is presented in this paper. The moss bags experiment was carried out during 2011 in the city tunnel in Belgrade, as well as in street canyons at different heights (4, 8 and 16 m) and in public garages. The moss bags were exposed for 5 and 10 weeks. The results revealed that the 10 weeks period represents suitable exposure time in screening Pb isotopic composition in active biomonitoring analysis. The obtained results showed that the SOM analysis, by recognizing slight differences among moss samples regarding exposure time, horizontal and vertical spatial distribution, with both, contribution of stable lead isotopes and Pb concentration, could be recommended in biomonitoring analysis of lead distribution in urban microenvironments.

The Use of Lead Isotope and Rare Earth Element Geochemistry for Forensic Geographic Provenancing

NASA Astrophysics Data System (ADS)

Carey, A.; Darrah, T.; Harrold, Z.; Prutsman-Pfeiffer, J.; Poreda, R.

2008-12-01

Lead isotope and rare earth element composition of modern human bones are analyzed to explore their utility for geographical provenancing. DNA analysis is the standard for identification of individuals. DNA analysis requires a DNA match for comparison. Thus, DNA analysis is of limited use in cases involving unknown remains. Trace elements are incorporated into bones and teeth during biomineralization, recording the characteristics of an individual's geochemical environment. Teeth form during adolescence, recording the geochemical environment of an individual's youth. Bones remodel throughout an individual's lifetime. Bones consist of two types of bone tissue (cortical and trabecular) that remodel at different rates, recording the geochemical environment at the time of biomineralization. Cortical bone tissue, forming the outer surface of bones, is dense, hard tissue that remodels in 25-30 yrs. Conversely, trabecular bone tissue, the inner cavity of bones, is low density, porous and remodels in 2-5 years. Thus, analyzing teeth and both bone tissues allows for the development of a geographical time line capable of tracking immigration patterns through time instead of only an individual's youth. Geochemical isotopic techniques (Sr, O, C, N) have been used for geographical provenancing in physical anthropology. The isotopic values of Sr, C, O, N are predominantly a function of soil compositions in areas where food is grown or water is consumed. Application of these provenancing techniques has become difficult as an individual's diet may reflect the isotopic composition of foods obtained at the local grocer as opposed to local soil compositions. Thus, we explore the use of REEs and Pb isotopes for geographical provenancing. Pb and REEs are likely more reliable indicators of modern geographical location as their composition are high in bio-available sources such as local soils, atmospheric aerosols, and dust as opposed to Sr, C, O, N that are controlled by food and drinking water. Lead isotope and REE analysis of trabecular and cortical bone tissue of 60 femoral heads resected during hip replacement surgery at the Univ. of Roch. Medical Center were analyzed by a combination of TIMS and ICP-MS. Results show that Pb compositions are consistent with local soil with variable inputs from known environmental sources. Several samples demonstrate inputs from known environmental sources (e.g. Mississippi Valley ore) that was used in paint, solder, and US gasoline. Additionally, results suggest bioincorporation of Pb with isotopic composition consistent with that observed for Canadian gasoline aerosols. Immigrants included in the study show Pb compositions distinctly different than local residents.

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.

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

U-Pb systematics in iron meteorites - Uniformity of primordial lead

NASA Astrophysics Data System (ADS)

Gopel, C.; Manhes, G.; Allegre, C. J.

1985-08-01

Pb isotopic compositions and U-Pb abundances were determined in the metal phase of six iron meteorites: Canyon Diablo IA, Toluca IA, Odessa IA, Youndegin IA, Deport IA, and Mundrabilla An. Prior to complete dissolution, samples were subjected to a series of leachings and partial dissolutions. Isotopic compositions and abundances of the etched Pb indicate a contamination by terrestrial Pb which is attributable to previous cutting of the meteorite. Pb isotopic compositions measured in the decontaminated samples are identical within 0.2 percent and essentially confirm the primordial Pb value defined by Tatsumoto et al. (1973). These data invalidate more radiogenic Pb isotopic compositions published for iron meteorites, which are the result of terrestrial Pb contamination introduced mainly by analytical procedure. The results of this study support the idea of a solar nebula which was isotopically homogeneous for Pb 4.55 Ga ago. The new upper limit for U-abundance in iron meteorites, 0.001 ppb, is in agreement with its expected thermodynamic solubility in the metal phase.

A young Moon-forming giant impact at 70-110 million years accompanied by late-stage mixing, core formation and degassing of the Earth.

PubMed

Halliday, Alex N

2008-11-28

New W isotope data for lunar metals demonstrate that the Moon formed late in isotopic equilibrium with the bulk silicate Earth (BSE). On this basis, lunar Sr isotope data are used to define the former composition of the Earth and hence the Rb-Sr age of the Moon, which is 4.48+/-0.02Ga, or 70-110Ma (million years) after the start of the Solar System. This age is significantly later than had been deduced from W isotopes based on model assumptions or isotopic effects now known to be cosmogenic. The Sr age is in excellent agreement with earlier estimates based on the time of lunar Pb loss and the age of the early lunar crust (4.46+/-0.04Ga). Similar ages for the BSE are recorded by xenon and lead-lead, providing evidence of catastrophic terrestrial degassing, atmospheric blow-off and significant late core formation accompanying the ca 100Ma giant impact. Agreement between the age of the Moon based on the Earth's Rb/Sr and the lead-lead age of the Moon is consistent with no major losses of moderately volatile elements from the Earth during the giant impact. The W isotopic composition of the BSE can be explained by end member models of (i) gradual accretion with a mean life of roughly 35Ma or (ii) rapid growth with a mean life of roughly 10Ma, followed by a significant hiatus prior to the giant impact. The former assumes that approximately 60 per cent of the incoming metal from impactors is added directly to the core during accretion. The latter includes complete mixing of all the impactor material into the BSE during accretion. The identical W isotopic composition of the Moon and the BSE limits the amount of material that can be added as a late veneer to the Earth after the giant impact to less than 0.3+/-0.3 per cent of ordinary chondrite or less than 0.5+/-0.6 per cent CI carbonaceous chondrite based on their known W isotopic compositions. Neither of these on their own is sufficient to explain the inventories of both refractory siderophiles such as platinum group elements and rhenium, and volatiles such as sulphur, carbon and water.

The Balmat-Edwards zinc-lead deposits-synsedimentary ore from Mississippi valley-type fluids.

USGS Publications Warehouse

Whelan, J.F.; Rye, R.O.; Delorraine, W.

1984-01-01

The Balmat-Edwards Zn-Pb district in New York is in Mid-Proterozoic Grenville marbles. Tabular to podiform, generally conformable massive sphalerite-galena orebodies occur at various horizons in the approx 1 km-thick marbles. Metamorphism obscured or obliterated most primary characteristics, whose reconstruction is attempted through detailed S, C, and O isotope studies of the Fowler orebody, and trace element and S isotope studies of sphalerite concentrates and composite ore samples from 22 orebodies. Sulphur isotope data reflect equilibration at near peak metamorphism with some indication of re-equilibration during retrograde metamorphism. The carbon and oxygen isotope composition of gangue carbonates suggests derivation from the host marbles. The oxygen isotope composition of gangue quartz is compatible with a chert origin or metamorphism-equilibration with other minerals. Sulphur and lead isotopes and sulphide mineralogy suggests that the ore fluids were evolved basin brines, chemically like those responsible for Mississippi Valley-type deposits. The large stratigraphic span (> 600 m) of the Balmat orebodies may be due to basin dewatering of million-year intervals. Stratigraphically increasing 34S values of evaporite-anhydrite are postulated to record hydrothermal events and to imply bacterial sulphate reduction on an unusually large scale. Such a stratigraphic increase may be a general exploration guide where sediment-hosted exhalative deposits or Mississippi Valley-type deposits occur.-G.J.N.

Changes in the lead isotopic composition of blood, diet and air in Australia over a decade: Globalization and implications for future isotopic studies

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

Gulson, Brian; Mizon, Karen; Korsch, Michael

2006-01-15

Source apportionment in biological or environmental samples using the lead isotope method, where there are diverse sources of lead, relies on a significant difference between the isotopic composition in the target media and the sources. Because of the unique isotopic composition of Australian lead, source apportionment has been relatively successful in the past. Over the period of a decade, the {sup 206}Pb/{sup 204}Pb ratio for Australian (mainly female) adults has shown an increase from a geometric mean of 16.8-17.3. Associated with this increase, there has been a decrease in mean blood lead concentration from 4.7 to 2.3 {mu}g/dL, or aboutmore » 5% per year, similar to that observed in other countries. Lead in air, which up until 2000 was derived largely from the continued use of leaded gasoline, showed an overall increase in the {sup 206}Pb/{sup 204}Pb ratio during 1993-2000 from 16.5 to 17.2. Since 1998 the levels of lead in air were less than 0.2 {mu}g/m{sup 3} and would contribute negligibly to blood lead. Over the 10-year period, the {sup 206}Pb/{sup 204}Pb ratio in diet, based mainly on quarterly 6-day duplicate diets, increased from 16.9 to 18.3. The lead concentration in diet showed a small decrease from 8.7 to 6.4 {mu}g Pb/kg although the daily intake increased markedly from 7.4 to 13.9 {mu}g Pb/day during the latter part of the decade probably reflecting differences in demographics. The changes in blood lead from sources such as lead in bone or soil or dust is not dominant because of the low {sup 206}Pb/{sup 204}Pb ratios in these media. Unless there are other sources not identified and analysed for these adults, it would appear that in spite of our earlier conclusions to the contrary, diet does make an overall contribution to blood lead, and this is certainly the case for specific individuals. Certain population groups from south Asia, south-east Asia, the Middle East and Europe (e.g. UK) are unsuitable for some studies as their isotopic ratios in blood are converging towards the increasing Australian values. The increases in blood {sup 206}Pb/{sup 204}Pb ratio combined with globalization, which has resulted in the increases in {sup 206}Pb/{sup 204}Pb ratio for diet, means that isotopic studies undertaken with a high degree of certainty of outcomes over a decade ago, are now considerably more difficult, not only in Australia but also in other countries where the isotopic differences are even less than in Australia.« less

The potential source of lead in the Permian Kupferschiefer bed of Europe and some selected Paleozoic mineral deposits in the Federal Republic of Germany

USGS Publications Warehouse

Wedepohl, K.H.; Delevaux, M.H.; Doe, B.R.

1978-01-01

New lead isotopic compositions have been measured for Paleozoic bedded and vein ore deposits of Europe by the high precision thermal emission (triple filament) technique. Eleven samples have been analyzed from the Upper Permian Kupferschiefer bed with representatives from Poland to England, three samples from the Middle Devonian Rammelsberg deposit and one from the Middle Devonian Meggen deposit, both of which are conformable ore lenses and are in the Federal Republic of Germany (FRG); and also two vein deposits from the FRG were analyzed, from Ramsbeck in Devonian host rocks and from Grund in Carboniferous host rocks. For Kupferschiefer bed samples from Germany, the mineralization is of variable lead isotopic composition and appears to have been derived about 250 m.y. ago from 1700 m.y. old sources, or detritus of this age, in Paleozoic sedimentary rocks. Samples from England, Holland, and Poland have different isotopic characteristics from the German samples, indicative of significantly different source material (perhaps older). The isotopic variability of the samples from the Kupferschiefer bed in Germany probably favors the lead containing waters coming from shoreward (where poor mixing is to be expected) rather than basinward (where better mixing is likely) directions. The data thus support the interpretation of the metal source already given by Wedepohl in 1964. Data on samples from Rammelsberg and Meggen tend to be slightly less radiogenic than for the Kupferschiefer, about the amount expected if the leads were all derived from the same source material but 100 to 150 m.y. apart in time. The vein galena from Ramsbeck is similar to that from Rammelsberg conformable ore lenses, both in rocks of Devonian age; vein galena from Grund in Upper Carboniferous country rocks is similar to some bedded Kupferschiefer mineralization in Permian rocks, as if the lead composition was formed at about the same time and from similar source material as the bedded deposits. Although heat has played a more significant role in the formation of some of these deposits (veins and Rammelsberg-Meggen) than in others (Kupferschiefer), there is no indication of radically different sources for the lead, all apparently coming from sedimentary source material containing Precambrian detritus. One feldspar lead sample from the Brocken-Oker Granite is not the same in isotopic composition as any of the ores analyzed. ?? 1978 Springer-Verlag.

Asian anthropogenic lead contamination in the North Pacific Ocean as evidenced by stable lead isotopic compositions

NASA Astrophysics Data System (ADS)

Zurbrick, Cheryl M.

This dissertation work determined the changing scope of lead (Pb) contamination in the North Pacific Ocean since the phase-out of leaded gasoline in most of the world. Chapters 1 and 2 consisted of validating our method for determining Pb concentrations and isotopic compositions in seawater. Chapter 3 established a baseline of Pb isotopic compositions (PbICs) in the western and central North Pacific in 2002. This was an ideal time to establish such a baseline because China had recently (mid-2000) ceased their use of leaded gasoline and simultaneously began consuming increasingly large amounts of coal, known to have relatively high Pb concentrations. We found subsurface waters were contaminated with Asian industrial Pb, predominantly Chinese coal emissions. In contrast, the abyssal waters were a mix of Asian industrial Pb and background (i.e., natural) Pb. Chapter 4 revisited the western and central North Pacific in 2009 -- 2011 to determine what, if any, changes had occurred in this short time period. We found that Pb in subsurface and abyssal waters of the western North Pacific were similar to Chinese aerosols. Such a large change in the PbICs of abyssal water in 9 years was unanticipated and attributed to the relatively large flux of particle-bound Pb from the euphotic zone to the deep ocean, which was in isotopic equilibrium with the reservoir of dissolved Pb. In contrast, the central North Pacific abyssal water PbICs were similar to values previously reported because of the relatively lower particulate export. Based on comparisons to baseline PbIC data, we determined that abyssal waters in the western and central North Pacific would be isotopically indistinguishable from surface waters in the next three decades. Sources of Pb to coastal California waters were reevaluated in Chapter 5. Prior studies had found that surface waters of the California Current System (CCS) were isotopically consistent with both Asian industrial Pb and US leaded gasoline, still in use at that point in time. In 2010 and 2011, we found that surface and subsurface waters of the CCS were isotopically similar to Asian industrial emissions. However, remobilized US gasoline Pb from sediments in the San Francisco Bay, California, were accumulating in the "mud belt" on the continental shelf and changing the isotopic composition of overlying waters. During periods of intense upwelling, this historic Pb was brought to the surface of the water. However, the much larger quantity of Pb from Asian industrial emissions made the isotopic composition of Pb from historic US gasoline unidentifiable in off-shore waters. A secondary research focus of this dissertation was to improve my own teaching abilities. Chapter 6 explored the intersection of system thinking and aquatic toxicology in undergraduate education. Among a wealth of information, I found that group concept mapping was no more useful to student learning than the same activity done individually. This was due to poor implementation of team learning strategies by me and inadequate time for students to adjust to non-traditional instruction methodologies.

Preliminary lead isotope investigations of brine from the Red Sea, Galena from the Kingdom of Saudi Arabia, and galena from United Arab Republic (Egypt)

USGS Publications Warehouse

Delevaux, M.H.; Doe, B.R.; Brown, G.F.

1967-01-01

The isotopic composition of lead in Red Sea chloride brine containing 0.5 ppm Pb is found to be similar to that of some Cenozoic ore leads such as galena at Rabigh in Saudi Arabia that may have formed during mineralization accompanying Tertiary rifting. Bir Ranga galena in Miocene sediments from United Arab Republic (Egypt) is also isotopically similar to lead in Red Sea brine. The chlorine brine must be considered a possible mineralizing fluid. Lead isotopes show promise for use in mineral prospect evaluation in that galena from Samrah is isotopically similar to that from Mahd adh Dhahab, which has been the only ore producer in Saudi Arabia since 1945. Drilling at Samrah does indicate a possible economic mineralization. The lead isotope data coupled with available geologic knowledge and geochronometry are used to tentatively divide the ore prospects of the Kingdom of Saudi Arabia into relative categories of mineralization age. Two Mesozoic and Cenozoic mineralizations are distinguished on the basis of a 207Pb/204Pb difference; an early Paleozoic mineralization grouping is outlined; and a late Precambrian mineralization period is suggested. ?? 1967.

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.

Stable isotope signatures and element stoichiometry of Fucus vesiculosus as indicators for environmental conditions in the Kiel Bight, Baltic Sea

NASA Astrophysics Data System (ADS)

Winde, Vera; Mahler, Annika; Voss, Maren; Böttcher, Michael E.

2014-05-01

In the frame of the BMBF project BIOACID II we aim for an understanding of the natural distribution and variation of isotopic composition and C-N-S stoichiometry in Fucus vesiculosus growing around the coast line of the Kiel fjord (part of the Kiel bight). Environmental conditions (aquatic chemistry, temperature, salinity) were monitored, too. Some changes in aquatic chemistry are related to stress factors like human activity (e.g., waste input) and further factors leading to specific changes in the composition of Fucus vesiculosus. Sampling was carried out at different stations at the west and east coast of the Kiel Fjord. For each sampling station the aquatic chemistry (TA, pH, salinity, d13C(DIC), main and trace elements and nutrients) as well as the composition of the Fucus organic tissues (stoichiometry and stable isotope composition of carbon, nitrogen) are analysed. The Fucus tissue was sampled in three size classes (small, medium, large). It is shown, that Fucus vesiculosus indicates clear differences in the N contents and stable isotopes between the west and the east site of the Kiel Fjord. Stable nitrogen isotope signatures in Fucus vesiculosus, are useful proxies to identify the influence factors in the Fucus habitat. From the data it is obtained that the influence of human activity (wastewater treatment plant, harbour), small stream and drainage channels, which flow from the near coastal area into the bight, leads to different Fucus vesiculosus compositions. In future work, it is intended to extend the investigation to trace element signatures to further estimate environmental impacts.

Lead isotopes reveal bilateral asymmetry and vertical continuity in the Hawaiian mantle plume.

PubMed

Abouchami, W; Hofmann, A W; Galer, S J G; Frey, F A; Eisele, J; Feigenson, M

2005-04-14

The two parallel chains of Hawaiian volcanoes ('Loa' and 'Kea') are known to have statistically different but overlapping radiogenic isotope characteristics. This has been explained by a model of a concentrically zoned mantle plume, where the Kea chain preferentially samples a more peripheral portion of the plume. Using high-precision lead isotope data for both centrally and peripherally located volcanoes, we show here that the two trends have very little compositional overlap and instead reveal bilateral, non-concentric plume zones, probably derived from the plume source in the mantle. On a smaller scale, along the Kea chain, there are isotopic differences between the youngest lavas from the Mauna Kea and Kilauea volcanoes, but the 550-thousand-year-old Mauna Kea lavas are isotopically identical to Kilauea lavas, consistent with Mauna Kea's position relative to the plume, which was then similar to that of present-day Kilauea. We therefore conclude that narrow (less than 50 kilometres wide) compositional streaks, as well as the larger-scale bilateral zonation, are vertically continuous over tens to hundreds of kilometres within the plume.

Sr isotopic composition of Afar volcanics and its implication for mantle evolution

NASA Astrophysics Data System (ADS)

Barberi, F.; Civetta, L.; Varet, J.

1980-10-01

Investigations of Rb-Sr systematics of basalts from the Afar depression (Ethiopia) indicate the presence of a heterogeneous mantle source region. The Sr isotopic compositions of the basalts from the Afar axial and transverse ranges identify source regions which are enriched in LIL elements and radiogenic Sr (axial ranges) and others which are relatively depleted (transverse ranges). Sr isotopic composition of basalts from the Red Sea, Gulf of Aden and Gulf of Tadjoura, which range from 0.70300 to 0.70340 are also reported and compared with the more radiogenic Afar region, which is characterized by 87Sr/ 86Sr ranging from 0.70328 to 0.70410. Available geochemical and isotopic data suggest that a relation exists between magma composition and the advancement of the rifting process through progressive lithosphere attenuation leading to continental break-up. However, the petrogenetic process is not simple and probably implies a vertically zoned mantle beneath the Afar region. Sr isotopic evidence suggests that the vertically zoned mantle is more radiogenic and enriched in LIL elements in its upper part.

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.

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

Facchetti, S.

Many studies were dedicated to the evaluation of the impact of automotive lead on the environment and to the assessment of its absorption in the human population. They can be subdivided into two groups, those based on changes of air and blood lead concentrations and those based on changes of air and blood lead isotopic compositions. According to various authors, 50-66% of the lead added to petrol is mobilized in the atmosphere, while most of the remainder adheres to the walls of the exhaust system from which it is expelled by mechanical and thermal shocks in the forms of easilymore » sedimented particles. The fraction directly emitted by engine exhaust fumes is found in the form of fine particles, which can be transferred a long way from the emitting sources. However important the contribution of petrol lead to the total airborne lead may be, our knowledge does not permit a straightforward calculation of the percentage of petrol lead in total blood lead, which of course can also originate from other sources (e.g., industrial, natural). To evaluate this percentage in 1973, the idea of the Isotopic Lead Experiment (ILE project) was conceived to label, on a regional scale, petrol with a nonradioactive lead of an isotopic composition sufficiently different from that of background lead and sufficiently stable in time. This Account summarizes the main results obtained by the ILE project.« less

Tracing fetal and childhood exposure to lead using isotope analysis of deciduous teeth

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

Shepherd, Thomas J.; British Geological Survey, Keyworth, Nottingham; Dirks, Wendy

We report progress in using the isotopic composition and concentration of Pb in the dentine and enamel of deciduous teeth to provide a high resolution time frame of exposure to Pb during fetal development and early childhood. Isotope measurements (total Pb and {sup 208}Pb/{sup 206}Pb, {sup 207}Pb/{sup 206}Pb ratios) were acquired by laser ablation inductively coupled mass spectrometry at contiguous 100 micron intervals across thin sections of the teeth; from the outer enamel surface to the pulp cavity. Teeth samples (n=10) were selected from two cohorts of children, aged 5–8 years, living in NE England. By integrating the isotope datamore » with histological analysis of the teeth, using the daily incremental lines in dentine, we were able to assign true estimated ages to each ablation point (first 2–3 years for molars, first 1–2 years for incisors+pre-natal growth). Significant differences were observed in the isotope composition and concentration of Pb between children, reflecting differences in the timing and sources of exposure during early childhood. Those born in 2000, after the withdrawal of leaded petrol in 1999, have the lowest dentine Pb levels (<0.2 µg Pb/g) with {sup 208}Pb/{sup 206}Pb (mean ±2σ: 2.126–2.079) {sup 208}Pb/{sup 206}Pb (mean ±2σ: 0.879–0.856) ratios that correlate very closely with modern day Western European industrial aerosols (PM{sub 10}, PM{sub 2.5}) suggesting that diffuse airborne pollution was probably the primary source and exposure pathway. Legacy lead, if present, is insignificant. For those born in 1997, dentine lead levels are typically higher (>0.4 µgPb/g) with {sup 208}Pb/{sup 206}Pb (mean ±2σ: 2.145–2.117) {sup 208}Pb/{sup 206}Pb (mean ±2σ: 0.898–0.882) ratios that can be modelled as a binary mix between industrial aerosols and leaded petrol emissions. Short duration, high intensity exposure events (1–2 months) were readily identified, together with evidence that dentine provides a good proxy for childhood changes in the isotope composition of blood Pb. Our pilot study confirms that laser ablation Pb isotope analysis of deciduous teeth, when carried out in conjunction with histological analysis, permits a reconstruction of the timing, duration and source of exposure to Pb during early childhood. With further development, this approach has the potential to study larger cohorts and appraise environments where the levels of exposure to Pb are much higher. - Highlights: • Reconstructing a high resolution chronology of early childhood exposure to lead. • Combined laser ablation lead isotope – histological analysis of children's teeth. • Using dentine to recover information on the intensity, duration and source of lead. • Importance of industrial airborne lead pollution in a post-leaded petrol era.« less

The isotopic composition of uranium and lead in Allende inclusions and meteoritic phosphates

NASA Technical Reports Server (NTRS)

Chen, J. H.; Wasserburg, G. J.

1981-01-01

The isotopic compositions of uranium and lead in Ca-Al-rich inclusions from the Allende chondrite and in whitlockite from the St. Severin chondrite and the Angra dos Reis achondrite are reported. Isoptopic analysis of acid soluble fractions of the Allende inclusions and the meteoritic whitlockite, which show isotopic anomalies in other elements, reveals U-235/U-238 ratios from 1/137.6 to 1/138.3, within 20 per mil of normal terrestrial U abundances. The Pb isotopic compositions of five coarse-grained Allende inclusions give a mean Pb-207/Pb-206 model age of 4.559 + or - 0.015 AE, in agreement with the U results. Pb isotope ratios of two fine-grained inclusions and a coarse-grained inclusion with strong mass fractionation and some nonlinear isotopic anomalies indicate that the U-Pb systems of these inclusions have evolved differently from the rest of Allende. Th/U abundance ratios in the Allende inclusions and meteoritic phosphate are found to range from 3.8 to 96, presumably indicating an optimal case for Cm/U fractionation, although the normal U concentrations do not support claims of abundant live Cm-247 or Cm-247/U-238 fractionation at the time of meteorite formation, in contrast to previous results. A limiting Cm-247/U-235 ratio of 0.004 at the time of meteorite formation is calculated which implies that the last major r process contribution at the protosolar nebula was approximately 100 million years prior to Al-26 formation and injection.

Investigation of off-site airborne transport of lead from a superfund removal action site using lead isotope ratios and concentrations

USGS Publications Warehouse

Pribil, Michael J.; Maddaloni, Mark A.; Staiger, Kimberly; Wilson, Eric; Magriples, Nick; Ali, Mustafa; Santella, Dennis

2014-01-01

Lead (Pb) concentration and Pb isotopic composition of surface and subsurface soil samples were used to investigate the potential for off-site air transport of Pb from a former white Pb processing facility to neighboring residential homes in a six block area on Staten Island, NY. Surface and subsurface soil samples collected on the Jewett White Pb site were found to range from 1.122 to 1.138 for 206Pb/207Pb and 2.393 to 2.411 for 208Pb/207Pb. The off-site surface soil samples collected from residential backyards, train trestle, near site grass patches and background areas varied from 1.144 to 1.196 for 206Pb/207Pb and 2.427 to 2.464 for 208Pb/207Pb. Two soil samples collected along Richmond Terrace, where Jewett site soils accumulated after major rain events, varied from 1.136 to 1.147 for 206Pb/207Pb and 2.407 to 2.419 for 208Pb/207Pb. Lead concentration for on-site surface soil samples ranged from 450 to 8000 ug/g, on-site subsurface soil samples ranged from 90,000 to 240,000 ug/g and off-site samples varied from 380 to 3500 ug/g. Lead concentration and isotopic composition for the Staten Island off-site samples were similar to previously published data for other northeastern US cities and reflect re-suspension and re-mobilization of local accumulated Pb. The considerable differences in both the Pb isotopic composition and Pb concentration of on-site and off-site samples resulted in the ability to geochemically trace the transport of particulate Pb. Data in this study indicate minimal off-site surface transport of Pb from the Jewett site into the neighboring residential area.

Lead-isotopic evidence for distinct source of granite and for distinct basement in the northern Appalachians, Maine.

USGS Publications Warehouse

Ayuso, R.A.

1986-01-01

Lead-isotopic compositions of feldspars in high-level Devonian granitic plutons across the northern Appalachians were measured. The presence of three fundamentally different sources of granites was indicated by three distinct lead-isotope groups. Plutons in the coastal lithotectonic block are the most radiogenic (206Pb/204Pb) 18.25-19.25; 207Pb/204Pb 15.59-15.67; 208Pb/204Pb 38.00-38.60); plutons in northern Maine are the least radiogenic (206Pb/204Pb 18.00-18.50; 207Pb/204Pb 15.51-15.55; 208Pb/204Pb 37.80-38.38). Intermediate lead-isotope values characterize the plutons in central Maine. All plutons show relatively radiogenic lead values for their ages and suggest the imprint of continental crustal sources, particularly in the coastal block. These plutons were formed in different crustal fragments in a continental environment, that were juxtaposed after emplacement of the granites.-L.C.H.

Pb isotope geochemistry of Piton de la Fournaise historical lavas

NASA Astrophysics Data System (ADS)

Vlastélic, Ivan; Deniel, Catherine; Bosq, Chantal; Télouk, Philippe; Boivin, Pierre; Bachèlery, Patrick; Famin, Vincent; Staudacher, Thomas

2009-07-01

Variations of Pb isotopes in historical lavas (1927-2007) from Piton de la Fournaise are investigated based on new (116 samples) and published (127 samples) data. Lead isotopic signal exhibits smooth fluctuations (18.87 < 206Pb/ 204Pb < 18.94) on which superimpose unradiogenic spikes ( 206Pb/ 204Pb down to 18.70). Lead isotopes are decoupled from 87Sr/ 86Sr and 143Nd/ 144Nd, which display small and barely significant variations, respectively. No significant change of Pb isotope composition occurred during the longest (> 3 years) periods of inactivity of the volcano (1939-1942, 1966-1972, 1992-1998), supporting previous inferences that Pb isotopic variations occur mostly during and not between eruptions. Intermediate compositions (18.904 < 206Pb/ 204Pb < 18.917) bracket the longest periods of quiescence. In this respect, the highly frequent occurrence of an intermediate composition (18.90 < 206Pb/ 204Pb < 18.91), which clearly defines an isotopic baseline during the most recent densely sampled period (1975-2007), either suggests direct sampling of plume melts or sampling of a voluminous magma reservoir that buffers Pb isotopic composition. Deviations from this prevalent composition occurred during well-defined time periods, namely 1977-1986 (radiogenic signature), 1986-1990 and 1998-2005 (unradiogenic signatures). The three periods display a progressive isotopic drift ending by a rapid return (mostly during a single eruption) to the isotopic baseline. The isotopic gradients could reflect progressive emptying of small magma reservoirs or magma conduits, which are expected to be more sensitive to wall-rock interactions than the main magma chamber. These gradients provide a lower bound ranging from 0.1 to 0.17 km 3 for the size of the shallow magma storage system. The isotopic shifts (March 1986, January 1990 and February 2005) are interpreted as refilling the plumbing system with deep melts that have not interacted with crustal components. The volume of magma erupted between the two major refilling events of March 1986 and February 2005 (0.28 km 3) could provide a realistic estimate of the magma reservoir size. Unradiogenic anomalies appear to be linked, more or less directly, to the eruption of olivine-rich lavas. The related samples have low 206Pb/ 204Pb and 208Pb/ 204Pb but normal 207Pb/ 204Pb, suggesting a recent decrease of U/Pb and Th/Pb, for instance through sequestration of Pb into sulfides. Olivine and sulfides, which are both denser than silicate melts, could be entrained with magma pulses, which give rise to high-flux oceanite eruptions.

Isotopic equilibration between dissolved and suspended particulate lead in the Atlantic Ocean - Evidence from Pb-210 and stable Pb isotopes

NASA Technical Reports Server (NTRS)

Sherrell, Robert M.; Boyle, Edward A.; Hamelin, Bruno

1992-01-01

Vertical profiles of, on one hand, the stable Pb isotopic composition, and on the other, the ratio of total Pb to Pb-210 in suspended particles, are noted to closely track contemporaneous depth variations in these ratios for dissolved Pb throughout the upper 2 km of the Sargasso Sea near Bermuda. A simple flux model suggests that the effect of deep ocean scavenging processes on the flux and isotopic composition of Pb sinking on large particles was minor throughout the preanthropogenic, and most of the anthropogenic era: but it has become more important as surface inputs decrease to preleaded gasoline levels, perhaps exceeding the contribution of surface-derived Pb flux in the next decade.

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

Stable water isotopic composition of the Antarctic subglacial Lake Vostok: implications for understanding the lake's hydrology.

PubMed

Ekaykin, Alexey A; Lipenkov, Vladimir Y; Kozachek, Anna V; Vladimirova, Diana O

2016-01-01

We estimated the stable isotopic composition of water from the subglacial Lake Vostok using two different sets of samples: (1) water frozen on the drill bit immediately after the first lake unsealing and (2) water frozen in the borehole after the unsealing and re-drilled one year later. The most reliable values of the water isotopic composition are: -59.0 ± 0.3 ‰ for oxygen-18, -455 ± 1 ‰ for deuterium and 17 ± 1 ‰ for d-excess. This result is also confirmed by the modelling of isotopic transformations in the water which froze in the borehole, and by a laboratory experiment simulating this process. A comparison of the newly obtained water isotopic composition with that of the lake ice (-56.2 ‰ for oxygen-18, -442.4 ‰ for deuterium and 7.2 ‰ for d-excess) leads to the conclusion that the lake ice is very likely formed in isotopic equilibrium with water. In turn, this means that ice is formed by a slow freezing without formation of frazil ice crystals and/or water pockets. This conclusion agrees well with the observed physical and chemical properties of the lake's accreted ice. However, our estimate of the water's isotopic composition is only valid for the upper water layer and may not be representative for the deeper layers of the lake, so further investigations are required.

Anomalous Lead Isotopic Composition of Galena and Age of Altered Uranium Minerals: a Case study of Chauli Deposits, Chatkal-Qurama District, Uzbekistan

NASA Astrophysics Data System (ADS)

Chernyshev, I. V.; Golubev, V. N.; Chugaev, A. V.

2017-11-01

The enrichment of lead isotopic composition of nonuranium minerals, in the first place galena in 206Pb and 207Pb, as compared to common lead is a remarkable feature of uranium deposits. The study of such lead isotopic composition anomalous in 206Pb and 207Pb in uranium minerals provides an opportunity for not only identification of superimposed processes resulting in transformation of uranium ores during deposit history but also calculation of age of these processes under certain model assumptions. Galena from the Chauli deposit in the Chatkal-Qurama district, Uzbekistan, a typical representative of hydrothermal uranium deposits associated with domains of Phanerozoic continental volcanism, has been examined with the highprecision (±0.02%) MC-ICP-MS method. Twenty microsamples of galena were taken from polished sections. Six of them are galena hosted in carbonate adjacent to pitchblende spherulites or filling thin veinlets (approximately 60 μm) cutting pitchblende. Isotopically anomalous lead with 206Pb/204Pb and 207Pb/204Pb values reaching 20.462 and 15.743, respectively, has been found in these six microsamples in contrast to another fourteen in which the Pb-Pb characteristics are consistent with common lead. On the basis of these data and with account for the 292 ± 2 Ma age for the Chauli deposit, the age of epigenetic transformation of uranium ores of this deposit has been estimated. During this process, radiogenic lead partly lost from pitchblende was captured into galena. The obtained date is 170 Ma. In the Chatkal-Qurama district, these epigenetic processes are apparently caused by the interaction of uranium minerals with activated underground water under tectonic activity and relief transformation, which took place from the post-Permian (i.e., after the Chauli formation) to the Jurassic period.

Triple Oxygen Isotope Constraints on Seawater δ18O and Temperature

NASA Astrophysics Data System (ADS)

Hayles, J.; Shen, B.; Homann, M.; Yeung, L.

2017-12-01

One point of contention among geoscientists is whether the 18O/16O ratio of seawater is roughly constant, or if it varies considerably throughout geologic time. On one hand, the oxygen isotope composition of the ocean is thought to be well buffered by high- and low-temperature interactions between seawater and seafloor rocks. If these interactions do not vary on billion-year timescales, the oxygen-isotope compositions of marine sedimentary rocks mostly relate to changes in seawater temperature and global ice volume. On the other hand, long-term cooling of the planetary interior would alter these water-rock interactions leading to a secular change in the oxygen isotope composition of seawater. Models suggest that this secular change would enrich seawater with heavy oxygen isotopes over time. In this study, we present new, high precision, triple-oxygen-isotope (18O/16O, 17O/16O) analyses of marine chert samples from 3.45 Ga to 460Ma. The results of these analyses are paired with a new theoretical quartz-water equilibrium curve and a simplified seawater model to provide possible pairings of δ'18O and Δ'17O for the water which these samples could have formed in equilibrium with. Analysis of the new sample data, in addition to published chert triple oxygen isotope compositions, shows a general trend of older chert samples being progressively incompatible with waters possessing a modern-like seawater triple oxygen isotope composition. Implications on constraining the secular evolution of seawater δ18O and temperature will be discussed.

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.

Tracing the origin of pollution in French Alpine snow and aerosols using lead isotopic ratios.

PubMed

Veysseyre, A M; Bollhöfer, A F; Rosman, K J; Ferrari, C P; Boutron, C F

2001-11-15

Fresh snow samples collected at 15 remote locations and aerosols collected at one location in the French Alps between November 1998 and April 1999 have been analyzed for Pb concentration and isotopic composition by thermal ionization mass spectrometry. The snow samples contained 19-1300 pg/g of Pb with isotopic ratios 206Pb/207Pb (208Pb/207Pb) of 1.1279-1.1607 (2.3983-2.4302). Airborne Pb concentrations at one sampling site ranged from 0.42 to 6.0 ng/m3 with isotopic ratios of 1.1321-1.1427 (2.4029-2.4160). Air mass trajectory analysis combined with isotopic compositions of potential source regions did not show discernible evidence of the long-range atmospheric transport of pollutants. Isotopic ratios in the Alpine snow samples and thus the free troposphere were generally higher than airborne Pb isotopic ratios in urban France, which coupled with the relatively high Pb concentrations suggested a regional anthropogenic Pb source, probably Italy but possibly Eastern Europe.

Source apportionment of lead in the blood of women of reproductive age living near tailings in Taxco, Guerrero, Mexico: An isotopic study.

PubMed

Vázquez Bahéna, Analine Berenice; Talavera Mendoza, Oscar; Moreno Godínez, Ma Elena; Salgado Souto, Sergio Adrián; Ruiz, Joaquín; Huerta Beristain, Gerardo

2017-04-01

The concentration and isotopic composition of lead in the blood of forty seven women of reproductive age (15-45y) exposed to multiple sources in two rural communities of the mining region of Taxco, Guerrero in southern Mexico were determined in order to identify specific contributing sources and their apportionment and to trace probable ingestion pathways. Our data indicate that >36% of the studied women have blood lead concentrations above 10μgdL -1 and up to 87% above 5μgdL -1 . Tailings contain between 2128 and 5988mgkg -1 of lead and represent the most conspicuous source in the area. Lead contents in indoor dust are largely variable (21.7-987mgkg -1 ) but only 15% of samples are above the Mexican Regulatory Guideline for urban soils (400mgkg -1 ). By contrast, 85% of glazed containers (range: 0.026-68.6mgkg -1 ) used for cooking and food storage are above the maximum 2mgL -1 of soluble lead established in the Mexican Guideline. The isotopic composition indicates that lead in the blood of 95% of the studied women can be modeled in terms of a mixing system between local ores (and derivatives), glazed pottery and Morelos bedrock, end-members, with the two former being largely the most important contributors. Only one sample shows influence of indoor paints. Indoor dust is dominated by ores and derivatives but some samples show evidence of contribution from a less radiogenic source very likely represented by interior paints. This study supports the application of lead isotopic ratios to identify potential sources and their apportionment in humans exposed to multiple sources of lead from both, natural and anthropogenic origin. Copyright © 2017 Elsevier B.V. All rights reserved.

Lead isotope compositions as guides to early gold mineralization: The North Amethyst vein system, Creede district, Colorado

USGS Publications Warehouse

Foley, Nora K.; Ayuso, Robert A.

1994-01-01

Pb isotope compositions from the late stage of the North Amethyst vein system and from the Bondholder and central and southern Creede mining districts are more radiogenic than the host volcanic rocks of the central cluster of the San Juan volcanic field. Our Pb isotope results indicate that early Au mineralization of the North Amethyst area may represent the product of an older and relatively local hydrothermal system distinct from that of the younger base metal and Ag mineralization found throughout the region. Fluids that deposited Au minerals may have derived their Pb isotope composition by a greater degree of interaction with shallow, relatively less radiogenic volcanic wall rocks. The younger, base metal and Ag-rich mineralization that overprints the Au mineralization in the North Amethyst area clearly has a more radiogenic isotopic signature, which implies that the later mineralization derived a greater component of its Pb from Proterozoic source rocks, or sediments derived from them.Paragenetically early sulfide-rich vein assemblages have the least radiogenic galenas and generally also have the highest Au contents. Thus, identification of paragenetically early vein assemblages with relatively unradiogenic Pb isotope compositions similar to those of the North Amethyst area provides an additional exploration tool for Au in the central San Juan Mountains area.

The isotope mass effect on chlorine diffusion in dacite melt, with implications for fractionation during bubble growth

NASA Astrophysics Data System (ADS)

Fortin, Marc-Antoine; Watson, E. Bruce; Stern, Richard

2017-12-01

Previous experimental studies have revealed that the difference in diffusivity of two isotopes can be significant in some media and can lead to an observable fractionation effect in silicate melts based on isotope mass. Here, we report the first characterization of the difference in diffusivities of stable isotopes of Cl (35Cl and 37Cl). Using a piston-cylinder apparatus, we generated quenched melts of dacitic composition enriched in Cl; from these we fabricated diffusion couples in which Cl atoms were induced to diffuse in a chemical gradient at 1200 to 1350 °C and 1 GPa. We analyzed the run products by secondary ion mass spectrometry (SIMS) for their isotopic compositions along the diffusion profiles, and we report a diffusivity ratio for 37Cl/35Cl of 0.995 ± 0.001 (β = 0.09 ± 0.02). No significant effect of temperature on the diffusivity ratio was discernable over the 150 °C range covered by our experiments. The observed 0.5% difference in diffusivity of the two isotopes could affect our interpretation of isotopic measurements of Cl isotopes in bubble-bearing or degassed magmas, because bubble growth is regulated in part by the diffusive supply of volatiles to the bubble from the surrounding melt. Through numerical simulations, we constrain the extent of Cl isotopic fractionation between bubble and host melt during this process. Bubble growth rates vary widely in nature-which implies a substantial range in the expected magnitude of isotopic fractionation-but plausible growth scenarios lead to Cl isotopic fractionations up to about 5‰ enrichment of 35Cl relative to 37Cl in the bubble. This effect should be considered when interpreting Cl isotopic measurements of systems that have experienced vapor exsolution.

Lead-isotopic data from sulfide minerals from the Cascade Range, Oregon and Washington

USGS Publications Warehouse

Church, S.E.; LeHuray, A.P.; Grant, A.R.; Delevaux, M.H.; Gray, J.E.

1986-01-01

Lead-isotopic studies of mineral deposits associated with Tertiary plutons found in the Cascade Range of Oregon and Washington demonstrate a rather uniform isotopic composition in various sulfide minerals ( 206Pb 204Pb = 18.84 to 19.05; 207Pb 204Pb = 15.57 to 15.62; 208Pb 204Pb = 38.49 to 38.74), show less variation than data from the volcanic rocks of the Cascade Range and fall within the mixing array defined by the MORB regression line and continental sediments. An evaluation of the role of crustal assimilation by hydrothermal convection during emplacement was made on five sulfide deposits associated with a single composite batholith, the Cloudy Pass pluton. The Pb-isotopic data and mass balance calculations suggest that only minor amounts of the lead were derived from the overlying Precambrian (?) Swakane Biotite Gneiss during emplacement. The bulk of the metal that occurs in sulfide deposits in the Cascade mineral belt appears to have been derived from subducted continental detritus. The variation of the Pb-isotopic signature of Sulfides from specific districts or deposits suggests that there is a correlation with age and structure of the crust. 206Pb 204Pb is greater than 18.92 in northern Washington and southern Oregon where deposits have intruded Mesozoic or older crust. However, the ore deposits between the northern Oregon border and central Oregon, south of Eugene, have intruded younger crust composed largely of mafic and andesitic volcanic rocks and 206Pb 204Pb lies between 18.84 and 18.92. This region, previously called the Columbia embayment, appears to be underlain by Tertiary volcanic rocks. Lead-isotopic data may be used to define the boundaries between discontinuous blocks of Mesozoic crust and Tertiary volcanic cover. ?? 1986.

Analysis of the interdecadal variability of summer precipitation in central Japan using a reconstructed 106 year long oxygen isotope record from tree ring cellulose

NASA Astrophysics Data System (ADS)

Kurita, Naoyuki; Nakatsuka, Takeshi; Ohnishi, Keiko; Mitsutani, Takumi; Kumagai, Tomo'omi

2016-10-01

We present a unique proxy for reconstructing the interannual variability of summer precipitation associated with the quasi-stationary front (Baiu front) in central Japan. The rainfall from the Baiu front has a relatively lower oxygen isotopic composition than other types of nonfrontal precipitation. The variability in the oxygen isotopes in summer rainfall is closely related to the Baiu frontal activity. In this study we used a mechanistic tree ring isotope model to reconstruct a 106 year long oxygen isotopic composition of precipitation during the early rainy season (June) based on the oxygen isotopic compositions of the annual rings of Chamaecyparis obtusa Endl trees from central Japan. The year-to-year variations of the isotopes over the most recent 25 years are associated with several teleconnection patterns that often lead to the Baiu precipitation anomalies in central Japan (such as the Pacific-Japan (PJ) pattern, Silk Road pattern, and wave train pattern along the polar jet). Yet none of these external forcing mechanisms apply further back in time. From the 1950s to 1980s, the interannual isotopic variability is predominantly related to local factors such as anomalous intensification/weakening of the Bonin High. Before the 1950s, the variability of the oxygen isotopic composition of precipitation is mainly associated with a wave train pattern along the polar jet. The isotopic variability is predominantly linked to the PJ pattern, while the PJ index is correlated with El Niño-Southern Oscillation. These findings suggest that the teleconnection patterns influencing Baiu precipitation variability vary according to interdecadal time scales during the twentieth century.

The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

NASA Astrophysics Data System (ADS)

von Sperber, Christian; Kries, Hajo; Tamburini, Federica; Bernasconi, Stefano M.; Frossard, Emmanuel

2014-01-01

Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. During the enzymatic hydrolysis an isotopic fractionation (ε) occurs leaving an imprint on the oxygen isotope composition of the released Pi which might be used to trace phosphorus in the environment. Therefore, enzymatic assays with acid phosphatases from wheat germ and potato tuber and alkaline phosphatase from Escherichia coli were prepared in order to determine the oxygen isotope fractionation caused by these enzymes. Adenosine 5‧ monophosphate and glycerol phosphate were used as substrates. The oxygen isotope fractionation caused by acid phosphatases is 20-30‰ smaller than for alkaline phosphatases, resulting in a difference of 5-7.5‰ in δ18O of Pi depending on the enzyme. We attribute the enzyme dependence of the isotopic fractionation to distinct reaction mechanisms of the two types of phosphatases. The observed difference is large enough to distinguish between the two enzymatic processes in environmental samples. These findings show that the oxygen isotope composition of Pi can be used to trace different enzymatic processes, offering an analytical tool that might contribute to a better understanding of the P-cycle in the environment.

Lead and strontium isotopic evidence for crustal interaction and compositional zonation in the source regions of Pleistocene basaltic and rhyolitic magmas of the Coso volcanic field, California

USGS Publications Warehouse

Bacon, C.R.; Kurasawa, H.; Delevaux, M.H.; Kistler, R.W.; Doe, B.R.

1984-01-01

The isotopic compositions of Pb and Sr in Pleistocene basalt, high-silica rhyolite, and andesitic inclusions in rhyolite of the Coso volcanic field indicate that these rocks were derived from different levels of compositionally zoned magmatic systems. The 2 earliest rhyolites probably were tapped from short-lived silicic reservoirs, in contrast to the other 36 rhyolite domes and lava flows which the isotopic data suggest may have been leaked from the top of a single, long-lived magmatic system. Most Coso basalts show isotopic, geochemical, and mineralogic evidence of interaction with crustal rocks, but one analyzed flow has isotopic ratios that may represent mantle values (87Sr/86Sr=0.7036,206Pb/204Pb=19.05,207Pb/204Pb=15.62,208Pb/204Pb= 38.63). The (initial) isotopic composition of typical rhyolite (87Sr/86Sr=0.7053,206Pb/204Pb=19.29,207Pb/204Pb= 15.68,208Pb/204Pb=39.00) is representative of the middle or upper crust. Andesitic inclusions in the rhyolites are evidently samples of hybrid magmas from the silicic/mafic interface in vertically zoned magma reservoirs. Silicic end-member compositions inferred for these mixed magmas, however, are not those of erupted rhyolite but reflect the zonation within the silicic part of the magma reservoir. The compositional contrast at the interface between mafic and silicic parts of these systems apparently was greater for the earlier, smaller reservoirs. ?? 1984 Springer-Verlag.

Oxygen Isotopic Analyses of Water Extracted from the Martian Meteorite NWA 7034

NASA Astrophysics Data System (ADS)

Nunn, M.; Agee, C. B.; Thiemens, M. H.

2012-12-01

Introduction: The NWA 7034 meteorite has been identified as Martian, but it is distinct from the Shergottite-Nakhlite-Chassignite (SNC) grouping of meteorites in its petrology (it is the only known Martian basaltic breccia) and bulk silicate oxygen isotopic composition (Δ17O = 0.56 ± 0.06 ‰, where Δ17O = δ17O - 0.528 x δ18O, compared to the average SNC Δ17O ≈ 0.3 ‰) [e.g., 1-2]. We report here measurements of the oxygen isotopic composition of water extracted from NWA 7034 by stepwise heating. Methods: A piece (~1.2g) of NWA 7034 was pumped to vacuum until outgassing had stopped before heating to 50, 150, 320, 500, and 1000°C. The sample was maintained at each temperature step for at least one hour while collecting evolved volatiles in a liquid nitrogen cold trap. Water was selectively converted to molecular oxygen, the oxygen isotopic composition of which was then measured on a double collecting isotope ratio mass spectrometer. Results: Our stepwise heating experiments indicate NWA 7034 contains 3330ppm water, and this water has an average oxygen isotopic composition of Δ17O = 0.330 ± 0.011‰. The oxygen isotopic composition of water in NWA 7034 is unlike that of the silicates from which it is extracted (Δ17O = 0.56 ± 0.06 ‰) but is comparable to the average SNC silicate composition (Δ17O ≈ 0.3 ‰). However, there is no consensus on the oxygen isotopic composition of water in SNCs because aliquots of water extracted from different samples (separate pieces of a single meteorite or from different meteorites) have different oxygen isotopic compositions [3]. Furthermore, carbonates and sulfates extracted from SNCs also possess distinct oxygen isotopic compositions [4]. The variation in oxygen isotopic composition among these phases most likely results from the existence of isotopically distinct oxygen reservoirs on Mars that were not equilibrated. On Earth, interaction of ozone (O3) and carbon dioxide (CO2) leads to a mass independent oxygen isotopic composition of atmospheric CO2 [5]. This anomaly is transferred by exchange from CO2 to water and subsequently to secondary minerals. The much larger CO2 to water ratio on Mars could allow this process to introduce a measurable oxygen isotopic anomaly to sulfates, carbonates, and water. The magnitude and variability of this anomaly would depend on the formation mechanism of the species (particularly the source of oxygen), as is consistent with measurements to date of phases in SNCs. References: [1] Franchi, I.A., et al. (1999) MAPS 34, 657-661. [2] Rumble, D. and Irving, A.J. (2009) LPSC XXXX, #2293 [3] Karlsson, H.R., et al. (1992) Science 255, 1409-1411. [4] Farquhar, J. and Thiemens, M.H. (2000) J. Geophys. Res. 105, 11991-11997. [5] Yung, Y.L., et al. (1991) Geophys. Res. Lett. 18, 13-16.

Post-17th-century changes of European lead emissions recorded in high-altitude alpine snow and ice.

PubMed

Schwikowski, Margit; Barbante, Carlo; Doering, Thomas; Gaeggeler, Heinz W; Boutron, Claude; Schotterer, Ulrich; Tobler, Leo; van de Velde, Katja; Ferrari, Christophe; Cozzi, Giulio; Rosman, Kevin; Cescon, Paolo

2004-02-15

Lead concentrations and lead isotope ratios were analyzed in two firn/ice cores covering the period from 1650 to 1994, which were obtained from the 4450 m high glacier saddle Colle Gnifetti located in the Monte Rosa massif at the Swiss-Italian border. This study presents the first glaciochemical time series with annual resolution, spanning several centuries of lead concentrations and lead isotopic compositions in precipitation in Europe. Lead concentrations in firn dated from the 1970s are approximately 25 times higher than in ice dated from the 17th century, confirming the massive rise in lead pollution in Europe during the last few centuries. A decline of the lead concentration is then observed during the last two decades, i.e., from 1975 to 1994. The lead isotope ratio 206Pb/207Pb decreased from about 1.18 in the 17th and 18th centuries to about 1.12 in the 1970s. These variations are in good agreement with available information on variations in anthropogenic lead emissions from West European countries, especially from the use of lead additives in gasoline.

Lead Isotope Characterization of Petroleum Fuels in Taipei, Taiwan

PubMed Central

Yao, Pei-Hsuan; Shyu, Guey-Shin; Chang, Ying-Fang; Chou, Yu-Chen; Shen, Chuan-Chou; Chou, Chi-Su; Chang, Tsun-Kuo

2015-01-01

Leaded gasoline in Taiwan was gradually phased out from 1983 to 2000. However, it is unclear whether unleaded gasoline still contributes to atmospheric lead (Pb) exposure in urban areas. In this study, Pb isotopic compositions of unleaded gasolines, with octane numbers of 92, 95, 98, and diesel from two local suppliers in Taipei were determined by multi-collector inductively coupled plasma mass spectrometry with a two-sigma uncertainty of ± 0.02 %. Lead isotopic ratios of vehicle exhaust (208Pb/207Pb: 2.427, 206Pb/207Pb: 1.148, as estimated from petroleum fuels) overlap with the reported aerosol data. This agreement indicates that local unleaded petroleum fuels, containing 10–45 ng·Pb·g−1, are merely one contributor among various sources to urban aerosol Pb. Additionally, the distinction between the products of the two companies is statistically significant in their individual 208Pb/206Pb ratios (p-value < 0.001, t test). Lead isotopic characterization appears to be applicable as a “fingerprinting” tool for tracing the sources of Pb pollution. PMID:25918913

The lead (Pb) isotope signature, behaviour and fate of traffic-related lead pollution in roadside soils in The Netherlands.

PubMed

Walraven, N; van Os, B J H; Klaver, G Th; Middelburg, J J; Davies, G R

2014-02-15

In this study the origin, behaviour and fate of anthropogenic Pb in sandy roadside soils were assessed by measuring soil characteristics, Pb isotope composition and content. In 1991 and 2003 samples were taken at different depth intervals at approximately 8 and 75 m from two highways in The Netherlands. The Pb isotope composition of the litter layer ((206)Pb/(207)Pb=1.12-1.14) differs from the deeper soil samples ((206)Pb/(207)Pb=1.20-1.21). Based on a mixing model it is concluded that the samples contain two Pb sources: natural Pb and anthropogenic Pb, the latter mainly derived from gasoline. (206)Pb/(207)Pb ratios demonstrate that the roadside soils were polluted to a depth of ~15 cm. Within this depth interval, anthropogenic Pb content is associated with organic matter. Although Pb pollution only reached a depth of ~15 cm, this does not mean that the topsoils retain all anthropogenic Pb. Due to the low pH and negligible binding capacity of soils at depths >15 cm, anthropogenic Pb migrated towards groundwater after reaching depths of >15 cm. The Pb isotope composition of the groundwater ((206)Pb/(207)Pb=1.135-1.185) establishes that groundwater is polluted with anthropogenic Pb. The contribution of anthropogenic Pb to the groundwater varies between ~30 and 100%. Based on the difference in soil Pb content and Pb isotope compositions over a period of 12 years, downward Pb migration is calculated to vary from 72 ± 95 to 324 ± 279 mg m(-2)y(-1). Assuming that the downward Pb flux is constant over time, it is calculated that 35-90% of the atmospherically delivered Pb has migrated to the groundwater. Copyright © 2013 Elsevier B.V. All rights reserved.

Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary

NASA Astrophysics Data System (ADS)

Chen, Mengli; Boyle, Edward A.; Lee, Jong-Mi; Nurhati, Intan; Zurbrick, Cheryl; Switzer, Adam D.; Carrasco, Gonzalo

2016-11-01

Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Origin of the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Evidence from regional Pb and Sr isotope sources

USGS Publications Warehouse

Ayuso, R.A.; Kelley, K.D.; Leach, D.L.; Young, L.E.; Slack, J.F.; Wandless, G.; Lyon, A.M.; Dillingham, J.L.

2004-01-01

Pb and Sr isotope data were obtained on the shale-hosted Zn-Pb-Ag Red Dog deposits (Qanaiyaq, Main, Aqqaluk, and Paalaaq), other shale-hosted deposits near Red Dog, and Zn-Pb-Ag sulfide and barite deposits in the western and central Brooks Range. The Red Dog deposits and other shale-hosted Zn-Pb-Ag deposits near Red Dog are hosted in the Mississippian Kuna Formation, which is underlain by a sequence of marine-deltaic clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. Ag-Pb-Zn vein-breccias are found in the Endicott Group. Galena formed during the main mineralization stages in the Red Dog deposits and from the Anarraaq and Wulik deposits have overlapping Pb isotope compositions in the range 206Pb/204Pb = 18.364 to 18.428, 207Pb/204Pb = 15.553 to 15.621, and 208Pb/204Pb = 38.083 to 38.323. Galena and sphalerite formed during the main ore-forming stages in the Red Dog deposits define a narrow field on standard uranogenic and thorogenic Pb isotope diagrams. Lead in sulfides of the Red Dog district is less radiogenic (238U/204Pb: ?? = 9.51-9.77) than is indicated by the average crustal lead evolution model (?? = 9.74), a difference consistent with a long history of evolution at low ratios of ?? before the Carboniferous. The homogeneous regional isotopic reservoir of Pb may indicate large-scale transport and leaching of minerals with various ?? ratios and Th/Pb ratios. Younger and genetically unrelated fluids did not significantly disturb the isotopic compositions of galena and sphalerite after the main mineralization event in the Red Dog district. Some pyrite shows evidence of minor Pb remobilization. The overall lead isotope homogeneity in the shale-hosted massive sulfide deposits is consistent with three types of control: a homogeneous regional source, mixing of lead during leaching of a thick sedimentary section and fluid transport, or mixing at the site of deposition. Isotopic variability of the hydrothermal fluids, as represented by galena in the Red Dog district, appears to be consistent with a simple mixing system. Evidence indicates that galena was deposited from largely similar hydrothermal solutions throughout the Red Dog district. A shared regional isotopic reservoir is also supported by the correspondence of Pb isotope compositions of galena in deposits of the Red Dog district and galena in clastic rocks (vein-breccias). Leaching of metals and progressive extraction of radiogenic lead from the clastic rocks in the Endicott Group may account for the trend of increasing 206Pb/204Pb in galena of the Red Dog district. Galena in the Red Dog deposits is unlikely to have been derived entirely from the same isotopic reservoir as that represented by the lead in the Kuna Formation or from the igneous rocks in the Red Dog district. Sr isotope data for barite, calcite, and witherite from the Red Dog deposits are compared with data from regional barite that is associated with sulfides and from barite in sulfide-poor occurrences. Fluids with heterogeneous Sr isotope signatures are indicated. Barite in the Main deposit extends to higher ratios of 87Sr/86Sr (0.709034-0.709899) than barite in the Anarraaq deposit (0.708615-0.709256). All barite is more radiogenic than Carboniferous seawater. Other Mississippian(?) shale-hosted deposits and mineral occurrences containing barite in the Red Dog district and barite in regional occurrences east of Red Dog in the western and central Brooks Range also have heterogeneous 87Sr/86Sr ratios. Carbonate (87Sr/86Sr = 0.710319-0.713637) and witherite (87 Sr/86 Sr = 0.710513) in the Main deposit are more radiogenic than barite. In contrast, carbonate (87Sr/86Sr = 0.708196-0.709740) intergrown with massive sulfides at Anarraaq has isotopic compositions similar to that of barite. Paragenetic and isotop ic studies suggest that early barite is similar to barite typically formed in cold seeps along continental margins. This early fine-grained barite formed before the main mineralizat

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

NASA Astrophysics Data System (ADS)

Shuai, Yanhua; Douglas, Peter M. J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael D.; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-02-01

Multiply isotopically substituted molecules ('clumped' isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature-time conditions corresponding to 'low,' 'mature,' and 'over-mature' stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions ('high' to 'over-mature' stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where 'secondary' cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

Galactic cosmic ray composition

NASA Technical Reports Server (NTRS)

Meyer, J. P.

1986-01-01

An assessment is given of the galactic cosmic ray source (GCRS) elemental composition and its correlation with first ionization potential. The isotopic composition of heavy nuclei; spallation cross sections; energy spectra of primary nuclei; electrons; positrons; local galactic reference abundances; comparison of solar energetic particles and solar coronal compositions; the hydrogen; lead; nitrogen; helium; and germanium deficiency problems; and the excess of elements are among the topics covered.

Nitrogen isotopic components in the early solar system

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1994-01-01

It is quite common to take the terrestrial atmospheric value of (15)N/(14)N (0.00366) as typical of nitrogen in the early solar system, but in fact there is little reason to suppose that this value had a nebula-wide significance. Indeed, it is not clear that there was a unique solar-system-wide (15)N/(14)N ratio, of whatever value. Here we review what is known about the distribution of the nitrogen isotopes among those solar-system objects that have been sampled so far and conclude that those isotopes reveal widespread inhomogeneity in the early solar system. Whether the isotopically distinct primordial components implied by this analysis were solid or gaseous or a mixture of both is not known. The isotopic composition of N in the Earth's mantle is controversial: estimates range from a 1.1 percent depletion in (15)N to a 1.4 percent enrichment. (Isotopic compositions will be expressed throughout as percent deviations from the terrestrial atmospheric value.) The present-day Martian atmosphere is characterized by a value of plus 62 percent but this enrichment in (15)N is attributed to selective loss of (14)N from the Martian exosphere. Modelling of this fractionation leads to an estimated primordial composition similar to the terrestrial atmospheric value, through the precision of this model-dependent result is unclear.

The lead isotopic composition of dust in the vicinity of a uranium mine in northern Australia and its use for radiation dose assessment.

PubMed

Bollhöfer, Andreas; Honeybun, Russell; Rosman, Kevin; Martin, Paul

2006-08-01

Airborne lead isotope ratios were measured via Thermal Ionisation Mass Spectrometry in samples from the vicinity of Ranger uranium mine in northern Australia. Dust deposited on leaves of Acacia spp. was washed off and analysed to gain a geographical snapshot of lead isotope ratios in the region. Aerosols were also collected on Teflon filters that were changed monthly over one seasonal cycle using a low volume diaphragm pump. Lead isotope ratios in dust deposited on leaves overestimate the relative amount of mine origin airborne lead, most likely due to a difference of the size distribution of particles collected on leaves and true aerosol size distribution. Seasonal measurements show that the annual average mine contribution to airborne lead concentrations in Jabiru East, approximately 2.5 km northwest of the mine, amounted to 13%, with distinct differences between the wet and dry season. The relative contribution of mine origin lead deposited on leaves in the dry season drops to less than 1% at a distance of 12.5 km from the mine along the major wind direction. An approach is outlined, in which lead isotope ratios are used to estimate the effective radiation dose received from the inhalation of mine origin radioactivity trapped in or on dust. Using the data from our study, this dose has been calculated to be approximately 2 microSv year(-1) for people living and working in the area.

Lead isotopes reveal different sources of lead in balsamic and other vinegars.

PubMed

Ndung'u, Kuria; Hibdon, Sharon; Véron, Alain; Flegal, A Russell

2011-06-15

Fifty-eight brands of balsamic vinegars were analyzed for lead concentrations and isotopic compositions ((204)Pb, (206)Pb, (207)Pb, and (208)Pb) to test the findings of a previous study indicating relatively high levels of lead contamination in some of those vinegars--more than two thirds (70%) of them exceeded California's State Maximum Level (34 μg/L) based on consumption rates ≥0.5 μg Pb per day. The lead isotopic fingerprints of all those vinegars with high lead concentrations were then found to be primarily anthropogenic. This isotopic analysis unquestionably reveals multiple contamination sources including atmospheric pollutant Pb and an unidentified contamination source, likely occurring after grape harvest. Organically grown grape vinegars display the same Pb content and isotopic signatures as other vinegars. This implies that pesticides might not be a significant source of pollutant Pb in vinegars. A significant post-harvest contamination would be inherited from chemicals added during production and/or material used during transport, processing or storage of these vinegars. This is consistent with the highest Pb levels being found in aged vinegars (112±112 μg/L) in contrast to other vinegars (41.6±28.9 μg/L) suggesting contamination during storage. It is, therefore, projected that lead levels in most vinegars, especially aged balsamic and wine vinegars, will decrease with improvements in their manufacture and storage processes consequential to recent concerns of elevated levels of lead in some vinegars. Copyright © 2011 Elsevier B.V. All rights reserved.

Biological and physical influences on the carbon isotope content of CO2 in a subalpine forest snowpack, Niwot Ridge, Colorado

Treesearch

D. R. Bowling; W. J. Massman; S. M. Schaeffer; S. P. Burns; R. K. Monson; M. W. Williams

2009-01-01

Considerable research has recently been devoted to understanding biogeochemical processes under winter snow cover, leading to enhanced appreciation of the importance of many winter ecological processes. In this study, a comprehensive investigation of the stable carbon isotope composition (δ 13C) of CO2 within a high-elevation subalpine...

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

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.

An isotopic perspective on growth and differentiation of Proterozoic orogenic crust: From subduction magmatism to cratonization

NASA Astrophysics Data System (ADS)

Johnson, Simon P.; Korhonen, Fawna J.; Kirkland, Christopher L.; Cliff, John B.; Belousova, Elena A.; Sheppard, Stephen

2017-01-01

The in situ chemical differentiation of continental crust ultimately leads to the long-term stability of the continents. This process, more commonly known as 'cratonization', is driven by deep crustal melting with the transfer of those melts to shallower regions resulting in a strongly chemically stratified crust, with a refractory, dehydrated lower portion overlain by a complementary enriched upper portion. Since the lower to mid portions of continental crust are rarely exposed, investigation of the cratonization process must be through indirect methods. In this study we use in situ Hf and O isotope compositions of both magmatic and inherited zircons from several felsic magmatic suites in the Capricorn Orogen of Western Australia to highlight the differentiation history (i.e. cratonization) of this portion of late Archean to Proterozoic orogenic crust. The Capricorn Orogen shows a distinct tectonomagmatic history that evolves from an active continental margin through to intracratonic reworking, ultimately leading to thermally stable crust that responds similarly to the bounding Archean Pilbara and Yilgarn Cratons. The majority of magmatic zircons from the main magmatic cycles have Hf isotopic compositions that are generally more evolved than CHUR, forming vertical arrays that extend to moderately radiogenic compositions. Complimentary O isotope data, also show a significant variation in composition. However, combined, these data define not only the source components from which the magmas were derived, but also a range of physio-chemical processes that operated during magma transport and emplacement. These data also identify a previously unknown crustal reservoir in the Capricorn Orogen.

The isotopic composition of ore lead of the Creede mining district and vicinity, San Juan Mountains, Colorado: Text of a talk presented at the San Juan Mountains symposium to honor Thomas A. Steven; Rocky Mountain Section meeting of the Geological Society of America, May 2, 1987, Boulder, Colorado

USGS Publications Warehouse

Foley, N.K.; Barton, P.B.; Bethke, P.M.; Doe, B.R.

1988-01-01

Recent work allows us to extend the results of Doe et al. and to consider alternative processes to explain the widespread homogeneity and radiogenic nature of the ore lead: 1) David Matty (pers. commun., 1986) has shown that some minor volcanic units in the area have unusually radiogneic lead values; magmas comparable in composition to the units are a possible, though improbable, source of the ore lead. 2) The uniformity of the isotopic values of galenas may have resulted from homogenization during an extensive potassium-metasomatic event that predated the ores; this possibility is being tested in an on-going study of feldspars from metasomatized and unmetasomatized rocks. 3) Recent regional studies suggest the possibility of a prevolcanic, NNW-trending graben system filled by clastic sediments derived from the Precambrian basement, a process that would have an homogenizing effect on the lead isotopes. This interpretation implies importation, deep within the Creede hydrologic system, of fluids from remote sources. These alternatives show that the Pbisotope systematics may have a profound impact on the interpretation of the Creede hydrothermal system, and that further study is warranted.

Lead isotopes in trade wind aerosols at Barbados - The influence of European emissions over the North Atlantic

NASA Technical Reports Server (NTRS)

Hamelin, B.; Grousset, F. E.; Biscaye, P. E.; Zindler, A.; Prospero, J. M.

1989-01-01

Previous studies have shown that Pb can be used as a transient tracer in the atmosphere and the ocean because of strong time-variability of industrial inputs and because Pb isotopic composition can be used to identify contributions from different sources. Pb isotopic measurements on aerosols collected from the North Atlantic Ocean in the trade wind belt are presented. Aerosols sampled at Barbados during the 1969-1985 period have a Pb isotopic composition different from that observed by previous investigators in Bermuda corals and Sargasso Sea waters. Barbados aerosols appear to contain significant amounts of relatively unradiogenic industrial and automotive Pb that is derived from Europe and carried to Barbados by the trade winds. In contrast, Bermuda corals and Sargasso sea waters are influenced mainly by U.S.-derived emissions, which contain more radiogenic Pb originating from Missouri-type ores. This difference generates a strong latitudinal Europe-U.S.A. isotopic gradient, thus allowing study of trans-Atlantic atmospheric transport and ocean mixing processes.

Isotopic Zonation Within Sulfate Evaporite Mineral Crystals Reveal Quantitative Paleoenvironment Details

NASA Astrophysics Data System (ADS)

Coleman, M.; Rhorssen, M.; Mielke, R. E.

2008-12-01

Isotopic variations measured within a single crystal of hydrated magnesium sulfate are greater than 30 permil for delta 2-H, almost 10 permil for δ18O in water of hydration; and greater than 3 permil in sulfate oxygen. These results are interpreted to indicate the relative humidity of the system during evaporation (15 to 20 percent in this test case) and constrain the volume of water involved. The theoretical basis of this system is the isotopic fractionation between the species in solution and those precipitated as evaporite salts. Precipitation preferentially accumulates more of the heavy isotopes of sulfur and oxygen in mineral sulfate, relative to sulfate in solution. During the course of mineral growth this leads to successive depletion of the respective heavier isotopes in the residual brine reflected in a parallel trend in successive precipitates or even in successive zones within a single crystal. The change in isotopic composition at any one time during the process, relative to the initial value, can be described by an isotopic version of the Rayleigh Fractionation equation, depending only on the extent of the completion of the process and the relevant fractionation factor. Evaporation preferentially removes isotopically lighter hydrogen and oxygen leading to successive extents of enrichment in the respective heavier isotopes in the residual water. However, the relative effects on hydrogen and oxygen isotopes differs as function of relative humidity [1]. ALL OF THESE CHANGES ARE PRESERVED IN THE MINERAL ISOTOPE COMPOSITIONS. We precipitated barium sulfate from epsomite or gypsum samples, which was reduced at 1450°C in the presence of graphite and glassy carbon in a Finnigan TC/EA to produce CO for O isotopic analysis in a Finnigan 253 mass spectrometer, while a separate subsample was oxidized to SO2 in a Costech Elemental Analyzer. However, to make progress with this approach we needed to make a large number of measurements of hydration water and so we developed a new analytical method [2]. We use a modification of the standard TC/EA continuous-flow protocol to measure both hydrogen and oxygen of water of hydration from the same small sample. We have proved the concept of this new approach by analyzing zones within crystals and individual grains, growing epsomite (magnesium sulfate heptahydrate) in the laboratory and by analysis of natural gypsum evaporites. We are now exploring the effects of varying the controlling parameters. Eventual application to Martian sulfates will reveal amount of water involved in sulfate formation, its isotopic composition(s) and details of the paleo-atmospheric humidity. [1] Gat JR and Gonfiantini R, (Eds) (1981) IAEA Technical Report Series. [2] Rohrssen MK, Brunner B Mielke RE and Coleman M (2008) Analyt. Chem. (in press).

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

NASA Astrophysics Data System (ADS)

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

2010-04-01

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

Post-eruptive alteration of silicic ignimbrites and lavas, Gran Canaria, Canary Islands - Strontium, neodymium, lead, and oxygen isotopic evidence

NASA Technical Reports Server (NTRS)

Cousens, Brian L.; Spera, Frank J.; Dobson, Patrick F.

1993-01-01

The isotopic composition of lavas from oceanic islands provides important information about the composition and evolution of the earth's mantle. Isotopic analyses of Miocene comenditic, pantelleritic, and trachyphonolitic ignimbrites and lavas from the Canary islands were performed. Results provide evidence for posteruptive mobility of Rb and Sr during low temperature postemplacement interaction with circulating ground water. Calculated Sr isotope ratios define a magmatic trend in the stratigraph section. 87Sr/86Sr ratios in hydrated vitrophyte and devitrified matrix separates indicate significant posteruptive interaction with meteoric water starting soon after deposition. This process extends patchily through the entire pyroclastic flow and may be ongoing. 87Sr/86Sr ratios determined by whole rock analysis of silicic rocks from oceanic islands are suspect and should not be incorporated into mantle tracer studies. Anorthoclase phenocrysts are resistant to these processes and may produce useful data.

The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

NASA Astrophysics Data System (ADS)

von Sperber, C.; Tamburini, F.; Bernasconi, S. M.; Frossard, E.

2013-12-01

Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi) (1-2). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. The enzymatic hydrolysis leads, via a nucleophilic attack, to the incorporation of one oxygen atom from the water into the newly formed Pi molecule. During the incorporation, an isotopic fractionation occurs, which might be used to identify the origin of Pi in the environment (3-6). While the effect of phosphomonoesterases and phosphodiesterases on the oxygen isotope composition of phosphate has been examined, there are, so far, no studies dealing with the effect of phytases (4-6). Phytases catalyze the hydrolysis of myo-inositol-hexakis-phosphate (IP6), which is an important component of organic P in many ecosystems (7). Enzymatic assays with phytase from wheat germ and Aspergillus niger were prepared under sterile and temperature controlled conditions in order to determine the effect of phytases on the oxygen isotope composition of phosphate, which has been liberated from IP6 via enzymatic hydrolysis. Assays with phytase from wheat germ lead to a turnover of the substrate close to 100%, while assays with phytase from Aspergillus niger lead to a turnover of the substrate close to 80%. In the case of the assays with phytase from wheat germ, our results indicate that one sixth of the total 24 oxygen which are associated to the phosphates in IP6 are exchanged with oxygen from water. From this we conclude that the incorporation of one oxygen atom from water occurs only at four phosphate molecules of IP6, while two phosphate molecules do not experience an incorporation of oxygen. This suggests that during the enzymatic hydrolysis, four P-O bonds and two C-O bonds are broken. Provided that, the isotopic fractionation can be calculated with an isotopic mass balance resulting in -8.4‰ (×3.6 SD). This is a value very similar to those reported for acid phosphatases (6). In contrast, the results from assays with phytase from Aspergillus niger indicate that the exchange of oxygen occurs at more than one third of the total 24 oxygen which are associated to the phosphates in IP6. In addition, we observe a change in the oxygen isotope composition of Pi when using myo-inositol and potassium-dihydrogen-phosphate as sole substrates in the enzymatic assays with phytase from Aspergillus niger. These observations suggest that the reformation of IP6 from the two products of the reaction (myo-inositol and Pi) is taking place at a rate, which is within the time scale of the experiment. In this case, the isotopic fractionation caused by phytase from Aspergillus niger will be determined by the equilibrium of the reaction. Further experiments are in process to verify these findings.

Mantle End-Members: The Trace Element Perspective

NASA Astrophysics Data System (ADS)

Willbold, M.; Stracke, A.; Hofmann, A. W.

2004-12-01

On the basis of their isotopic composition, ocean island basalts (OIB) have been classified into three to four end-members; HIMU with the most radiogenic Pb isotope ratios of OIB and Enriched Mantle 1 and 2 (EM1, EM2) with less radiogenic but variable Pb isotope and highly radiogenic Sr isotope signatures. It has also been argued that each of these isotopic families has common trace element characteristics that distinguish them from one another and so substantiated this classification. Here, we present new high-precision trace element data for samples from St. Helena, Tristan da Cunha and Gough in the Atlantic Ocean. The overall data-set is augmented by OIB data from the GEOROC database and includes data from all major isotopic families (HIMU: St. Helena, Mangaia, Tubuai, and Rururtu; EM1: Tristan da Cunha, Gough, Pitcairn; and EM2: Samoa, Marquesas, and Society). For each locality we use only islands defining the most extreme isotopic compositions. The entire data-set has been screened to exclude altered and highly differentiated samples. HIMU basalts have a very uniform trace element composition. Compared to HIMU-type basalts, EM-type basalts are enriched in Rb, Ba, and K, and depleted in U, Nb, and Ta, relative to La. Different EM-type OIBs from the same isotopic family (EM1 or EM2), have distinct trace element characteristics that can ultimately only be caused by different source compositions. For example, Ba/Th ratios in samples from both Tristan da Cunha (EM1) and Samoa (EM2) are similarly high (ca. 110) whereas Ba/Th ratios in samples from Pitcairn (EM1) and Society (EM2) samples are consistently lower (ca. 70). Thus on the basis of their trace element composition, EM-type OIB cannot be classified into EM1 and EM2 type basalts, nor can any other grouping be identified. The remarkably uniform isotopic and trace element composition of HIMU-type basalts suggests derivation from a single common source reservoir, most likely subduction-modified oceanic crust. Although there are some trace element characteristics common to all EM-type basalts, which distinguish them from HIMU-type basalts (e.g. uniformly high Th/U ratios of 4.7 ± 0.3, and enrichment in Cs-U), each suite of EM-type basalts has unique trace element signatures that distinguish them from any other suite of EM-type basalts. This is especially obvious when comparing the trace element composition of EM basalts from one isotopic family, for example EM1-type basalts from Tristan, Gough and Pitcairn. Consequently, the trace element systematics of EM-type basalts suggest that there are many different EM-type sources, whereas the isotopic composition of EM-type basalts suggest derivation from two broadly similar sources, i.e. EM1 and EM2. The large variability in subducting sediments with respect to both parent-daughter (e.g. Rb/Sr, Sm/Nd, U/Pb, Th/Pb,...) and other trace element ratios makes it unlikely that there are reproducible mixtures of sediments leading to two different isotopic evolution paths (EM1 and EM2) while preserving a range of incompatible element contents for each isotopic family, as would be required to reconcile the isotopic and trace element characteristics of EM-type basalts. Although this does not a priori argue against sediments as possible source components for OIB, it does argue against two distinct groups of sediments as EM1 and EM2 sources. Further characterization of sources with the same general origin (e.g. a certain type of crust or lithosphere) or identification of processes leading to reservoirs with similar parent-daughter ratio characteristics but different incompatible trace element contents could resolve the apparent conundrum.

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.

THE NITROGEN ISOTOPIC COMPOSITION OF METEORITIC HCN

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

Pizzarello, Sandra, E-mail: pizzar@asu.edu

2014-12-01

HCN is ubiquitous in extraterrestrial environments and is central to current theories on the origin of early solar system organic compounds such as amino acids. These compounds, observed in carbonaceous meteorites, were likely important in the origin and/or evolution of early life. As part of our attempts to understand the origin(s) of meteoritic CN{sup –}, we have analyzed the {sup 15}N/{sup 14}N isotopic composition of HCN gas released from water extracts of the Murchison meteorite and found its value to be near those of the terrestrial atmosphere. The findings, when evaluated viz-a-viz molecular abundances and isotopic data of meteoritic organicmore » compounds, suggest that HCN formation could have occurred during the protracted water alteration processes known to have affected the mineralogy of many asteroidal bodies during their solar residence. This was an active synthetic stage, which likely involved simple gasses, organic molecules, their presolar precursors, as well as mineral catalysts and would have lead to the formation of molecules of differing isotopic composition, including some with solar values.« less

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Mechanisms controlling the silicon isotopic compositions of river waters

NASA Astrophysics Data System (ADS)

Georg, R. B.; Reynolds, B. C.; Frank, M.; Halliday, A. N.

2006-09-01

It has been proposed that silicon (Si) isotopes are fractionated during weathering and biological activity leading to heavy dissolved riverine compositions. In this study, the first seasonal variations of stable isotope compositions of dissolved riverine Si are reported and compared with concomitant changes in water chemistry. Four different rivers in Switzerland were sampled between March 2004 and July 2005. The unique high-resolution multi-collector ICP-MS Nu1700, has been used to provide simultaneous interference-free measurements of 28Si, 29Si and 30Si abundances with an average limiting precision of ± 0.04‰ on δ 30Si. This precision facilitates the clarification of small temporal variations in isotope composition. The average of all the data for the 40 samples is δ 30Si = + 0.84 ± 0.19‰ (± 1σ SD). Despite significant differences in catchment lithologies, biomass, climate, total dissolved solids and weathering fluxes the averaged isotopic composition of dissolved Si in each river is strikingly similar with means of + 0.70 ± 0.12‰ for the Birs,+ 0.95 ± 0.22‰ for the Saane,+ 0.93 ± 0.12‰ for the Ticino and + 0.79 ± 0.19‰ for the Verzasca. However, the δ 30Si undergoes seasonal variations of up to 0.6‰. Comparisons between δ 30Si and physico-chemical parameters, such as the concentration of dissolved Si and other cations, the discharge of the rivers, and the resulting weathering fluxes, permits an understanding of the processes that control the Si budget and the fate of dissolved Si within these rivers. The main mechanism controlling the Si isotope composition of the mountainous Verzasca River appears to be a two component mixing between the seepage of soil/ground waters, with heavier Si produced by clay formation and superficial runoff associated with lighter Si during high discharge events. A biologically-mediated fractionation can be excluded in this particular river system. The other rivers display increasing complexity with increases in the proportion of forested and cultivated landscapes as well as carbonate rocks in the catchment. In these instances it is impossible to resolve the extent of the isotopic fractionation and contributed flux of Si contributed by biological processes as opposed to abiotic weathering. The presence of seasonal variations in Si isotope composition in mountainous rivers provides evidence that extreme changes in climate affect the overall composition of dissolved Si delivered to the oceans. The oceanic Si isotope composition is very sensitive to even small changes in the riverine Si isotope composition and this parameter appears to be more critical than plausible changes in the Si flux. Therefore, concurrent changes in weathering style may need to be considered when using the Si isotopic compositions of diatoms, sponges and radiolaria as paleoproductivity proxies.

Pb, Sr, and Nd isotopic compositions of a suite of Large Archean, igneous rocks, eastern Beartooth Mountains - Implications for crust-mantle evolution

NASA Technical Reports Server (NTRS)

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

1988-01-01

Compositionally diverse Late Archean rocks (2.74-2.79 Ga old) from the eastern Beartooth Mountains (Montana and Wyoming) were studied and shown to have the same initial Pb, Sr, and Nd isotopic ratios. Lead and Sr initial ratios are higher and Nd initial values lower than predicted for rocks derived from model mantle sources and strongly indicate the involvement of an older crustal reservoir in the genesis of these rocks. A model involving subduction of continental detritus and contamination of the overlying mantle is suggested.

Lead and zinc dust depositions from ore trains characterised using lead isotopic compositions.

PubMed

Kristensen, L J; Taylor, M P; Morrison, A L

2015-03-01

This study investigates an unusual source of environmental lead contamination - the emission and deposition of lead and zinc concentrates along train lines into and out of Australia's oldest silver-lead-zinc mine at Broken Hill, Australia. Transport of lead and zinc ore concentrates from the Broken Hill mines has occurred for more than 125 years, during which time the majority was moved in uncovered rail wagons. A significant amount of ore was lost to the adjoining environments, resulting in soil immediately adjacent to train lines elevated with concentrations of lead (695 mg kg(-1)) and zinc (2230 mg kg(-1)). Concentrations of lead and zinc decreased away from the train line and also with depth shown in soil profiles. Lead isotopic compositions demonstrated the soil lead contained Broken Hill ore in increasing percentages closer to the train line, with up to 97% apportioned to the mined Broken Hill ore body. SEM examination showed ceiling dusts collected from houses along the train line were composed of unweathered galena particles, characteristic of the concentrate transported in the rail wagons. The loss of ore from the uncovered wagons has significantly extended the environmental footprint of contamination from local mining operations over an area extending hundreds of kilometres along each of the three train lines.

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

USGS Publications Warehouse

Shuai, Yanhua; Douglas, Peter M.J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-01-01

Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

Chemical data and lead isotopic compositions of geochemical baseline samples from streambed sediments and smelter slag, lead isotopic compositions in fluvial tailings, and dendrochronology results from the Boulder River watershed, Jefferson County, Montana

USGS Publications Warehouse

Unruh, Daniel M.; Fey, David L.; Church, Stan E.

2000-01-01

IntroductionAs a part of the U.S. Geological Survey Abandoned Mine Lands Initiative, metal-mining related wastes in the Boulder River study area in northern Jefferson County, Montana, have been evaluated for their environmental effects. The study area includes a 24-km segment of the Boulder River in and around Basin, Montana and three principal tributaries to the Boulder River: Basin Creek, Cataract Creek, and High Ore Creek. Mine and prospect waste dumps and mill wastes are located throughout the drainage basins of these tributaries and in the Boulder River. Mine-waste material has been transported into and down streams, where it has mixed with and become incorporated into the streambed sediments. In some localities, mine waste material was placed directly in stream channels and was transported downstream forming fluvial tailings deposits along the stream banks. Water quality and aquatic habitat have been affected by trace-element-contaminated sediment that moves from mine wastes into and down streams during snowmelt and storm runoff events within the Boulder River watershed.Present-day trace element concentrations in the streambed sediments and fluvial tailings have been extensively studied. However, in order to accurately evaluate the impact of mining on the stream environments, it is also necessary to evaluate the pre-mining trace-element concentrations in the streambed sediments. Three types of samples have been collected for estimation of pre-mining concentrations: 1) streambed sediment samples from the Boulder River and its tributaries located upstream from historical mining activity, 2) stream terrace deposits located both upstream and downstream of the major tributaries along the Boulder River, and 3) cores through sediment in overbank deposits, in abandoned stream channels, or beneath fluvial tailings deposits. In this report, we present geochemical data for six stream-terrace samples and twelve sediment-core samples and lead isotopic data for six terrace and thirteen core samples. Sample localities are in table 1 and figures 1 and 2, and site and sample descriptions are in table 2.Geochemical data have been presented for cores through fluvial tailings on High Ore Creek, on upper Basin Creek, and on Jack Creek and Uncle Sam Gulch. Geochemical and lead isotopic data for modern streambed-sediment samples have been presented by Fey and others.Lead isotopic determinations in bed sediments have been shown to be an effective tool for evaluating the contributions from various sources to the metals in bed sediments. However, in order to make these calculations, the lead isotopic compositions of the contaminant sources must also be known. Consequently, we have determined the lead isotopic compositions of five streambed-sediment samples heavily contaminated with fluvial mine waste immediately downstream from large mines in the Boulder River watershed in order to determine the lead isotopic signatures of the contaminants. Summary geochemical data for the contaminants are presented here and geochemical data for the streambed-sediment samples are given by Fey and others.Downstream from the Katie mill site and Jib tailings, fluvial deposits of mill tailings are present on a 10-m by 50-m bar in the Boulder River below the confluence with Basin Creek. The source of these tailings is not known, but fluvial tailings are also present immediately downstream from the Katie mill site, which is immediately upstream from the confluence with Basin Creek. Nine cores of fluvial tailings from this bar were analyzed.Dendrochronology samples were taken at several stream terrace localities to provide age control on the stream terrace deposits. Trees growing on the surfaces of stream terraces provide a minimum age for the terrace deposits, although floods subsequent to the trees' growth could have deposited post-mining overbank deposits around the trees. Historical data were also used to provide estimates of minimum ages of cultural features and to bracket the age of events.

Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary

PubMed Central

Chen, Mengli; Lee, Jong-Mi; Nurhati, Intan; Zurbrick, Cheryl; Switzer, Adam D.; Carrasco, Gonzalo

2016-01-01

Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035266

Testing sequential extraction methods for the analysis of multiple stable isotope systems from a bone sample

NASA Astrophysics Data System (ADS)

Sahlstedt, Elina; Arppe, Laura

2017-04-01

Stable isotope composition of bones, analysed either from the mineral phase (hydroxyapatite) or from the organic phase (mainly collagen) carry important climatological and ecological information and are therefore widely used in paleontological and archaeological research. For the analysis of the stable isotope compositions, both of the phases, hydroxyapatite and collagen, have their more or less well established separation and analytical techniques. Recent development in IRMS and wet chemical extraction methods have facilitated the analysis of very small bone fractions (500 μg or less starting material) for PO43-O isotope composition. However, the uniqueness and (pre-) historical value of each archaeological and paleontological finding lead to preciously little material available for stable isotope analyses, encouraging further development of microanalytical methods for the use of stable isotope analyses. Here we present the first results in developing extraction methods for combining collagen C- and N-isotope analyses to PO43-O-isotope analyses from a single bone sample fraction. We tested sequential extraction starting with dilute acid demineralization and collection of both collagen and PO43-fractions, followed by further purification step by H2O2 (PO43-fraction). First results show that bone sample separates as small as 2 mg may be analysed for their δ15N, δ13C and δ18OPO4 values. The method may be incorporated in detailed investigation of sequentially developing skeletal material such as teeth, potentially allowing for the investigation of interannual variability in climatological/environmental signals or investigation of the early life history of an individual.

Reconstruction of Late Quaternary Climate in Central Europe - A Comparison of Stable Isotope and Trace Element Variations in Speleothems From Different Cave Systems in Germany.

NASA Astrophysics Data System (ADS)

Nordhoff, P.; Wiegand, B.; Simon, K.; Rosendahl, W.; Hansen, B. T.; Kempe, S.

2003-12-01

Speleothems (stalagmites, stalactites, flowstones) are important archives for Late Quaternary continental climatic and paleo-environmental reconstruction. Speleothems form when calcium carbonate precipitates from solutions seeping into caves hosted e.g. in limestone or dolomite complexes. Information of past climate variability and changes in local environmental conditions can be obtained from signatures of the stable isotopes of oxygen and carbon as well as trace element pattern recorded in speleothems. Reconstruction of paleo-temperature and past environmental conditions from stable isotopes, however, require isotopic equilibrium between the drip water and the precipitating calcium carbonate. Results from Dietzel et al. (1992) and Johnson and Ingram (2001) indicate that the formation of modern travertine and speleothem calcite occurs under isotopic equilibrium. Factors that influence the stable oxygen and carbon isotope composition during speleothem precipitation include e.g. the moisture source and precipitation, photosynthetic pathways, the bedrock proportion, and the drip rate. This often leads to a situation with several variables. However, a specific interpretation is possible when dealing with environments where only one of the factors is dominant, or specific settings are assumed to be invariant, or further proxies like trace element variations help to define the frame conditions during speleothem formation. Concentrations of trace elements (e.g. Sr, Mg) which are co-precipitated with calcite are related to changes in the composition of the solution and strongly depend on the dissolution/precipitation dynamics along drip water flow paths. In a multiproxy approach they are a valuable tool for the interpretation of the recorded stable isotope variations. We present first results from different cave systems located in the Swabian Alps and the Harz Mountains (Germany). Our study includes a high-resolution multiproxy approach, using U/Th-TIMS data, stable oxygen/carbon isotope data, and geochemical compositions of speleothems, covering ages from the Late Pleistocene to the Early Holocene. The results are compared to geochemical data from host rocks, soil zones, cave sediments, drip water compositions, and recent calcium carbonate precipitates. Understanding the response of a cave system to the actual climatic, hydrologic and environmental regimen is a main requirement for the interpretation of "paleo-information" conserved in speleothems in order to lead to a coherent picture of past continental climate dynamics. References: Dietzel M., Usdowski E., and Hoefs J., (1992): Applied Geochemistry 7: 177-184. Johnson, K.R. and Ingram, B.L. (2001): Abstract volume, 4th Internat. Symp. On Applied Isotope Geochemistry, Pacific Groove, USA: 70-72.

Plio-Pleistocene evolution of water mass exchange and erosional input at the Atlantic-Arctic gateway

NASA Astrophysics Data System (ADS)

Teschner, Claudia; Frank, Martin; Haley, Brian A.; Knies, Jochen

2016-05-01

Water mass exchange between the Arctic Ocean and the Norwegian-Greenland Seas has played an important role for the Atlantic thermohaline circulation and Northern Hemisphere climate. We reconstruct past water mass mixing and erosional inputs from the radiogenic isotope compositions of neodymium (Nd), lead (Pb), and strontium (Sr) at Ocean Drilling Program site 911 (leg 151) from 906 m water depth on Yermak Plateau in the Fram Strait over the past 5.2 Myr. The isotopic compositions of past bottom waters were extracted from authigenic oxyhydroxide coatings of the bulk sediments. Neodymium isotope signatures obtained from surface sediments agree well with present-day deepwater ɛNd signature of -11.0 ± 0.2. Prior to 2.7 Ma the Nd and Pb isotope compositions of the bottom waters only show small variations indicative of a consistent influence of Atlantic waters. Since the major intensification of the Northern Hemisphere Glaciation at 2.7 Ma the seawater Nd isotope composition has varied more pronouncedly due to changes in weathering inputs related to the waxing and waning of the ice sheets on Svalbard, the Barents Sea, and the Eurasian shelf, due to changes in water mass exchange and due to the increasing supply of ice-rafted debris (IRD) originating from the Arctic Ocean. The seawater Pb isotope record also exhibits a higher short-term variability after 2.7 Ma, but there is also a trend toward more radiogenic values, which reflects a combination of changes in input sources and enhanced incongruent weathering inputs of Pb released from freshly eroded old continental rocks.

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.

LEAD POISONING IN LAYSAN ALBATROSS (PHOESBASTRIA IMMUTABILIS) CHICKS: EVALUATION OF CONTAMINANT SOURCES ON MIDWAY ATOLL USING STABLE LEAD ISOTOPIC COMPOSITION. (U915730)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios.

PubMed

Yoo, Eun-Jin; Lee, Jung-A; Park, Jae-Seon; Lee, Khanghyun; Lee, Won-Seok; Han, Jin-Seok; Choi, Jong-Woo

2014-02-01

This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the (203)Tl/(205)Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios ((207)Pb/(206)Pb) found were 0.85073 ± 0.0004~0.85373 ± 0.0003 for the main stream, while they were 0.83736 ± 0.0010 for the tributary and 0.84393 ± 0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60%. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.

Historic and Industrial Lead within the Northwest Pacific Ocean Evidenced by Lead Isotopes in Seawater.

PubMed

Zurbrick, Cheryl M; Gallon, Céline; Flegal, A Russell

2017-02-07

We report the continued lead (Pb) contamination of the Northwest Pacific Ocean in 2002 and present the first comprehensive Pb isotope data set for that region. In the upper ocean, a Pb concentration maxima (64-113 pmol kg -1 ) extended throughout the entire North Pacific Subtropical Gyre (NPSG). We determined most of the Pb in this feature was from industrial emissions by many nations in the 1980s and 1990s, with the largest contributions from leaded gasoline emissions. In contrast, the deep water (>1000 m) Pb concentrations were lower (6-37 pmol kg -1 ), and constituted a mix of background (natural) Pb and anthropogenic Pb inputs from preceding decades. Deep water below the Western Subarctic Gyre (WSAG) contained more industrial Pb than below the NPSG, which was attributed to a calculated 60-fold greater flux of particulate Pb to abyssal waters near the Asian continent. Assuming Pb isotope compositions in the North Pacific Ocean were homogeneous prior to large-scale 20th century anthropogenic inputs, this evidence suggests a relatively faster change in Pb isotope ratios of North Pacific deep water below the WSAG versus the NPSG.

Coral-based history of lead and lead isotopes of the surface Indian Ocean since the mid-20th century

NASA Astrophysics Data System (ADS)

Lee, Jong-Mi; Boyle, Edward A.; Suci Nurhati, Intan; Pfeiffer, Miriam; Meltzner, Aron J.; Suwargadi, Bambang

2014-07-01

Anthropogenic lead (Pb) from industrial activities has greatly altered the distribution of Pb in the present-day oceans, but no continuous temporal Pb evolution record is available for the Indian Ocean despite rapidly emerging industries around the region. Here, we present the coral-inferred annual history of Pb concentration and isotope ratios in the surface Indian Ocean since the mid-20th century (1945-2010). We analyzed Pb in corals from the Chagos Archipelago, western Sumatra and Strait of Singapore - which represent the central Indian Ocean via nearshore sites. Overall, coral Pb/Ca increased in the mid-1970s at all the sites. However, coral Pb isotope ratios evolve distinctively at each site, suggesting Pb contamination arises from different sources in each case. The major source of Pb in the Chagos coral appears to be India's Pb emission from leaded gasoline combustion and coal burning, whereas Pb in western Sumatra seems to be largely affected by Indonesia's gasoline Pb emission with additional Pb inputs from other sources. Pb in the Strait of Singapore has complex sources and its isotopic composition does not reflect Pb from leaded gasoline combustion. Higher 206Pb/207Pb and 208Pb/207Pb ratios found at this site may reflect the contribution of Pb from coals and ores from southern China, Indonesia, and Australia, and local Pb sources in the Strait of Singapore. It is also possible that the Pb isotope ratios of Singapore seawater were elevated through isotope exchange with natural fluvial particles considering its delta setting.

Sources and drains: Major controls of hydrothermal fluid flow in the Kokanee Range, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Beaudoin, Georges; Therrien, René

1999-10-01

Vein fields are fractured domains of the lithosphere that have been infiltrated by hydrothermal fluids, which deposited minerals in response to changing physico-chemical conditions. Because oxygen is a major component of the infiltrating fluid and the surrounding rock matrix, the oxygen isotope composition of minerals found in veins is used to decipher ancient fluid flow within the lithosphere. We use a numerical model to simulate oxygen isotope transport in the Kokanee Range silver-lead-zinc vein field. The model considers advective, dispersive, and reactive transport in a three-dimensional porous rock matrix intersected by high-permeability planes representing fracture zones. Here we show that it is the geometrical configuration of the sources and of the drains of hydrothermal fluids, combined with the fracture pattern, that exerts the main control on the oxygen isotope distribution. Other factors that affect, to a lesser extent, the values and positions of oxygen isopleths are the fluids and rock-matrix isotopic compositions, the isotopic fractionation, the reaction rate constant, and hydraulic conductivities of the rock matrix and fracture zones.

Lead isotopes in trade wind aerosols at Barbados: the influence of European emissions over the North Atlantic

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

Hamelin, B.; Grousset, F.E.; Biscaye, P.E.

1989-11-15

Previous studies have shown that Pb can be used as a transient tracer in the atmosphere and the ocean because of strong time-variability of industrial inputs and because Pb isotopic composition can be used to identify contribution from different sources. We present Pb isotopic measurements on aerosols collected from the North Atlantic Ocean in the trade wind belt. Aerosols sampled at Barbados during the 1969--1985 period have a Pb isotopic compositions different from that observed by previous investigators in Bermuda corals and Sargasso Sea waters. Barbados aerosols appear to contain significant amounts of relatively unradiogenic industrial and automotive Pb thatmore » is derived from Europe and carried to Barbados by the trade winds. In contrast, Bermuda corals and Sargasso sea waters are influenced mainly by U.S.-derived emissions, which contain more radiogenic Pb originating from Missouri-type ores. This difference generates a strong latitudinal Europe-U.S.A. isotopic gradient, thus allowing study of trans-Atlantic atmospheric transport and ocean mixing processes. {copyright} American Geophysical Union 1989« less

Monitoring steel bridge renovation using lead isotopic tracing.

PubMed

Salome, Fred; Gulson, Brian; Chiaradia, Massimo; Davis, Jeffrey; Morris, Howard

2017-05-01

Monitoring removal of lead (Pb) paint from steel structures usually involves analysis of environmental samples for total lead and determination of blood Pb levels of employees involved in the Pb paint removal. We used high precision Pb isotopic tracing for a bridge undergoing Pb paint removal to determine if Pb in the environmental and blood samples originated from the bridge paint. The paint system on the bridge consisted of an anti-corrosive red Pb primer top-coated with a Micaceous Iron Oxide (MIO) alkyd. Analysis of the red Pb primer gave uniform isotopic ratios indicative of Pb from the geologically-ancient Broken Hill mines in western New South Wales, Australia. Likewise waste abrasive material, as anticipated, had the same isotopic composition as the paint. The isotopic ratios for other samples lay on 2 separate linear arrays on a 207 Pb/ 204 Pb versus 206 Pb/ 204 Pb diagram, one largely defined by gasoline and the majority of the ambient air data, and the other by data for one sample each of gasoline and ambient air and underwater sediments. Isotopic ratios in background ambient air samples for the project were characteristic of leaded gasoline. Air sampling during paint removal showed a contribution of paint Pb ranging from about 20 to 40%. Isotopic ratios in the blood of 8 employees prior to the commencement of work showed that 6 of these had been previously exposed to the Broken Hill Pb possibly from earlier bridge paint removal projects. One subject appeared to have increased exposure to Pb probably from the paint renovations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Constraining late stage melt-peridotite interaction in the lithospheric mantle of southern Ethiopia: evidence from lithium elemental and isotopic compositions

NASA Astrophysics Data System (ADS)

Alemayehu, Melesse; Zhang, Hong-Fu; Seitz, Hans-Michael

2017-10-01

Lithium (Li) elemental and isotopic compositions for mineral separates of coexisting olivine, orthopyroxene and clinopyroxene of mantle xenoliths from the Quaternary volcanic rocks of southern Ethiopian rift (Dillo and Megado) reveal the influence of late stage melt-peridotite interaction on the early depleted and variably metasomatized lithospheric mantle. Two types of lherzolites are reported (LREE-depleted La/Sm(N) = 0.11-0.37 × Cl and LREE-enriched, La/Sm(N) = 1.88-15.72 × Cl). The depleted lherzolites have variable range in Li concentration (olivine: 2.1-5.4 ppm; opx: 1.1-2.3 ppm; cpx: 1.0-1.8 ppm) and in Li isotopic composition (δ7Li in olivine: -9.4 to 1.5‰; in opx: -4.5 to 3.6‰; in cpx: -17.0 to 4.8‰), indicating strong disequilibrium in Li partitioning and Li isotope fractionation between samples. The enriched lherzolites have limited range in both Li abundances (olivine: 2.7-3.0 ppm; opx: 1.1-3.1 ppm; cpx: 1.1-2.3 ppm) and Li isotopic compositions (δ7Li in olivine: -1.3 to +1.3‰; in opx: -2.0 to +5.0‰; in cpx: -7.5 to +4.8‰), suggest that the earlier metasomatic event which lead to LREE enrichment could also homogenize the Li contents and its isotopes. The enriched harzburgite and clinopyroxenite minerals show limited variation in Li abundances and variable Li isotopic compositions. The Li enrichments of olivine and clinopyroxene correlate neither with the incompatible trace element enrichment nor with the Sr-Nd isotopic compositions of clinopyroxene. These observations indicate that the metasomatic events which are responsible for the LREE enrichment and for the Li addition are distinct, whereby the LREE-enrichment pre-dates the influx of Li. The presence of large Li isotopic disequilibria within and between minerals of depleted and enriched peridotites suggest that the lithospheric mantle beneath the southern Ethiopian rift has experienced recent melt-peridotite interaction. Thus, the Li data set reported in this study offer new additional evidence for the existence of late stage metasomatism, which probably occurred at shallow depth briefly before and/or during entrainment and ascent of mantle xenoliths to the surface.

Synanthropic Primates in Asia: Potential Sentinels for Environmental Toxins

PubMed Central

Engel, Gregory; O’Hara, Todd M.; Cardona-Marek, Tamara; Heidrich, John; Chalise, Mukesh K.; Kyes, Randall; Jones-Engel, Lisa

2010-01-01

Macaques are similar to humans both physiologically and behaviorally. In South and Southeast Asia they are also synanthropic, ecologically associated with humans. Synanthropy with humans raises the possibility that macaques come into contact with anthropogenic toxicants, such as lead and mercury, and might be appropriate sentinels for human exposures to certain toxic materials. We measured lead (Pb) and mercury (Hg) levels and characterized the stable isotopic compositions of δ15N and δ13C in hair from three groups of free-ranging macaques at the Swoyambhu temple in Kathmandhu, Nepal, an urban population that has abundant contact with humans. Hair lead levels were significantly higher among young macaques and differed among the three groups of macaques that were sampled. Hair Hg levels were low. No statistical association was found between stable isotopic compositions (δ15N and δ13C) and Pb and Hg levels. Our data did not find evidence that lead levels were associated with diet. We conclude that, in this population of macaques, behavioral and/or physiologic factors may play a significant role in determining exposure to lead. Chemical analysis of hair is a promising, noninvasive technique for determining exposure to toxic elements in free-ranging nonhuman primates. PMID:20033917

Deuterium values from volcanic glass: A paleoelevation proxy for Oregon's Cascade Range

NASA Astrophysics Data System (ADS)

Carlson, T. B.; Bershaw, J. T.

2016-12-01

Hydrated volcanic glass has been used as a proxy to constrain Cenozoic paleoclimate across many of the world's mountain ranges. However, there are concerns that volcanic glass may not preserve the isotopic composition of syndepositional meteoric water. The Cascades are an excellent location to study the validity of hydrated volcanic glass as a paleoenvironmental proxy for several reasons. Moisture is derived from a single oceanic source and falls as orographic precipitation in the Cascades, leading to a characteristic altitude effect, or inverse relationship between elevation and the isotopic composition of meteoric water (δD). In addition, past studies have inferred uplift of the Cascades and an increase in the rain shadow effect since the Eocene through independent methods such as changing fossil assemblages, and other isotopic proxies including carbonates and fossil teeth. In this study, δD values of two hydrated tuff samples are compared: one prior to ( 29 Ma) and one following ( 5 Ma) the onset of High Cascade volcanism. The isotopic composition of these samples are interpreted in the context of modern water across the range to understand the potential of volcanic glass as a proxy for paleoelevation in the Pacific Northwest.

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

USGS Publications Warehouse

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

1992-01-01

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

A two century record of lead isotopes in high altitude Alpine snow and ice

NASA Astrophysics Data System (ADS)

Rosman, K. J. R.; Ly, C.; Van de Velde, K.; Boutron, C. F.

2000-03-01

A 140 m snow/ice core drilled at Mont Blanc, France, has been analysed for Pb isotopes, Pb and Ba concentrations. The 206Pb/ 207Pb ratio, which was measured by thermal ionisation mass spectrometry, decreased steadily from ˜1.18 about two centuries ago to ˜1.17 in 1960, then fell rapidly to ˜1.15 by 1968. Evidence of the Italian (Turin) isotopic lead experiment (IILE) was found in samples dated ˜1977 where the ratio dipped to 1.117. By the early 1990s it had returned to mid 1960s values. Large seasonal variations were found in Pb and Ba concentrations. Summer samples were associated with smooth changes in the 206Pb/ 207Pb ratio while larger fluctuations were encountered in winter which is consistent with a low altitude inversion near Mont Blanc in the winter and free transfer of pollutants from lower to higher altitudes at other times. A plot of 208Pb/ 207Pb versus 206Pb/ 207Pb ratios reveals three isotopic groupings, associated with the periods pre-1923, 1923-1968 and 1969-1991. In the first group, the isotopic composition is consistent with local mining, smelting and coal burning, while in the second, motor vehicle exhaust emissions dominate. In the third group, motor vehicle emissions also dominate but the Pb is even less radiogenic. During this period the IILE occurred and there was a reduction in the use of leaded gasoline in Europe. A comparison of the Mont Blanc and Summit (central Greenland) records shows they contain similar 206Pb/ 207Pb ratios between 1960 and 1968, although small differences in isotopic composition can be detected by also considering the 208Pb/ 207Pb ratio. However, after 1969 the two records diverge markedly, with the Greenland ratios being dominated by the highly radiogenic Mississippi valley-type Pb from the USA and with the Mont Blanc ratios moving to lower values particularly about the time of the IILE.

Pyroxene Homogenization and the Isotopic Systematics of Eucrites

NASA Technical Reports Server (NTRS)

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

1996-01-01

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

Metasomatism-induced magnesium isotope fractionation in ultramafic rocks: Evidence from the Franciscan Complex, California

NASA Astrophysics Data System (ADS)

Li, W. Y.; Teng, F. Z.; Xiao, Y.

2016-12-01

To investigate the behaviour of Mg isotopes during metasomatic reactions between peridotites and infiltrating fluids along the slab-mantle interface, we analyzed Mg isotopic compositions of a set of well-characterized samples from the ultramafic blocks in the Franciscan Complex of California [1]. The Group 1 and Group 2 samples that were defined by the initial serpentinization and complete serpentinization of peridotites at temperatures of 450-500 ºC, respectively [1], have δ26Mg values (from -0.26 to -0.14‰) clustered around the mantle value. This suggests that Mg isotope fractionation during serpentinization by slab-derived fluids, if any, is small. By contrast, the Group 3 samples that were defined by the replacement of serpentine by talc [1], are enriched in heavy Mg isotopes (δ26Mg of -0.13 to -0.01‰). This may reflect the loss of light Mg isotopes into fluids during the dehydration reaction that produced talc from serpentine, which is consistent with previous observations that secondary clay minerals preferentially incorporate heavy Mg isotopes during water-rock interactions [2, 3]. The Group 4 samples that were defined by the further replacement of talc by tremolite [1], however, have light Mg isotopic compositions (δ26Mg of -0.50 to -0.41‰). Such a shift towards light Mg isotopic compositions likely results from metasomatism by fluids that derived from isotopically light carbonates, which is supported by the remarkably higher CaO content of Group 4 samples (from 6.9 to 9.2 wt%) than Group 3 ones (from 1.1 to 1.4 wt%). Collectively, significant Mg isotopic variations occur during metasomatism of peridotites in the mantle wedge, which would potentially lead to heterogeneous Mg isotopic compositions in arc lavas [4]. Therefore, Mg isotopes can be used as a powerful tracer of crust-mantle interaction at subduction zones. [1] King et al. (2003) Geol. Soc. Am. Bull. 115, 1097-1109. [2] Teng et al. (2010) Earth Planet. Sci. Lett. 300, 63-71. [3] Wimpenny et al. (2014) Geochim. Cosmochim. Acta 128, 178-194. [4] Teng et al. (2016) Proc. Natl. Acad. Sci. 113, 7082-7087. et al. (2016) Proc. Natl. Acad. Sci. 113, 7082-7087.

Isotope effect of mercury diffusion in air

PubMed Central

Koster van Groos, Paul G.; Esser, Bradley K.; Williams, Ross W.; Hunt, James R.

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature. PMID:24364380

Isotope effect of mercury diffusion in air.

PubMed

Koster van Groos, Paul G; Esser, Bradley K; Williams, Ross W; Hunt, James R

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature.

Product ion isotopologue pattern: A tool to improve the reliability of elemental composition elucidations of unknown compounds in complex matrices.

PubMed

Kaufmann, A; Walker, S; Mol, G

2016-04-15

Elucidation of the elemental compositions of unknown compounds (e.g., in metabolomics) generally relies on the availability of accurate masses and isotopic ratios. This study focuses on the information provided by the abundance ratio within a product ion pair (monoisotopic versus the first isotopic peak) when isolating and fragmenting the first isotopic ion (first isotopic mass spectrum) of the precursor. This process relies on the capability of the quadrupole within the Q Orbitrap instrument to isolate a very narrow mass window. Selecting only the first isotopic peak (first isotopic mass spectrum) leads to the observation of a unique product ion pair. The lighter ion within such an isotopologue pair is monoisotopic, while the heavier ion contains a single carbon isotope. The observed abundance ratio is governed by the percentage of carbon atoms lost during the fragmentation and can be described by a hypergeometric distribution. The observed carbon isotopologue abundance ratio (product ion isotopologue pattern) gives reliable information regarding the percentage of carbon atoms lost in the fragmentation process. It therefore facilitates the elucidation of the involved precursor and product ions. Unlike conventional isotopic abundances, the product ion isotopologue pattern is hardly affected by isobaric interferences. Furthermore, the appearance of these pairs greatly aids in cleaning up a 'matrix-contaminated' product ion spectrum. The product ion isotopologue pattern is a valuable tool for structural elucidation. It increases confidence in results and permits structural elucidations for heavier ions. This tool is also very useful in elucidating the elemental composition of product ions. Such information is highly valued in the field of multi-residue analysis, where the accurate mass of product ions is required for the confirmation process. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

O and C stable isotopes in cryogenic cave calcite (CCC) - possible proxy for past climate changes

NASA Astrophysics Data System (ADS)

-Andreea, Badaluta Carmen; Ersek, Vasile; Piotrowska, Natalia; Persoiu, Aurel

2017-04-01

Perennial ice deposits in caves host various proxies of past climate variability, most notable, the isotopic composition of ice, which has been shown to reflect, generally, the temperature outside the cave during the formation of ice (usually, autumn though spring). This ice forms by the freezing of water, water that contains large amounts of dissolved calcium carbonate. The freezing is accompanied by degassing of CO2, and precipitation of cryogenic cave calcite (CCC) under strong kinetic conditions. These kinetic processes could lead to the alteration of the original putative climatic signal carried by the isotopic composition of CCC. Here, we present a possibly climatic explanation of the isotopic composition of CCC from a 1000 years old cave ice deposit from Scărișoara Ice Cave (SIC) in Romania, Eastern Europe. In a 7 m core from the Great Hall of SIC we have analyzed the isotopic composition of the water (oxygen and hydrogen) and CCC (oxygen and carbon) from individual ice layers in the core, as well as that of precipitation , outside the cave. The isotopic composition of precipitation from the cave area varies between -3.6 ‰ for δˡ⁸O and -22 ‰ for δ2H in summer, and -17.8 ‰ for δˡ⁸O and -22 ‰ for δ2H in winter, with mean values of -9.1 ‰ for δˡ⁸O and -62 ‰ for δ2H. A positive correlation between air temperature and the isotopic composition of precipitation, as well as drip water in the cave has been found. The mean values in the ice core during the past 1000 years are -10.3‰ for δ18O and -71 ‰ for δ2H. The water isotopic values in the ice core show low values up to 900 AD, higher values between 900 and 1300 AD (Medieval Warm Period, MWP), and again lower values after 1300 AD (Little Ice Age, LIA), reaching their minimum after 1800 AD. The isotopic composition of CCC shows slightly higher values in the MWP and lower in LIA, possibly suggesting a climatic influence. Modern observations are too short to be able to calibrate this putative signal. Further, clumped isotope thermometry has shown that the kinetic fractionation that dominates during the freezing of water leads to unusual reconstructed formative temperature: +20°C. However, δˡ3C and δˡ⁸O values in CCC have higher values for samples from the MWP than those from the LIA. CCC results from the deposition of CaCO3 from Ca(CO3)2. The main source of CO2 to form carbonic acid is soil CO2, produced by root respiration. Previous studies have shown that δˡ⁸O of this CO2 is in equilibrium with the δˡ⁸O of water, so that the higher (lower) δˡ⁸O values of CCC could reflect warmer (colder) conditions during the MPW (LIA). The interpretation of δˡ3C values of CCC is less straightforward. Higher δˡ3C values in soil CO2 are determined by moisture limitation on plants, either due to low moisture or higher evaporative conditions. While the MWP was warmer in the study area, conflicting data exists on precipitation, with studies suggesting both drier and wetter conditions, so that is difficult to interpret our carbon isotope data. Apart from the direct climatic influence, the depth of soil could have also played a part, as deeper soils, as expected under birch forests that dominated during the MWP, would have had more enrichment in the heavy isotopes with depth, than the thiner soils of the LIA (formed under mostly spruce forests). Further, drought/higher temperatures could also influence the kinetics of the reaction, which can be large enough to overprint any soil signal in δˡ3C.

Multi isotopic characterization (Li-Cu-Zn-Pb) of waste waters pollution in a small watershed (Loire River basin, France)

NASA Astrophysics Data System (ADS)

Millot, R.; Desaulty, A. M.; Perret, S.; Bourrain, X.

2016-12-01

The goal of this study is to use multi-isotopic signature to track the pollution in surface waters, and to understand the complex processes causing the metals mobilization and transport in the environment. In the present study, we investigate waste water releases from a hospital water treatment plant and its potential impact in a small river basin near Orléans in France (Egoutier watershed: 15 km²and 5 km long). We decided to monitor this small watershed which is poorly urbanized in the Loire river basin. Its spring is located in a pristine area (forested area), while it is only impacted some kilometers further by the releases rich in metals coming from a hospital water treatment plant. A sampling of these liquid effluents as well as dissolved load and sediment from upstream to downstream was realized and their concentrations and isotopic data were determined. Isotopic ratios were measured using a MC-ICP-MS at BRGM, after a specific protocol of purification for each isotopic systematics. Lithium isotopic compositions are rather homogeneous in river waters along the main course of the stream. The waste water signal is very different from the natural background with significant heavy lithium contribution (high δ7Li). Lead isotopic compositions are rather homogenous in river waters and sediments with values close to geologic background. For Zn, the sediments with high concentrations and depleted isotopic compositions (low δ66Zn), typical of an anthropic pollution, are strongly impacted. The analyses of Cu isotopes in sediments show the impact of waster waters, but also isotopic fractionations due to redox processes in the watershed. To better understand these processes controlling the release of metals in water, sequential extractions on sediments are in progress under laboratory conditions and will provide important constraints for metal distribution in this river basin.

Formation of medical radioisotopes 111In, 117 m Sn, 124Sb, and 177Lu in photonuclear reactions

NASA Astrophysics Data System (ADS)

Danagulyan, A. S.; Hovhannisyan, G. H.; Bakhshiyan, T. M.; Avagyan, R. H.; Avetisyan, A. E.; Kerobyan, I. A.; Dallakyan, R. K.

2015-06-01

The possibility of the photonuclear production of radioisotopes 111In, 117 m Sn, 124Sb, and 177Lu is discussed. Reaction yields were measured by the gamma-activation method. The enriched tin isotopes 112, 118Sn and Te and HfO2 of natural isotopic composition were used as targets. The targets were irradiated at the linear electron accelerator of Alikhanian National Science Laboratory (Yerevan) at the energy of 40 MeV. The experimental results obtained in this way reveal that the yield and purity of radioisotopes 111In and 117 mSn are acceptable for their production via photonuclear reactions. Reactions proceeding on targets from Te and HfO2 of natural isotopic composition and leading to the formation of 124Sb and 177Lu have small yields and are hardly appropriate for the photoproduction of these radioisotopes even in the case of enriched targets.

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

Monna, F.; Aiuppa, A.; Varrica, D.

A total of 25 lichen thalli of Parmelia conspersa (Ehrh), collected at Vulcano island and at Mt. Etna, during a one-year biogeochemical survey, were analyzed for Pb, br, Al, Sc,[sup 206]Pb/[sup 207]Pb, and [sup 208]Pb/[sup 206]Pb ratios. Lead isotope ratios were also measured on aerosol samples from urban areas and industrial sites of Sicily. The observed [sup 206]Pb/[sup 207]Pb range for urban and industrial aerosols matches the anthropogenic signature. Lichens instead, are closer to the compositional field of [sup 206]Pb rich geogenic sources. This natural input is more evident at Vulcano island than at Mt. Etna, where the anthropogenic activitiesmore » are considerably more effective. On the basis of lead isotope data, Pb/Br ratios and calculated lead enrichment factors, a natural lead pollution from volcanoes is suggested. Volcanic lead contribution ranges from 10 to 30% at Mt. Etna to 10--80% at Vulcano island.« less

Monitoring Lead (Pb) Pollution and Identifying Pb Pollution Sources in Japan Using Stable Pb Isotope Analysis with Kidneys of Wild Rats.

PubMed

Nakata, Hokuto; Nakayama, Shouta M M; Oroszlany, Balazs; Ikenaka, Yoshinori; Mizukawa, Hazuki; Tanaka, Kazuyuki; Harunari, Tsunehito; Tanikawa, Tsutomu; Darwish, Wageh Sobhy; Yohannes, Yared B; Saengtienchai, Aksorn; Ishizuka, Mayumi

2017-01-10

Although Japan has been considered to have little lead (Pb) pollution in modern times, the actual pollution situation is unclear. The present study aims to investigate the extent of Pb pollution and to identify the pollution sources in Japan using stable Pb isotope analysis with kidneys of wild rats. Wild brown ( Rattus norvegicus , n = 43) and black ( R. rattus , n = 98) rats were trapped from various sites in Japan. Mean Pb concentrations in the kidneys of rats from Okinawa (15.58 mg/kg, dry weight), Aichi (10.83), Niigata (10.62), Fukuoka (8.09), Ibaraki (5.06), Kyoto (4.58), Osaka (4.57), Kanagawa (3.42), and Tokyo (3.40) were above the threshold (2.50) for histological kidney changes. Similarly, compared with the previous report, it was regarded that even structural and functional kidney damage as well as neurotoxicity have spread among rats in Japan. Additionally, the possibility of human exposure to a high level of Pb was assumed. In regard to stable Pb isotope analysis, distinctive values of stable Pb isotope ratios (Pb-IRs) were detected in some kidney samples with Pb levels above 5.0 mg/kg. This result indicated that composite factors are involved in Pb pollution. However, the identification of a concrete pollution source has not been accomplished due to limited differences among previously reported values of Pb isotope composition in circulating Pb products. Namely, the current study established the limit of Pb isotope analysis for source identification. Further detailed research about monitoring Pb pollution in Japan and the demonstration of a novel method to identify Pb sources are needed.

Monitoring Lead (Pb) Pollution and Identifying Pb Pollution Sources in Japan Using Stable Pb Isotope Analysis with Kidneys of Wild Rats

PubMed Central

Nakata, Hokuto; Nakayama, Shouta M. M.; Oroszlany, Balazs; Ikenaka, Yoshinori; Mizukawa, Hazuki; Tanaka, Kazuyuki; Harunari, Tsunehito; Tanikawa, Tsutomu; Darwish, Wageh Sobhy; Yohannes, Yared B.; Saengtienchai, Aksorn; Ishizuka, Mayumi

2017-01-01

Although Japan has been considered to have little lead (Pb) pollution in modern times, the actual pollution situation is unclear. The present study aims to investigate the extent of Pb pollution and to identify the pollution sources in Japan using stable Pb isotope analysis with kidneys of wild rats. Wild brown (Rattus norvegicus, n = 43) and black (R. rattus, n = 98) rats were trapped from various sites in Japan. Mean Pb concentrations in the kidneys of rats from Okinawa (15.58 mg/kg, dry weight), Aichi (10.83), Niigata (10.62), Fukuoka (8.09), Ibaraki (5.06), Kyoto (4.58), Osaka (4.57), Kanagawa (3.42), and Tokyo (3.40) were above the threshold (2.50) for histological kidney changes. Similarly, compared with the previous report, it was regarded that even structural and functional kidney damage as well as neurotoxicity have spread among rats in Japan. Additionally, the possibility of human exposure to a high level of Pb was assumed. In regard to stable Pb isotope analysis, distinctive values of stable Pb isotope ratios (Pb-IRs) were detected in some kidney samples with Pb levels above 5.0 mg/kg. This result indicated that composite factors are involved in Pb pollution. However, the identification of a concrete pollution source has not been accomplished due to limited differences among previously reported values of Pb isotope composition in circulating Pb products. Namely, the current study established the limit of Pb isotope analysis for source identification. Further detailed research about monitoring Pb pollution in Japan and the demonstration of a novel method to identify Pb sources are needed. PMID:28075384

Isotopic data for Late Cretaceous intrusions and associated altered and mineralized rocks in the Big Belt Mountains, Montana

USGS Publications Warehouse

du Bray, Edward A.; Unruh, Daniel M.; Hofstra, Albert H.

2017-03-07

The quartz monzodiorite of Mount Edith and the concentrically zoned intrusive suite of Boulder Baldy constitute the principal Late Cretaceous igneous intrusions hosted by Mesoproterozoic sedimentary rocks of the Newland Formation in the Big Belt Mountains, Montana. These calc-alkaline plutonic masses are manifestations of subduction-related magmatism that prevailed along the western edge of North America during the Cretaceous. Radiogenic isotope data for neodymium, strontium, and lead indicate that the petrogenesis of the associated magmas involved a combination of (1) sources that were compositionally heterogeneous at the scale of the geographically restricted intrusive rocks in the Big Belt Mountains and (2) variable contamination by crustal assimilants also having diverse isotopic compositions. Altered and mineralized rocks temporally, spatially, and genetically related to these intrusions manifest at least two isotopically distinct mineralizing events, both of which involve major inputs from spatially associated Late Cretaceous igneous rocks. Alteration and mineralization of rock associated with the intrusive suite of Boulder Baldy requires a component characterized by significantly more radiogenic strontium than that characteristic of the associated igneous rocks. However, the source of such a component was not identified in the Big Belt Mountains. Similarly, altered and mineralized rocks associated with the quartz monzodiorite of Mount Edith include a component characterized by significantly more radiogenic strontium and lead, particularly as defined by 207Pb/204Pb values. The source of this component appears to be fluids that equilibrated with proximal Newland Formation rocks. Oxygen isotope data for rocks of the intrusive suite of Boulder Baldy are similar to those of subduction-related magmatism that include mantle-derived components; oxygen isotope data for altered and mineralized equivalents are slightly lighter.

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.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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.

Cenozoic changes in atmospheric lead recorded in central Pacific ferromanganese crusts

NASA Astrophysics Data System (ADS)

Klemm, Veronika; Reynolds, Ben; Frank, Martin; Pettke, Thomas; Halliday, Alex N.

2007-01-01

The possible sources of pre-anthropogenic Pb contributed to the world's oceans have been the focus of considerable study. The role of eolian dust versus riverine inputs has been of particular interest. With better calibration of isotopic records from central Pacific ferromanganese crusts using Os isotope stratigraphy it now appears that deep water Pb isotopic compositions were effectively homogeneous over a distance of 5000 km for the past 80 Myr. The composition shifted slightly from high 206Pb/ 204Pb ratios in the range of 18.87 ± 0.02 before 65 Ma to lower values of 18.62 ± 0.02 by 45 Ma and then gradually increased again very slightly to the present day ratio of 18.67 ± 0.02. The regional homogeneity provides evidence of a dominant well-mixed atmospheric source the most likely candidate for which is volcanic aerosols contributed either directly or as soluble condensates on eolian dust. The slight shift in Pb isotope composition of deep waters in the central Pacific between 65 and 45 Ma may be the result of a regional- or perhaps global-scale change in the sources of volcanic exhalations and volcanic activity caused by an increase in the importance of melting and assimilation of older continental crustal components over the Cenozoic.

Barium-isotopic fractionation in seawater mediated by barite cycling and oceanic circulation

NASA Astrophysics Data System (ADS)

Horner, Tristan J.; Kinsley, Christopher W.; Nielsen, Sune G.

2015-11-01

The marine biogeochemical cycle of Ba is thought to be controlled by particulate BaSO4 (barite) precipitation associated with the microbial oxidation of organic carbon and its subsequent dissolution in the BaSO4-undersaturated water column. Despite many of these processes being largely unique to Ba cycling, concentrations of Ba and Si in seawater exhibit a strong linear correlation. The reasons for this correlation are ambiguous, as are the depth ranges corresponding to the most active BaSO4 cycling and the intermediate sources of Ba to particulate BaSO4. Stable isotopic analyses of dissolved Ba in seawater should help address these issues, as Ba-isotopic compositions are predicted to be sensitive to the physical and biogeochemical process that cycle Ba. We report a new methodology for the determination of dissolved Ba-isotopic compositions in seawater and results from a 4500 m depth profile in the South Atlantic at 39.99° S, 0.92° E that exhibit oceanographically-consistent variation with depth. These data reveal that water masses obtain their [Ba] and Ba-isotopic signatures when at or near the surface, which relates to the cycling of marine BaSO4. The shallow origin of these signatures requires that the substantial Ba-isotopic variations in the bathypelagic zone were inherited from when those deep waters were last ventilated. Indeed, the water column below 600 m is well explained by conservative mixing of water masses with distinct [Ba] and Ba-isotopic compositions. This leads us to conclude that large scale oceanic circulation is important for sustaining the similar oceanographic distributions of Ba and Si in the South Atlantic, and possibly elsewhere. These data demonstrate that the processes of organic carbon oxidation, BaSO4 cycling, and Ba-isotopic fractionation in seawater are closely coupled, such that Ba-isotopic analyses harbor great potential as a tracer of the carbon cycle in the modern and paleo-oceans.

Iron isotope fractionation during hydrothermal ore deposition and alteration

NASA Astrophysics Data System (ADS)

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

2006-06-01

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

Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

2018-04-01

Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy Fe isotopes compositions of the sulfides from the SMAR may suggest the equilibrium fractionation process under high temperature conditions. The red Fe oxides are enriched in heavy Fe isotopes, indicating that the oxidative weathering processes result in the occurrence of significant Fe-isotope fractionation and the preferential enrichment of heavy Fe isotopes in the oxidation product.

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.

Simultaneous measurement of sulfur and lead isotopes in sulfides using nanosecond laser ablation coupled with two multi-collector inductively coupled plasma mass spectrometers

NASA Astrophysics Data System (ADS)

Yuan, Honglin; Liu, Xu; Chen, Lu; Bao, Zhian; Chen, Kaiyun; Zong, Chunlei; Li, Xiao-Chun; Qiu, Johnson Wenhong

2018-04-01

We herein report the coupling of a nanosecond laser ablation system with a large-scale multi-collector inductively coupled plasma mass spectrometer (Nu1700 MC-ICPMS, NP-1700) and a conventional Nu Plasma II MC-ICPMS (NP-II) for the simultaneous laser ablation and determination of in situ S and Pb isotopic compositions of sulfide minerals. We found that the required aerosol distribution between the two spectrometers depended on the Pb content of the sample. For example, for a sulfide containing 100-3000 ppm Pb, the aerosol was distributed between the NP-1700 and the NP-II spectrometers in a 1:1 ratio, while for lead contents >3000 and <100 ppm, these ratios were 5:1 and 1:3, respectively. In addition, S isotopic analysis showed a pronounced matrix effect, so a matrix-matched external standard was used for standard-sample bracketing correction. The NIST NBS 977 (NBS, National Bureau of Standards; NIST, National Institute of Standards & Technology) Tl (thallium) dry aerosol internal standard and the NIST SRM 610 (SRM, standard reference material) external standard were employed to obtain accurate results for the analysis of Pb isotopes. In tandem experiments where airflow conditions were similar to those employed during stand-alone analyses, small changes in the aerosol carrier gas flow did not significantly influence the accurate determination of S and Pb isotope ratios. In addition, careful optimization of the flow ratio of the aerosol carrier (He) and makeup (Ar) gases to match stand-alone analytical conditions allowed comparable S and Pb isotope ratios to be obtained within an error of 2 s analytical uncertainties. Furthermore, the results of tandem analyses obtained using our method were consistent with those of previously reported stand-alone techniques for the S and Pb isotopes of chalcopyrite, pyrite, galena, and sphalerite, thus indicating that this method is suitable for the simultaneous analysis of S and Pb isotopes of natural sulfide minerals, and provides an effective tool to determine S and Pb isotope compositions of sulfides formed through multi-stage deposition routes.

D/H Ratios in Lipids as a Tool to Elucidate Microbial Metabolism

NASA Astrophysics Data System (ADS)

Wijker, R. S.; Sessions, A. L.

2015-12-01

Large D/H fractionations have been observed in the lipids and growth water of most organisms studied today. These fractionations have generally been assumed to be constant across most biota because they originate solely from isotope effects imposed by the highly conserved lipid biosynthetic pathway. Recent data is illustrating this conclusion as incomplete. Lipids from field and laboratory samples exhibit huge variations in D/H fractionation. In environmental samples, lipids vary in δD by up to 300 ‰ and in laboratory cultures the documented variation is up to 500 ‰ within the same organism. Remarkably, the isotope fractionation appears to be correlated with the type of metabolism employed by the host organism. However, the underlying biochemical mechanisms leading to these isotopic variations are not yet fully understood. Because the largest proportion of H-bound C in fatty acids is derived directly from NADPH during biosynthesis, the original hypothesis was that large differences in the isotopic composition of NADPH, generated by different central metabolic pathways, were the primary source of D/H variation in lipids. However, recent observations indicate that this cannot be the whole story and lead us to the conclusion that additional processes must affect the isotope composition of NADPH. These processes may include the isotopic exchange of NADPH with water as well as fractionation of NADPH by transhydrogenases, interconverting NADH to NADPH by exhibiting large isotope effects. In this project, our objective is to ascertain whether D/H fractionation and these biochemical processes are correlated. We investigate correlations between cellular NADPH/NADP+ as well as NADH/NAD+ pool sizes and the D/H fractionation in a set of different microorganisms and will present the first trends here. Our results will contribute to a more comprehensive understanding of the basic biological regulations over D/H fractionation and potentially enables their use as tracers and proxies across earth and biological sciences.

D/H Ratios in Lipids as a Tool to Elucidate Microbial Metabolism

NASA Astrophysics Data System (ADS)

Wijker, Reto S.; Sessions, Alex L.

2016-04-01

Large D/H fractionations have been observed in the lipids and growth water of most organisms studied today. These fractionations have generally been assumed to be constant across most biota because they originate solely from isotope effects imposed by the highly conserved lipid biosynthetic pathway. Recent data is illustrating this conclusion as incomplete. Lipids from field and laboratory samples exhibit huge variations in D/H fractionation. In environmental samples, lipids vary in δD by up to 300 ‰ and in laboratory cultures the documented variation is up to 500 ‰ within the same organism. Remarkably, the isotope fractionation appears to be correlated with the type of metabolism employed by the host organism. However, the underlying biochemical mechanisms leading to these isotopic variations are not yet fully understood. Because the largest proportion of H-bound C in fatty acids is derived directly from NADPH during biosynthesis, the original hypothesis was that large differences in the isotopic composition of NADPH, generated by different central metabolic pathways, were the primary source of D/H variation in lipids. However, recent observations indicate that this cannot be the whole story and lead us to the conclusion that additional processes must affect the isotope composition of NADPH. These processes may include the isotopic exchange of NADPH with water as well as fractionation of NADPH by transhydrogenases, interconverting NADH to NADPH by exhibiting large isotope effects. In this project, our objective is to ascertain whether D/H fractionation and these biochemical processes are correlated. We investigate correlations between cellular NADPH/NADP+ as well as NADH/NAD+ pool sizes and the D/H fractionation in a set of different microorganisms and will present the trends here. Our results will contribute to a more comprehensive understanding of the basic biological regulations over D/H fractionation and potentially enables their use as tracers and proxies across earth and biological sciences.

Electrochemically controlled iron isotope fractionation

NASA Astrophysics Data System (ADS)

Black, Jay R.; Young, Edward D.; Kavner, Abby

2010-02-01

Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

Asymptotic Analysis of Time-Dependent Neutron Transport Coupled with Isotopic Depletion and Radioactive Decay

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

Brantley, P S

2006-09-27

We describe an asymptotic analysis of the coupled nonlinear system of equations describing time-dependent three-dimensional monoenergetic neutron transport and isotopic depletion and radioactive decay. The classic asymptotic diffusion scaling of Larsen and Keller [1], along with a consistent small scaling of the terms describing the radioactive decay of isotopes, is applied to this coupled nonlinear system of equations in a medium of specified initial isotopic composition. The analysis demonstrates that to leading order the neutron transport equation limits to the standard time-dependent neutron diffusion equation with macroscopic cross sections whose number densities are determined by the standard system of ordinarymore » differential equations, the so-called Bateman equations, describing the temporal evolution of the nuclide number densities.« less

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.

Analysis of High Frequency Site-Specific Nitrogen and Oxygen Isotopic Composition of Atmospheric Nitrous Oxide at Mace Head, Ireland

NASA Astrophysics Data System (ADS)

McClellan, M. J.; Harris, E. J.; Olszewski, W.; Ono, S.; Prinn, R. G.

2014-12-01

Atmospheric nitrous oxide (N2O) significantly impacts Earth's climate due to its dual role as an inert potent greenhouse gas in the troposphere and as a reactive source of ozone-destroying nitrogen oxides in the stratosphere. However, there remain significant uncertainties in the global budget of this gas. The marked spatial 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 climate. Source and sink processes of N2O lead to varying concentrations of N2O isotopologues (14N14N16O, 14N15N16O, 15N14N16O, and 14N14N18O being measured) due to preferential isotopic production and elimination in different environments. Estimation of source and sink fluxes can be improved by combining isotopically resolved N2O observations with simulations using a chemical transport model with reanalysis meteorology and treatments of isotopic signatures of specific surface sources and stratospheric intrusions. We present the first few months of site-specific nitrogen and oxygen isotopic composition data from the Stheno-TILDAS instrument (Harris et al, 2013) at Mace Head, Ireland and compare these to results from MOZART-4 (Model for Ozone and Related Chemical Tracers, version 4) chemical transport model runs including N2O isotopic fractionation processes and reanalysis meterological fields (NCEP/NCAR, MERRA, and GEOS-5). This study forms the basis for future inverse modeling experiments that will improve the accuracy of isotopically differentiated N2O emission and loss estimates. Ref: Harris, E., D. Nelson, W. Olszewski, M. Zahniser, K. Potter, B. McManus, A. Whitehill, R. Prinn, and S. Ono, Development of a spectroscopic technique for continuous online monitoring of oxygen and site-specific nitrogen isotopic composition of atmospheric nitrous oxide, Analytical Chemistry, 2013; DOI: 10.1021/ac403606u.

Calcium Isotopic Compositions of Normal Mid-Ocean Ridge Basalts From the Southern Juan de Fuca Ridge

NASA Astrophysics Data System (ADS)

Zhu, Hongli; Liu, Fang; Li, Xin; Wang, Guiqin; Zhang, Zhaofeng; Sun, Weidong

2018-02-01

Mantle peridotites show that Ca is isotopically heterogeneous in Earth's mantle, but the mechanism for such heterogeneity remains obscure. To investigate the effect of partial melting on Ca isotopic fractionation and the mechanism for Ca isotopic heterogeneity in the mantle, we report high-precision Ca isotopic compositions of the normal Mid-Ocean Ridge Basalts (N-MORB) from the southern Juan de Fuca Ridge. δ44/40Ca of these N-MORB samples display a small variation ranging from 0.75 ± 0.05 to 0.86 ± 0.03‰ (relative to NIST SRM 915a, a standard reference material produced by the National Institute of Standards and Technology), which are slightly lower than the estimated Upper Mantle value of 1.05 ± 0.04‰ and the Bulk Silicate Earth (BSE) value of 0.94 ± 0.05‰. This phenomenon cannot be explained by fractional crystallization, because olivine and orthopyroxene fractional crystallization has limited influence on δ44/40Ca of N-MORB due to their low CaO contents, while plagioclase fractional crystallization cannot lead to light Ca isotopic compositions of the residue magma. Instead, the lower δ44/40Ca of N-MORB samples compared to their mantle source is most likely caused by partial melting. The offset in δ44/40Ca between N-MORB and BSE indicates that at least 0.1-0.2‰ fractionation would occur during partial melting and light Ca isotopes are preferred to be enriched in magma melt, which is in accordance with the fact that δ44/40Ca of melt-depleted peridotites are higher than fertile peridotites in literature. Therefore, partial melting is an important process that can decrease δ44/40Ca in basalts and induce Ca isotopic heterogeneity in Earth's mantle.

Kinetic analysis of lead metabolism in healthy humans

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

Rabinowitz, M.B.; Wetherill, G.W.; Kopple, J.D.

The steady state kinetics of lead metabolism were studied in five healthy men with stable isotope tracers. Subjects lived in a metabolic unit and ate constant low lead diets. Their intake was supplemented each day with 79 to 204 ..mu..g of enriched lead-204 as nitrate which was ingested with meals for 1 to 124 days. The concentration and isotopic composition of lead was determined serially in blood, urine, feces, and diet and less commonly in hair, nails, sweat, bone, and alimentary tract secretions by isotopic dilution, mass spectrometric analysis. The data suggest a three-compartmental model for lead metabolism. The firstmore » compartment encompasses blood and is 1.5 to 2.2 times larger than the blood mass. It contains approximately 1.7 to 2.0 mg of lead and has a mean life of 35 days. This pool is in direct communication with ingested lead, urinary lead, and pools two and three. The second compartment is largely composed of soft tissue, contains about 0.3 to 0.9 mg of lead, and has a mean life of approximately 40 days. This pool gives rise to lead in hair, nails, sweat, and salivary, gastric, pancreatic, and biliary secretions. Pool three resides primarily in the skeleton, contains the vast quantity of body lead, and has a very slow mean life. Bones appear to differ in their rates of lead turnover. Within the relatively small changes in blood lead observed in the present study, the transfer coefficients between the pools remained constant.« less

Higher mass-independent isotope fractionation of methylmercury in the pelagic food web of Lake Baikal (Russia).

PubMed

Perrot, Vincent; Pastukhov, Mikhail V; Epov, Vladimir N; Husted, Søren; Donard, Olivier F X; Amouroux, David

2012-06-05

Mercury undergoes several transformations that influence its stable isotope composition during a number of environmental and biological processes. Measurements of Hg isotopic mass-dependent (MDF) and mass-independent fractionation (MIF) in food webs may therefore help to identify major sources and processes leading to significant bioaccumulation of methylmercury (MeHg). In this work, δ(13)C, δ(15)N, concentration of Hg species (MeHg, inorganic Hg), and stable isotopic composition of Hg were determined at different trophic levels of the remote and pristine Lake Baikal ecosystem. Muscle of seals and different fish as well as amphipods, zooplankton, and phytoplankton were specifically investigated. MDF during trophic transfer of MeHg leading to enrichment of heavier isotopes in the predators was clearly established by δ(202)Hg measurements in the pelagic prey-predator system (carnivorous sculpins and top-predator seals). Despite the low concentrations of Hg in the ecosystem, the pelagic food web reveals very high MIF Δ(199)Hg (3.15-6.65‰) in comparison to coastal fish (0.26-1.65‰) and most previous studies in aquatic organisms. Trophic transfer does not influence MIF signature since similar Δ(199)Hg was observed in sculpins (4.59 ± 0.55‰) and seal muscles (4.62 ± 0.60‰). The MIF is suggested to be mainly controlled by specific physical and biogeochemical characteristics of the water column. The higher level of MIF in pelagic fish of Lake Baikal is mainly due to the bioaccumulation of residual MeHg that is efficiently turned over and photodemethylated in deep oligotrophic and stationary (i.e., long residence time) freshwater columns.

Sedimentary sulfides in dune sands of Spiekeroog Island, southern North Sea: A biogeochemical study of sulfur isotope partitioning

NASA Astrophysics Data System (ADS)

Seibert, Stephan; Schubert, Florian; Schmiedinger, Iris; Böttcher, Michael E.; Massmann, Gudrun

2017-04-01

The formation of iron sulfides in sandy sediments and the associated development of stable isotope signatures is still mechanistically not understood. In dune sands under impact of both fresh and saline water several physico-chemical gradients may develop leading to distinctly different biogeochemical zones. In the present study, a 10 m long core from a dune base at the North Eastern part of Spiekeroog Island, southern North Sea, was investigated for the elemental and stable isotope composition. The pyrite (TRIS) content was quantitatively extracted via an acidic Cr(II) distillation procedure and the stable sulfur isotope composition was determined by means of C-irmMS. The pore waters display a downcore increase in salt contents and a mixing between fresh and salt water. The accumulation of metabolites at depth indicate an increasing superimposition of mixing by microbial decomposition of dissolved organic matter with only limited net sulfate reduction. This indicates an essential open system with respect to dissolved sulfate. The sands were found to be very low in TOC, TIC, and TRIS and dominated by quartz minerals. Under the assumption that North Sea water sulfate was the only substantial sulfate source (d34S = + 21per mil), the sedimentary sulfides indicate an overall sulfur isotope discrimination upon microbial sulfate reduction between 39 and 52 per mil, which is within the range of results from other fully marine sands from the Spiekeroog area and laboratory studies with pure cultures of sulfate-reducing bacteria under low cellular sulfate reduction rates. Further investigations are on the way to understand the processes leading to the iron sulfide formation in these organic-poor substrates.

Interaction of Solar-Flare-Accelerated Nuclei with the Solar Photosphere and the Isotopic Composition of the Solar Wind

NASA Astrophysics Data System (ADS)

Vasil'ev, G. I.; Ostryakov, V. M.; Pavlov, A. K.; Chakchurina, M. E.

2017-12-01

The nuclear interactions of solar-flare-accelerated protons and ions with the solar atmosphere and the deeper layers of the Sun lead to the formation of several stable and radioactive isotopes. This article examines the GEANT4 depth profiles of 2H, 3H, 3He, 6Li, 7Li, 10Be, and 14C. When accelerated particles pass through a layer of 0.1-2 g cm-2, 6Li, 7Li, 10Be, and 14C isotopes form in sufficient amounts to explain their anomalous abundances in lunar soil samples. It is assumed that they escape into interplanetary space with coronal mass ejections immediately after the flare.

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.

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.

Potential of Opuntia ficus-indica for air pollution biomonitoring: a lead isotopic study.

PubMed

El Hayek, Eliane; El Samrani, Antoine; Lartiges, Bruno; Kazpard, Veronique; Benoit, Mathieu; Munoz, Marguerite

2015-11-01

Opuntia ficus-indica (Ofi) is a long-domesticated cactus that is widespread throughout arid and semiarid regions. Ofi is grown for both its fruits and edible cladodes, which are flattened photosynthetic stems. Young cladodes develop from mother cladodes, thus forming series of cladodes of different ages. Therefore, successive cladodes may hold some potential for biomonitoring over several years the local atmospheric pollution. In this study, cladodes, roots, dust deposited onto the cladodes, and soil samples were collected in the vicinity of three heavily polluted sites, i.e., a fertilizer industry, the road side of a highway, and mine tailings. The lead content was analyzed using atomic absorption spectroscopy (AAS) and inductively coupled plasma-mass spectrometry (ICP-MS). Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) was used to characterize the cladode surfaces and the nature of dust deposit, and the lead isotopes were analyzed to identify the origin of Pb. The results show that (i) Ofi readily bioaccumulates Pb, (ii) the lead isotopic composition of cladodes evidences a foliar pathway of lead into Ofi and identifies the relative contributions of local Pb sources, and (iii) an evolution of air quality is recorded with successive cladodes, which makes Ofi a potential biomonitor to be used in environmental and health studies.

Recent advances in understanding atmospheric CO based on stable isotope measurements

NASA Astrophysics Data System (ADS)

Popa, Maria Elena; Naus, Stijn; Ferrero Lopez, Noelia; Vijverberg, Sem; de Leeuw, Selma; Röckmann, Thomas

2017-04-01

Carbon monoxide (CO) plays an important role for atmospheric chemistry and for carbon cycling in the atmosphere. Via its reaction with the OH radical it influences concentrations of many other trace gases, it is an important precursor for O3 formation, and its oxidation leads to the formation of about 1 Pg C per year of CO2. The natural and anthropogenic sources of CO are subject to relatively large temporal changes due to natural variability (e.g. biomass burning), industrial activity and mitigation measures (e.g. fossil fuel burning), variations in precursor compounds (e.g. CH4 and VOC) and variations in the abundance of the OH radical in the atmosphere, which are difficult to quantify. Isotope measurements can be used to distinguish between the effects of individual sources and sinks to put tighter constrains on its budget, but the isotopic characterization of the CO sources is in many cases still based on a few relatively old measurements that did not allow to account for dependence on parameters. We will present an update of the isotopic composition of several sources and removal processes of CO that have been carried out in the past years with the automated continuous-flow IRMS system at Utrecht University. This includes: - the previously unknown isotopic composition of direct biogenic CO emissions - a surprisingly large variability in the isotopic composition of CO emitted by different vehicles and single vehicles under various driving conditions - previously very poorly investigated signatures, like the fractionation in the removal of CO by soils, and its interaction with CO that is simultaneously emitted from soil. These results from process specific investigations will be linked to recent atmospheric measurements at various locations.

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.

Isotopic Composition of Molybdenum and Barium in Single Presolar Silicon Carbide Grains of Type A+B

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.

2003-01-01

Presolar SiC grains fall into several groups based on C, N, and Si isotopic compositions. Approximately 93% are defined as mainstream, having 10 less than C-12/C-13 less than 100 and N-14/N-15 ranging from 50 to 20,000. A number of studies have shown that the most likely sources of mainstream grains are low mass asymptotic giant branch stars. Models of nucleosynthesis in AGB stars reproduce the s-process enhancements seen in the heavy elements in mainstream SiC grains. Among the less common grains, A+B grains, which comprise approximately 3-4% of presolar SiC, are perhaps the least well understood. Recent studies by Amari et al. show that A+B grains can be divided into at least 4 groups based on their trace element concentration patterns. Of 20 grains studied, 7 showed trace element patterns consistent with condensation from a gas of solar system composition, while the rest had varying degrees of process enhancements. Our previous measurements on 3 A+B grains showed Mo of solar isotopic composition, but Zr with a strong enhancement in 96Zr, which is an r-process isotope but can be made in an sprocess if the neutron density is high enough to bridge the unstable Zr-95 (T(sub 1/2)= 64 d). The observation of Mo with solar system isotopic composition in the same grains is puzzling however. Meyer et al. have recently shown that a neutron burst mechanism can produce a high Zr-96/Zr-94 without enhancing Mo-100, however this model leads to enhancements in Mo-95 and Mo-97 not observed in A+B grains. We report here results of Mo measurements on 7 additional A+B grains, and Ba measurements on 2 A+B grains, and compare these to the previous studies.

SrNdPb isotopic and trace element evidence for crustal contamination of plume-derived flood basalts: Oligocene flood volcanism in western Yemen

NASA Astrophysics Data System (ADS)

Baker, J. A.; Thirlwall, M. F.; Menzies, M. A.

1996-07-01

Oligocene flood basalts from western Yemen have a relatively limited range in initial isotopic composition compared with other continental flood basalts: 87Sr/86Sr = 0.70365-0.70555 ; 143Nd/144Nd = 0.5129-0.51248 ( ɛNd = +6.0 to -2.4) ; 206pb/204Pb = 17.9-19.3 . Most compositions lie outside the isotopic ranges of temporally and spatially appropriate mantle source compositions observed in this area, i.e., Red Sea/Gulf of Aden MORB mantle, the Afar plume, and Pan-African lithospheric mantle Correlations between indices of fractionation, silica, and isotope ratios suggest that crustal contamination has substantially modified the primary isotopic and incompatible trace element characteristics of the flood basalts. However, significant scatter in these correlations was produced by: (a) the heterogeneous isotopic composition of Pan-African crust; (b) the difference in susceptibility of magmas to contamination as a result of variable incompatible trace element contents in primary melts produced by differing degrees of partial melting; (c) the presence or absence of plagioclase as a fractionating phase generating complex contamination trajectories for Sr; (d) sampling over a wide area not representing a single coherent magmatic system; and (e) variation in contamination mechanisms from assimilation associated with fractionation (AFC) to assimilation by hot mafic magmas with little concomitant fractionation. The presence of plagioclase as a fractionating phase in some suites that were undergoing AFC requires assimilation to have taken place within the crust and, coupled with the limited LREE-enrichment accompanying isotopic variations, excludes the possibility that an AFC-type process took place during magma transfer through the lithospheric mantle. Isotopic compositions of some of the inferred crustal assimilants are similar to those postulated by other workers for an enriched lithospheric mantle source of many flood basalts in southwestern Yemen, Ethiopia, and Djibouti. The western Yemen flood basalts contain 0-30% crust which largely swamps their primary lead isotopic signature, but the primary SrNd isotopic signature is close to that of the least contaminated and isotopically most depleted flood basalts. LREE/HFSE and LILE/HFSE ratios also correlate with isotopic data as a result of crustal contamination. However, Nb/La and K/Nb ratios of >1.1 and <150, respectively, in least contaminated samples require an OIB-like source. The pre-contamination isotopic signature is estimated to be: 87Sr/86Sr ˜ 0.7036; 143Nd/144Nd ˜ 0.51292 ; 206Pb/204Pb ˜ 18.4-19.0 . This, coupled with low LILE/HFSE ratios, suggest the source has characteristics akin to the Afar plume. A mantle source isotopically more depleted than Bulk Earth, but not as depleted as MORB, coupled with LILE depletion, also characterises other examples of plume-derived flood volcanism. This mantle reservoir is responsible for the second largest outbursts of volcanism on Earth and has radiogenic isotopic characteristics akin to PREMA mantle, but the incompatible trace element signature of HIMU mantle.

A change in coral extension rates and stable isotopes after El Niño-induced coral bleaching and regional stress events

NASA Astrophysics Data System (ADS)

Hetzinger, S.; Pfeiffer, M.; Dullo, W.-Chr.; Zinke, J.; Garbe-Schönberg, D.

2016-09-01

Coral reefs are biologically diverse ecosystems threatened with effective collapse under rapid climate change, in particular by recent increases in ocean temperatures. Coral bleaching has occurred during major El Niño warming events, at times leading to the die-off of entire coral reefs. Here we present records of stable isotopic composition, Sr/Ca ratios and extension rate (1940-2004) in coral aragonite from a northern Venezuelan site, where reefs were strongly impacted by bleaching following the 1997-98 El Niño. We assess the impact of past warming events on coral extension rates and geochemical proxies. A marked decrease in coral (Pseudodiploria strigosa) extension rates coincides with a baseline shift to more negative values in oxygen and carbon isotopic composition after 1997-98, while a neighboring coral (Siderastrea siderea) recovered to pre-bleaching extension rates simultaneously. However, other stressors, besides high temperature, might also have influenced coral physiology and geochemistry. Coastal Venezuelan reefs were exposed to a series of extreme environmental fluctuations since the mid-1990s, i.e. upwelling, extreme rainfall and sediment input from landslides. This work provides important new data on the potential impacts of multiple regional stress events on coral isotopic compositions and raises questions about the long-term influence on coral-based paleoclimate reconstructions.

A change in coral extension rates and stable isotopes after El Niño-induced coral bleaching and regional stress events.

PubMed

Hetzinger, S; Pfeiffer, M; Dullo, W-Chr; Zinke, J; Garbe-Schönberg, D

2016-09-13

Coral reefs are biologically diverse ecosystems threatened with effective collapse under rapid climate change, in particular by recent increases in ocean temperatures. Coral bleaching has occurred during major El Niño warming events, at times leading to the die-off of entire coral reefs. Here we present records of stable isotopic composition, Sr/Ca ratios and extension rate (1940-2004) in coral aragonite from a northern Venezuelan site, where reefs were strongly impacted by bleaching following the 1997-98 El Niño. We assess the impact of past warming events on coral extension rates and geochemical proxies. A marked decrease in coral (Pseudodiploria strigosa) extension rates coincides with a baseline shift to more negative values in oxygen and carbon isotopic composition after 1997-98, while a neighboring coral (Siderastrea siderea) recovered to pre-bleaching extension rates simultaneously. However, other stressors, besides high temperature, might also have influenced coral physiology and geochemistry. Coastal Venezuelan reefs were exposed to a series of extreme environmental fluctuations since the mid-1990s, i.e. upwelling, extreme rainfall and sediment input from landslides. This work provides important new data on the potential impacts of multiple regional stress events on coral isotopic compositions and raises questions about the long-term influence on coral-based paleoclimate reconstructions.

Atomic Weights and Isotopic Compositions

National Institute of Standards and Technology Data Gateway

SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

Magnesium isotopic composition of the Earth and chondrites

NASA Astrophysics Data System (ADS)

Teng, Fang-Zhen; Li, Wang-Ye; Ke, Shan; Marty, Bernard; Dauphas, Nicolas; Huang, Shichun; Wu, Fu-Yuan; Pourmand, Ali

2010-07-01

To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ 25Mg and ±0.07‰ on δ 26Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL). Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ 25Mg = -0.13 ± 0.05 (2SD) and δ 26Mg = -0.26 ± 0.07 (2SD) for global oceanic basalts ( n = 110) and δ 25Mg = -0.13 ± 0.03 (2SD) and δ 26Mg = -0.25 ± 0.04 (2SD) for global peridotite xenoliths ( n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ 25Mg = -0.15 ± 0.04 (2SD) and δ 26Mg = -0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes. Collectively, the Mg isotopic composition of the Earth's mantle, based on oceanic basalts and peridotites, is estimated to be -0.13 ± 0.04 for δ 25Mg and -0.25 ± 0.07 for δ 26Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites. The chondritic composition of the Earth implies that Mg isotopes were well mixed during accretion of the inner solar system.

Remobilisation of industrial lead depositions in ash during Australian wildfires.

PubMed

Wu, Liqin; Taylor, Mark Patrick; Handley, Heather K

2017-12-01

This study examined the recycling of lead (Pb) in ash from wildfires, its source and potential contribution to environmental contamination. Ash from wildfires was collected from four Australian sites following uncontrolled fires during 2012 to 2013 close to major urban populations in Sydney (New South Wales), Hobart (Tasmania) and Adelaide (South Australia). The samples were analysed for their total Pb concentration and Pb isotopic composition to determine the sources of Pb and the extent, if any, of industrial contamination and its recycling into the ecosystem. Median ash concentrations (23mg/kg) released from a wildfire close to Australia's largest city, Sydney, exceeded the median ash Pb concentrations from wildfires from the less populated locations of Hobart, Adelaide and NSW Central Coast. Lead isotopic compositions of Duffys Forest wildfire ash demonstrate that anthropogenic inputs from legacy leaded petrol depositions were the predominant source of contamination. Despite the cessation of leaded petrol use in Australia in 2002, historic petrol Pb deposits continue to be a substantial source of contamination in ash: petrol Pb contributed 35% of the Pb in the Woy Woy ash, 73% in Duffys Forest ash, 39% in Forcett ash and 5% in Cherryville ash. The remobilisation of legacy industrial Pb depositions by wildfires in ash results in it being a persistent and problematic contaminant in contemporary environmental systems because of its known toxicity. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

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.

Lead isotopic evidence for mixed sources of Proterozoic granites and pegmatites, Black Hills, South Dakota, USA

NASA Astrophysics Data System (ADS)

Krogstad, Eirik J.; Walker, Richard J.; Nabelek, Peter I.; Russ-Nabelek, Carol

1993-10-01

The lead isotopic compositions of K-feldspars separated from the ca. 1700 Ma Harney Peak Granite complex and spatially associated granitic pegmatites indicate that these rocks were derived from at least two sources. It has been reported previously that the core of the Harney Peak Granite complex is dominated by relatively lower/ gd18O (avg. 11.5 %.) granites, whereas higher / gd18O (avg. 13.2%.) granites occur around the periphery of the complex. The higher δ 18O granites and one simple pegmatite have low values of 207Pb /204Pb for their 206Pb /204Pb Thus, they likely were derived from a source with a short crustal residence time. This source may have been the pelitic schists into which the Harney Peak Granite complex and pegmatites were intruded. Feldspars from granites with lower / gd18O values have significantly higher 207Pb /204Pb for their 206Pb /204Pb . The data define a linear array with a slope equivalent to an age of ca. 2.6 Ga with t 2 defined to be 1.7 Ga. Such a slope could represent a mixing array or a secondary isochron for the source. These low δ18O granites could have been derived from a source with a high U/ Pb and with a crustal residence beginning before the Proterozoic. The source (s) of these granites may have been a sediment derived from late Archean continental crust. The highly evolved Tin Mountain pegmatite has lead isotopic systematics intermediate between those of the two granite groups, suggesting either a mixed source or contamination. Two late Archean granites, the Little Elk Granite and the Bear Mountain Granite, had precursors with high U/Pb and low Th/U histories. The Th/U history of the Bear Mountain Granite is too low for this rock to have been an important component of the source of the Proterozoic granites. However, crustal rocks with lead isotopic compositions similar to those of the Little Elk Granite were an important source of lead for some of the Proterozoic granitic rocks.

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 ...

Tracing of ca 800 yr old mining activity in peat bog using Pb elemental concentrations and isotope compositions.

NASA Astrophysics Data System (ADS)

Baron, S.; Carignan, J.; Ploquin, A.

2003-04-01

Sixty sites of slags have been documented on the Mont-Lozère in southern France. The petrographic analysis shows that slags are metallurgical wastes (800 to 850 yr BP) which certainly result from smelting activity for lead and silver extraction (Ploquin et al., 2001). The aims of this study are: 1) to trace the source of Pb ores which supplied the smelting sites, by using the Pb isotopic composition of several surrounding Pb deposits, 2) to evaluate the actual pollution caused by these slags, by using elemental and isotopic compositions of soils, water and vegetation, and 3) to document the pollution history of the region, by using elemental and isotopic compositions of peat bog cores collected in the neighbourhood of the historical smelting sites. The lead isotopic composition of galena collected in most surrounding ores is very similar to that of different slag samples. On the other hand, the high precision of the results allowed us to select the mineralised areas which were probably the ore sources. The Pb isotopic composition of slags is even more homogeneous: 208/206 Pb: 2.092±0.002; 206/207 Pb: 1.179±0.001; 208/204 Pb: 38.663±0.025; 207/204 Pb: 15.665±0.006; 206/204 Pb: 18.476±0.023, and will allow source tracing in the environment. The "Narses Mortes" peat bog, around which two smelting sites have been reported, is strongly minerotrophic and contains 8 to 60% ash. A 1.40 m core have been retrieved and divided into 58 individual samples. Minerotrophic peat bog records both atmospheric deposition, soils leaching and the grounwater influence. The measured metal concentrations are normalised to Al contents of peat bog samples and the metal/Al ratios are compared to that of the Mont-Lozère granite: relative excess in metal concentrations are found in peat bog samples. An increasing excess of most metals (Pb, Zn, Cd...) was measured for surface samples, from 55 cm depth to the top of the core (23 cm depth). This profil might be attributed to atmospheric input during the last centuries. Pb and As alone are also enriched in some deeper samples (between 120--90 cm depth). At the moment, no sedimentation rates are available for this section of the peat bog. However, according to palynological data (de Beaulieu, in progress), the bottom of the core might be as old as 5000 years BP. This would place the medieval activities at the base of the surface metal enrichment (˜55 cm depth), having no large effect in Pb concentrations measured in peat bog. The older Pb-As enrichment remain enigmatic and may correspond to earlier anthropogenic activities (2000--2500 BP), a period for which very few traces of metallurgical activities are found in Occidental Europe. 14C dating and Pb isotope works are going on peat bog samples trying to discriminate metals sources.

Tamil Chola Bronzes and Swamimalai Legacy: Metal Sources and Archaeotechnology

NASA Astrophysics Data System (ADS)

Srinivasan, Sharada

2016-08-01

This review explores the great copper alloy image casting traditions of southern India from archaeometallurgical and ethnometallurgical perspectives. The usefulness of lead isotope ratio and compositional analysis in the finger-printing and art historical study of more than 130 early historic, Pallava, Chola, later Chola, and Vijayanagara sculptures (fifth-eighteenth centuries) is highlighted, including Nataraja, Buddha, Parvati, and Rama images made of copper, leaded bronze, brass, and gilt copper. Image casting traditions at Swamimalai in Tamil Nadu are compared with artistic treatises and with the technical examination of medieval bronzes, throwing light on continuities and changes in foundry practices. Western Indian sources could be pinpointed for a couple of medieval images from lead isotope analysis. Slag and archaeometallurgical investigations suggest the exploitation of some copper and lead-silver sources in the Andhra and Karnataka regions in the early historic Satavahana period and point to probable copper sources for the medieval images in Karnataka, Tamil Nadu, and Andhra Pradesh. The general lower iron content in southern Indian bronzes perhaps renders the proximal copper-magnetite reserves of Seruvila in Sri Lanka as a less likely source. Given the lack of lead deposits in Sri Lanka, however, the match of the lead isotope signatures of a well-known Ceylonese Buddhist Tara in British Museum with a Buddha image from Nagapattinam in Tamil Nadu may underscore ties between the island nation and the southern Indian Tamil regions.

Rb-Sr whole-rock and mineral ages, K-Ar, 40Ar/39Ar, and U-Pb mineral ages, and strontium, lead, neodymium, and oxygen isotopic compositions for granitic rocks from the Salinian Composite Terrane, California:

USGS Publications Warehouse

Kistler, R.W.; Champion, D.E.

2001-01-01

This report summarizes new and published age and isotopic data for whole-rocks and minerals from granitic rocks in the Salinian composite terrane, California. Rubidium-strontium whole-rock ages of plutons are in two groups, Early Cretaceous (122 to 100 Ma) and Late Cretaceous (95 to 82 Ma). Early Cretaceous plutons occur in all granitic rock exposures from Bodega Head in the north to those from the Santa Lucia and Gabilan Ranges in the central part of the terrane. Late Cretaceous plutons have been identified in the Point Reyes Peninsula, the Santa Lucia and the Gabilan Ranges, and in the La Panza Range in the southern part of the terrane. Ranges of initial values of isotopic compositions are 87Sr/86Sr, 0.7046-0.7147, δ18O, +8.5 to +12.5 per mil, 206Pb/204Pb, 18.901-19.860, 207Pb/204Pb, 15.618-15.814, 208Pb/204Pb, 38.569- 39.493, and εNd, +0.9 to -8.6. The initial 87Sr/86Sr=0.706 isopleth is identified in the northern Gabilan Range and in the Ben Lomond area of the Santa Cruz Mountains, in Montara Mountain, in Bodega Head, and to the west of the Farallon Islands on the Cordell Bank. This isotopic boundary is offset about 95 miles (160km) by right-lateral displacements along the San Gregorio-Hosgri and San Andreas fault systems.

Utilizing Stable Isotopes and Isotopic Anomalies to Study Early Solar System Formation Processes

NASA Technical Reports Server (NTRS)

Simon, Justin

2017-01-01

Chondritic meteorites contain a diversity of particle components, i.e., chondrules and calcium-, aluminum-rich refractory inclusions (CAIs), that have survived since the formation of the Solar System. The chemical and isotopic compositions of these materials provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of the processes and reservoirs in which solids formed in the solar nebula, an important step leading to the accretion of planetesimals. Isotopic anomalies associated with nucleosynthetic processes are observed in these discrete materials, and can be compared to astronomical observations and astrophysical formation models of stars and more recently proplyds. The existence and size of these isotopic anomalies are typically thought to reflect a significant state of isotopic heterogeneity in the earliest Solar System, likely left over from molecular cloud heterogeneities on the grain scale, but some could also be due to late stellar injection. The homogenization of these isotopic anomalies towards planetary values can be used to track the efficiency and timescales of disk wide mixing,

Upper Mississippi Pb as a mid-1800s chronostratigraphic marker in sediments from seasonally anoxic lakes in Eastern Canada

NASA Astrophysics Data System (ADS)

Gobeil, Charles; Tessier, André; Couture, Raoul-Marie

2013-07-01

Sediment cores from eight headwater lakes located in Southern Québec, Eastern Canada, were analyzed for Pb, stable Pb isotopes, and the radioelements 210Pb, 137Cs, 241Am and 226Ra. The depth profiles of stable Pb isotope ratios show, for the post-19th century period, the influence of several isotopically distinct anthropogenic lead sources, mainly including emissions from two Canadian smelters and from leaded gasoline combustion in Canada and in the United States. A most interesting feature of the profiles, however, is the presence of sharp stable Pb isotope ratio peaks near the depth horizon, where excess 210Pb becomes undetectable. Using a binary mixing model and assuming that natural Pb concentrations and isotopic compositions from the catchment are given by the pre-industrial sediments at the bottom of the cores, we find that a significant part of the anthropogenic Pb supplied to the sediments at this horizon originated from smelting activities in the Upper Mississippi Valley. We assess that the Pb isotope ratio peaks, also observed in the laminated sediments of the Pettaquamscutt Estuary, Rhode Island, USA, are an accurate chronostratigraphic marker for the validation of mid-19th century 210Pb-derived dates. Given that the study lakes are located up to 2000 km from the Mississippi Valley, we conclude that this isotopic Pb signal provides a widely distributed time-marker that is key to validate 210Pb chronologies in environmental archives from Eastern North America.

Cometary coma chemical composition (C4) mission. [Abstract only

NASA Technical Reports Server (NTRS)

Carle, G. C.; Clark, B. C.; Niemann, H. B.; Alexander, M.; Knocke, P. C.; O'Hara, B. J.

1994-01-01

Cometary missions are of enormous fundamental importance for many different space science disciplines, including exobiology. Comets are presumed relics of the earliest, most primitive material in the solar nebula and are related to the planetesimals. They undoubtedly provided a general enrichment of volatiles to the inner solar system (contributing to atmospheres and oceans) and may have been key to the origin of life. A Discovery class, comet rendezvous mission, the Cometary Coma Chemical Composition (C4) Mission, was selected for further study by NASA earlier this year. The C4 Mission is a highly focused and usefully-limited subset of the Cometary Rendezvous Asteroid Flyby (CRAF) Mission, concentrating exclusively on measurements which will lead to an understanding of the chemical composition and make-up of the cometary nucleus. The scientific goals of the Cometary Coma Chemical Composition (C4) Mission are to rendezvous with a short-period comet and (1) to determine the elemental, chemical, and isotopic composition of the nucleus and (2) to characterize the chemical and isotopic nature of its atmosphere. Further, it is a goal to obtain preliminary data on the development of the coma (dust and gas composition) as a function of time and orbital position.

Stable isotope variations (δ18O and δD) in modern waters across the Andean Plateau

NASA Astrophysics Data System (ADS)

Bershaw, John; Saylor, Joel E.; Garzione, Carmala N.; Leier, Andrew; Sundell, Kurt E.

2016-12-01

Environmental parameters that influence the isotopic composition of meteoric water (δ18O and δD) are well characterized up the windward side of mountains, where orographic precipitation results in a predictable relationship between the isotopic composition of precipitation and elevation. The topographic and climatic evolution of the Andean Plateau and surrounding regions has been studied extensively by exploiting this relationship through the use of paleowater proxies. However, interpretation on the plateau itself is challenged by a poor understanding of processes that fractionate isotopes during vapor transport and rainout, and by the relative contribution of unique moisture sources. Here, we present an extensive dataset of modern surface water samples for the northern Andean Plateau and surrounding regions to elucidate patterns and causes of isotope fractionation in this continental environment. These data show a progressive increase in δ18O of stream water west of the Eastern Cordillera (∼1‰/70 km), almost identical to the rate observed across the Tibetan Plateau, attributed to a larger fraction of recycled water in precipitation and/or increased evaporative enrichment downwind. This may lead to underestimates of paleoelevation, particularly for sites deep into the rainshadow of the Eastern Cordilleran crest. That said, elevation is a primary control on the isotopic composition of surface waters across the entire Andean Plateau and its flanks when considering the most negative δ18O values, highlighting the need for sufficiently large datasets to distinguish minimally evaporated samples. There is a general increase in δ18O on the plateau from north to south, concomitant with an increase in aridity and decrease in convective moistening (amount effect). Lastly, stable isotope and seasonal precipitation patterns suggest easterlies provide the vast majority of moisture that falls as precipitation across the Andean Plateau and Western Cordillera, from Peru to northern Bolivia (-13° to -20° latitude), with Pacific-derived moisture contributing a minor amount at low elevations near the coast.

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.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

[Determination of deuterium concentration in foods and influence of water with modified isotopic composition on oxidation parameters and heavy hydrogen isotopes content in experimental animals].

PubMed

Basov, A A; Bykov, I M; Baryshev, M G; Dzhimak, S S; Bykov, M I

2014-01-01

The article presents the results of the study of the deuterium (D) content in food products as well as the influence of deuterium depleted water (DDW) on the concentration of heavy hydrogen isotopes in the blood and lyophilized tissues of rats. The most significant difference in the content of D was found between potato and pork fat, which indexes the standard delta notation (δ) D in promille, related to the international standard SMOW (Standard Mean Ocean of Water) amounted to -83,2 per thousand and -250,7 per thousand, respectively (p<0,05). Among the investigated samples of water deuterium concentration ranged from -75,5 per thousand (Narzan) to +72,1 per thousand (Kubai), that indicates the ability of some food products to increase the concentration of heavy hydrogen atoms in the body. The data obtained in the experimental modeling of the diet of male Wistar rats in the age of 5-6 mo (weight 235 ± 16 g) using DDW (δD = -743,2 per thousand) instead of drinking water (δD = -37,0 per thousand) with identical mineral composition showed that after 2 weeks significant (p <0,05) formation of isotopic (deuterium-protium, D/H) gradient in the body is possible. Changing the direction of isotopic D/H gradient in laboratory animals in comparison with its physiological indicators (72-127 per thousand, "plasma>tissue") is due to different rates ofisotopic exchange reactions in plasma and tissues (liver, kidney, heart), which can be explained by entering into the composition of a modified diet of organic substrates with more than DDW concentration D, which are involved in the construction of cellular structures and eventually lead to a redistribution of D and change direction of D/H gradient "plasma

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.

A change in the geodynamics of continental growth 3 billion years ago.

PubMed

Dhuime, Bruno; Hawkesworth, Chris J; Cawood, Peter A; Storey, Craig D

2012-03-16

Models for the growth of continental crust rely on knowing the balance between the generation of new crust and the reworking of old crust throughout Earth's history. The oxygen isotopic composition of zircons, for which uranium-lead and hafnium isotopic data provide age constraints, is a key archive of crustal reworking. We identified systematic variations in hafnium and oxygen isotopes in zircons of different ages that reveal the relative proportions of reworked crust and of new crust through time. Growth of continental crust appears to have been a continuous process, albeit at variable rates. A marked decrease in the rate of crustal growth at ~3 billion years ago may be linked to the onset of subduction-driven plate tectonics.

Uranium isotope fractionation induced by aqueous speciation: Implications for U isotopes in marine CaCO3 as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Chen, Xinming; Romaniello, Stephen J.; Anbar, Ariel D.

2017-10-01

Natural variations of 238U/235U in marine CaCO3 rocks are being explored as a novel paleoredox proxy to investigate oceanic anoxia events. Although it is generally assumed that U isotopes in CaCO3 directly record 238U/235U of seawater, recently published laboratory experiments demonstrate slight U isotope fractionation during U(VI) incorporation into abiotic calcium carbonates. This fractionation is hypothesized to depend on aqueous U(VI) speciation, which is controlled by pH, ionic strength, pCO2 and Mg2+ and Ca2+ concentrations. Secular variation in seawater chemistry could lead to changes in aqueous U(VI) speciation, and thus, may affect the extent of U isotope fractionation during U(VI) incorporation into CaCO3. In this study, we combine estimates of seawater composition over the Phanerozoic with a model of aqueous U speciation and isotope fractionation to explore variations in the expected offset between the U isotope composition of seawater and primary marine CaCO3 through time. We find that U isotope fractionation between U in primary marine CaCO3 and seawater could have varied between 0.11 and 0.23‰ over the Phanerozoic due to secular variations in seawater chemistry. Such variations would significantly impact estimates of the extent of marine anoxia derived from the U isotope record. For example, at the Permo-Triassic boundary, this effect might imply that the estimated extent of anoxia is ∼32% more extreme than previously inferred. One significant limitation of our model is that the existing experimental database covers only abiotic carbonate precipitation, and does not include a possible range of biological effects which might enhance or suppress the range of isotopic fractionation calculated here. As biotic carbonates dominate the marine carbonate record, more work is need to assess controls on U isotopic fractionation into biotic marine carbonates.

Tracing cadmium, zinc and lead sources in bivalves from the coasts of western Canada and the USA using isotopes

NASA Astrophysics Data System (ADS)

Shiel, Alyssa E.; Weis, Dominique; Orians, Kristin J.

2012-01-01

Environmental monitoring and remediation require techniques to identify the source and fate of metals emissions. The measurement of heavy metal isotopic signatures, made possible by the advent of the MC-ICP-MS, is a powerful new geochemical tool, which may be used to trace the source of these metals in the environment. In a multi-tracer study, Cd, Zn and Pb isotopic compositions (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from western Canada (British Columbia), Hawaii, and the USA East Coast. Variability in the δ 114/110Cd values of bivalves (-1.20‰ to -0.09‰) is attributed to differences in the relative contributions of Cd from natural and anthropogenic sources between sites. Cadmium isotopic compositions (δ 114/110Cd = -0.69‰ to -0.09‰) identify high Cd levels in B.C. oysters as primarily natural (i.e., upwelling of Cd rich intermediate waters in the North Pacific), with some variability attributed to anthropogenic sources (e.g., mining and smelting). Variability in the δ 66/64Zn values exhibited by the B.C. bivalves is relatively small (0.28-0.36‰). Despite the low Pb levels found in B.C. oysters, Pb isotopes are used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as significant metal sources. Although the Cd concentrations of the USA East Coast bivalves are primarily lower than those of B.C. oysters, their relatively light Cd isotopic compositions (δ 114/110Cd = -1.20‰ to -0.54‰) indicate the significance of anthropogenic Cd sources and are attributed to the high prevalence of industry on this coast. The δ 114/110Cd values of USA East Coast bivalves include the lightest ever reported, with the exception of values reported for extraterrestrial materials. In addition, the Pb isotopic compositions of bivalves from the USA East Coast indicate Pb emissions from the combustion of coal are an important source of Pb, consistent with the high consumption of coal for power production on this coast. 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 "fingerprinting" techniques.

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.

Can the evolution of nitrogen cycle be traced by the N isotopic composition in mica?

NASA Astrophysics Data System (ADS)

Pinti, D. L.; Hashizume, K.

2011-12-01

A significant portion of nitrogen present in sedimentary rocks has a biological origin, trapped either in organic form, or as ammonium ion substituting potassium in mica. Mica might preserve biological N isotopic signatures (δ15N) in the geological record, allowing the evolution of the N cycle to be traced. However, diagenetic or metamorphic events can modify the pristine N isotopic signature leading to inaccurate interpretations. For example, devolatilization of the rock leads to a reduction in the N abundance and a contemporary increase of the δ15N because 14N escapes faster than 15N. We measured N isotopic compositions in whole rock, mica and feldspars separates from two Archean suites of cherts: 3.5 Ga Kitty's Gap and North Pole sequences in Pilbara, Western Australia and from the 3.45 Ga Hooggenoeg Fm, Barberton Greenstone Belt, South Africa. N was compared with the argon elemental and isotopic composition, because a relation between NH4+, which replaces K+ and radiogenic 40Ar*, which is produced by electron capture of K+ is expected. Both Pilbara and Barberton cherts show a clear correlation between N and 40Ar*, confirming the occurrence of a common speciation. K-Ar dating of the Hooggenoeg Formation mica and feldspars give ages of 2.1 and 1.1 Ga, respectively, indicating that loosely-bounded noble gas 40Ar* is lost from the host mineral during known metamorphic events. Observed correlations between 40Ar* and N suggests that nitrogen, although more strongly bounded as ammonium is also lost, possibly leading to isotopic fractionation. Measured δ15N values, however, are relatively constant (+8.1±0.6% for whole rock and +10.9±1.2% for mica) and do not display an inverse correlation with N abundances. This suggests either 1) that isotopic fractionation is not produced during N loss or; 2) that a process other than devolatilization fractionate N isotopes. Measured δ15N values are at levels far greater than those expected for Early Archean kerogens (0±2%) thus suggesting that fractionation took place but probably is induced by a process other than devolatilization. Step-combustion analyses of N and Ar from Kitty's Gap cherts reveals the presence of an inverse correlation between δ15N values and the 40Ar*/N ratios indicating mixing between two isotopically distinct components. The first, released at temperatures between 400° and 700° C from hydrous minerals, has a δ15N value close or below 0% and is accompanied by radiogenic Ar. The second, void of radiogenic Ar, is released at temperatures >800° C from anhydrous phases and has a δ15N value of +6 to +8%. The first component is likely ammonium replacing K in mica while the second is possibly ammonium adsorbed in-between negatively charged layers of clay minerals. Upon dehydration, the inter-layer site will be "closed", and loosely adsorbed cations are finally trapped in the mineral while noble gas Ar is lost. The higher δ15N in mica is possibly due either to (1) trapping of N representing a later (post-Archean) event, or; (2) fractionation of N with negative δ15N value due to partial release of N from the adsorption site. Mixing between different aliquots of these two components might possibly explain the observed N isotopic variability among micas in the Archean.

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.

Platinum stable isotopes in ferromanganese crust and nodules

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

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.

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.

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.

Long-term data set analysis of stable isotopic composition in German rivers

NASA Astrophysics Data System (ADS)

Reckerth, Anne; Stichler, Willibald; Schmidt, Axel; Stumpp, Christine

2017-09-01

Stable isotopes oxygen-18 (18O) and deuterium (2H) are commonly used to investigate hydrological processes in catchments. However, only a few isotope studies have been conducted on a large scale and rarely over long time periods. The objective of this study was to identify the spatial and seasonal variability of isotopic composition in river water and how it is affected by geographical and hydrological factors. The stable isotopic composition of river water has been measured in nine large river catchments in Germany for a time period of 12 years or 26 years. We conducted time series and correlation analyses to identify spatial and temporal patterns of the isotopic composition in the rivers. Further, we compared it to isotopic composition in local precipitation and catchments characteristics. In the majority of the rivers, the spatial and temporal patterns of precipitation were directly reflected in river water. The isotopic signals of the river water were time shifted and show attenuated amplitudes. Further deviations from isotopic compositions in local precipitation were observed in catchments with complex flow systems. These deviations were attributed to catchment processes and influences like evaporation, damming and storage. The seasonality of the isotopic composition was mainly determined by the discharge regimes of the rivers. We found correlations between isotopic long-term averages and catchment altitude as well as latitude and longitude, resulting in a northwest-southeast gradient. Furthermore, it was shown that long-term averages of d-excess were inversely related to flow length and catchment size, which indicates that evaporation enrichment has an impact on the isotopic composition even in catchments of humid climates. This study showed that isotopic composition in rivers can serve as a proxy for the local precipitation and can be utilized as an indicator for hydrological processes even in large river basins. In future, such long time series will help to also understand the impact of changes in the hydrological cycle on the larger scales. They can also be used for calibration and validation of flow and transport models at catchment and sub-catchment scale.

Lead isotope ratios for bullets, forensic evaluation in a Bayesian paradigm.

PubMed

Sjåstad, Knut-Endre; Lucy, David; Andersen, Tom

2016-01-01

Forensic science is a discipline concerned with collection, examination and evaluation of physical evidence related to criminal cases. The results from the activities of the forensic scientist may ultimately be presented to the court in such a way that the triers of fact understand the implications of the data. Forensic science has been, and still is, driven by development of new technology, and in the last two decades evaluation of evidence based on logical reasoning and Bayesian statistic has reached some level of general acceptance within the forensic community. Tracing of lead fragments of unknown origin to a given source of ammunition is a task that might be of interest for the Court. Use of data from lead isotope ratios analysis interpreted within a Bayesian framework has shown to be suitable method to guide the Court to draw their conclusion for such task. In this work we have used isotopic composition of lead from small arms projectiles (cal. .22) and developed an approach based on Bayesian statistics and likelihood ratio calculation. The likelihood ratio is a single quantity that provides a measure of the value of evidence that can be used in the deliberation of the court. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

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.

Field isotopic study of lead fate and compartmentalization in earthworm-soil-metal particle systems for highly polluted soil near Pb recycling factory.

PubMed

Goix, Sylvaine; Mombo, Stéphane; Schreck, Eva; Pierart, Antoine; Lévêque, Thibaut; Deola, Frédéric; Dumat, Camille

2015-11-01

Earthworms are important organisms in soil macrofauna and play a key role in soil functionality, and consequently in terrestrial ecotoxicological risk assessments. Because they are frequently observed in soils strongly polluted by metals, the influence of earthworm bioturbation on Pb fate could therefore be studied through the use of Pb isotopes. Total Pb concentrations and isotopic composition ((206)Pb, (207)Pb and (208)Pb) were then measured in earthworms, casts and bulk soils sampled at different distance from a lead recycling factory. Results showed decreasing Pb concentrations with the distance from the factory whatever the considered matrix (bulk soils, earthworm bodies or cast samples) with higher concentrations in bulk soils than in cast samples. The bivariate plot (208)Pb/(206)Pb ratios versus (206)Pb/(207)Pb ratios showed that all samples can be considered as a linear mixing between metallic process particulate matter (PM) and geochemical Pb background. Calculated anthropogenic fraction of Pb varied between approximately 84% and 100%. Based on Pb isotopic signatures, the comparison between casts, earthworms and bulk soils allowed to conclude that earthworms preferentially ingest the anthropogenic lead fraction associated with coarse soil organic matter. Actually, soil organic matter was better correlated with Pb isotopic ratios than with Pb content in soils. The proposed hypothesis is therefore a decrease of soil organic matter turnover due to Pb pollution with consequences on Pb distribution in soils and earthworm exposure. Finally, Pb isotopes analysis constitutes an efficient tool to study the influence of earthworm bioturbation on Pb cycle in polluted soils. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Zn isotopes in hydrothermal sulfides and their oxidation products along the south mid-Atlantic ridge: evidence of hydrothermal fluid deposition

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Lei, Jijiang; Wang, Hao; Li, Zhenggang

2018-04-01

Significant Zn isotope fractionation occurs during seafloor hydrothermal activities. Therefore, exploring variations in Zn isotope composition affected by hydrothermal fluids and oxidative processes would help to better understand hydrothermal fluid cycling and sulfide deposition on mid-ocean ridges. In this paper, the Zn isotope compositions of different types of sulfides and their oxidation products obtained from hydrothermal fields on the South Mid-Atlantic Ridge (13-15°S) were analyzed using a Neptune plus MC-ICP-MS. The δ66Zn ratios range from -0.14‰ to +0.38‰, and the average δ66Zn ratio is +0.12±0.06‰ ( n=21, 2 SD) for all the studied sulfides and oxidation products. The Cu-rich sulfides have a slightly heavier Zn isotope composition (average δ66Zn=+0.19±0.07‰, n=6) than the Zn-rich sulfides (average δ66Zn=-0.02±0.06‰, n=5). The Zn isotope compositions of the oxidation products are similar to those of the Cu-rich sulfides, with an average δ66Zn ratio of 0.14±0.06‰ ( n=10, 2 SD). The Zn isotope compositions of all the samples are generally within the ranges of sulfides from hydrothermal fields on other mid-ocean ridges, such as the East Pacific Rise (9°N, 21°N) and the Trans-Atlantic Geotraverse. However, the average Zn isotope composition indicates the presence of significantly lighter Zn isotopes relative to those reported in the literature (average δ66Zn=+0.39‰). The significant enrichment of the Zn-rich sulfides with light Zn isotopes reveals that kinetic fractionation likely occurs during mineral deposition. Furthermore, the Zn isotope compositions of the sulfides and their oxidation products (average δ66Zn=+0.12‰) are significantly lighter than the average Zn isotope composition of the ocean (δ66Zn=+0.5‰), which could further constrain the modern Zn isotope cycle in the ocean by serving as a sink for light Zn isotopes.

Along and across arc geochemical variations in NW Central America: Evidence for involvement of lithospheric pyroxenite

NASA Astrophysics Data System (ADS)

Heydolph, Ken; Hoernle, Kaj; Hauff, Folkmar; Bogaard, Paul van den; Portnyagin, Maxim; Bindeman, Ilya; Garbe-Schönberg, Dieter

2012-05-01

The Central American Volcanic Arc (CAVA) has been the subject of intensive research over the past few years, leading to a variety of distinct models for the origin of CAVA lavas with various source components. We present a new model for the NW Central American Volcanic Arc based on a comprehensive new geochemical data set (major and trace element and Sr-Nd-Pb-Hf-O isotope ratios) of mafic volcanic front (VF), behind the volcanic front (BVF) and back-arc (BA) lava and tephra samples from NW Nicaragua, Honduras, El Salvador and Guatemala. Additionally we present data on subducting Cocos Plate sediments (from DSDP Leg 67 Sites 495 and 499) and igneous oceanic crust (from DSDP Leg 67 Site 495), and Guatemalan (Chortis Block) granitic and metamorphic continental basement. We observe systematic variations in trace element and isotopic compositions both along and across the arc. The data require at least three different endmembers for the volcanism in NW Central America. (1) The NW Nicaragua VF lavas require an endmember with very high Ba/(La, Th) and U/Th, relatively radiogenic Sr, Nd and Hf but unradiogenic Pb and low δ18O, reflecting a largely serpentinite-derived fluid/hydrous melt flux from the subducting slab into a depleted N-MORB type of mantle wedge. (2) The Guatemala VF and BVF mafic lavas require an enriched endmember with low Ba/(La, Th), U/Th, high δ18O and radiogenic Sr and Pb but unradiogenic Nd and Hf isotope ratios. Correlations of Hf with both Nd and Pb isotopic compositions are not consistent with this endmember being subducted sediments. Granitic samples from the Chiquimula Plutonic Complex in Guatemala have the appropriate isotopic composition to serve as this endmember, but the large amounts of assimilation required to explain the isotope data are not consistent with the basaltic compositions of the volcanic rocks. In addition, mixing regressions on Nd vs. Hf and the Sr and O isotope plots do not go through the data. Therefore, we propose that this endmember could represent pyroxenites in the lithosphere (mantle and possibly lower crust), derived from parental magmas for the plutonic rocks. (3) The Honduras and Caribbean BA lavas define an isotopically depleted endmember (with unradiogenic Sr but radiogenic Nd, Hf and Pb isotope ratios), having OIB-like major and trace element compositions (e.g. low Ba/(La, Th) and U/Th, high La/Yb). This endmember is possibly derived from melting of young, recycled oceanic crust in the asthenosphere upwelling in the back-arc. Mixing between these three endmember types of magmas can explain the observed systematic geochemical variations along and across the NW Central American Arc.

Hypoxia induces copper stable isotope fractionation in hepatocellular carcinoma, in a HIF-independent manner.

PubMed

Bondanese, Victor P; Lamboux, Aline; Simon, Melanie; Lafont, Jérôme E; Albalat, Emmanuelle; Pichat, Sylvain; Vanacker, Jean-Marc; Telouk, Philippe; Balter, Vincent; Oger, Philippe; Albarède, Francis

2016-11-09

Hepatocellular carcinoma (HCC) is the most frequent type of primary liver cancer, with increasing incidence worldwide. The unrestrained proliferation of tumour cells leads to tumour hypoxia which in turn promotes cancer aggressiveness. While changes in the concentration of copper (Cu) have long been observed upon cancerization, we have recently reported that the isotopic composition of copper is also altered in several types of cancer. In particular, we showed that in hepatocellular carcinoma, tumour tissue contains heavier copper compared to the surrounding parenchyma. However, the reasons behind such isotopic signature remained elusive. Here we show that hypoxia causes heavy copper enrichment in several human cell lines. We also demonstrate that this effect of hypoxia is pH, HIF-1 and -2 independent. Our data identify a previously unrecognized cellular process associated with hypoxia, and suggests that in vivo tumour hypoxia determines copper isotope fractionation in HCC and other solid cancers.

Isotopic evidence of spatial magnitude of the Pb deposition near a lead smelter

NASA Astrophysics Data System (ADS)

Flament, P.; Franssens, M.; Debout, K.; Weis, D.

2003-05-01

In order to détermine the dry deposition of lead around a Pb-Zn refinery, two cross-sectional sampling experiments, using deposition plates, have been performed on a daiiy basis, ucder representative meteorological situations (north-easterly and south-westerly winds). The amount of lead deposited as well as its isotopic composition (expressed by the ^{206}Pb/^{207}Pb ratio) are systematically measured. For a daily production of approximately 670 metric tons of (Pb+Zn) the dry fallout, greater than 1000 μg Pb.h^{-1}.m^{-2} on the edge of the plant, falls to about 100 μg Pb.h^{-1}.m^{-2}, four kilometres away from the refinery. This value is still ten times higher than th urban background (<10 μg Pb.h^{-1}.m^{-2}). The spatial extension of the dry deposition plume is evidenced by the evolution of the isotopic signature of the refinery (1.10<^{206}Pb/^{207}), clearly distinct from the urban backgrounde signature (1.15<^{206}Pb/^{207}Pb<1.16). As a first estimate, the extension of the deposition plume seems not to be linked to the wind speed. At the opposite, diffuse emissions from slag heaps are related to this parameter.

The Oxygen Isotopic Composition of the Sun

NASA Astrophysics Data System (ADS)

McKeegan, K. D.; Kallio, A.; Heber, V. S.; Jarzebinski, G.; Mao, P.; Coath, C.; Kunihiro, T.; Wiens, R. C.; Judith, A.; Burnett, D. S.

2010-12-01

An accurate and precise determination of the oxygen isotopic composition of the Sun is the highest priority scientific goal of the Genesis Mission [1] as such data would provide a baseline from which one could interpret the oxygen isotopic anomalies found at all spatial scales in inner solar system materials. We have measured oxygen isotope compositions of implanted solar wind in 40 spots along a radial traverse of the Genesis SiC target sample 60001 by depth profiling with the UCLA MegaSIMS [2]. Mass-dependent fractionation induced by the solar wind concentrator [3] ion optics was corrected by comparison of the concentrator 22Ne/20Ne with that measured in a bulk solar wind target (diamond-like carbon on Si, [4]). The solar wind captured at L1 has an isotopic composition of (δ18O, δ17O) ≈ (-99, -79)‰, a value which is far removed from the terrestrial mass fractionation line. Profiles from the central portion of the target, where solar concentrations are highest and background corrections minimal, yield a mean Δ17O = -28.3 ± 1.8 ‰ indicating that the Earth and other planetary materials from the inner solar system are highly depleted in 16O relative to the solar wind. A mass-dependent fractionation of ~ -20%/amu in the acceleration of solar wind is required if we hypothesize that the photospheric oxygen isotope value, which represents the bulk starting composition of the solar system, is on the 16O-mixing line characteristic of refractory phase in primitive meteorites [5]. With this assumption, our preferred value for the bulk solar oxygen isotope composition is δ18O ≈ δ17O ≈ -57‰. A mechanism is required to fractionate oxygen isotopes in a non-mass-dependent manner to deplete 16O by ~6 to 7% in the rocky materials of the solar nebula. As oxygen is the third most abundant element in the solar system, and the most abundant in the terrestrial planets, this mechanism must operate on a large scale. Isotope-selective photochemistry, for example as in self-shielding of CO, operating in the solar nebula [6,7] or its precursor cloud [8] is a leading candidate; other models involving molecular symmetry-dependent reactions are also viable [9,10]. References: [1] D. Burnett et al. (2003) Space Sci. Rev. 105, 509. [2] K. McKeegan et al. (2008) LPSC XXIX, #2020. [3] R.Wiens et al. (2003) Space Sci. Rev. 105, 601. [4] V. Heber et al. Space Sci. Rev. 130, 309. [5] R. Clayton and T. Mayeda (1978) EPSL 40, 168. [6] R. Clayton (2002) Nature 415, 860. [7] J. Lyons and E. Young (2005) Nature 434, 317. [8] H. Yurimoto and K. Kuramoto (2004) Science 305, 1763. [9] M. Thiemens (1999) Science 283, 341. [10] R. Marcus (2004) J. Chem. Phys. 121, 8201.

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.

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.

The silicon isotope composition of the upper continental crust

NASA Astrophysics Data System (ADS)

Savage, Paul S.; Georg, R. Bastian; Williams, Helen M.; Halliday, Alex N.

2013-05-01

The upper continental crust (UCC) is the major source of silicon (Si) to the oceans and yet its isotopic composition is not well constrained. In an effort to investigate the degree of heterogeneity and provide a robust estimate for the average Si isotopic composition of the UCC, a representative selection of well-characterised, continentally-derived clastic sediments have been analysed using high-precision MC-ICPMS. Analyses of loess samples define a narrow range of Si isotopic compositions (δ30Si = -0.28‰ to -0.15‰). This is thought to reflect the primary igneous mineralogy and predominance of mechanical weathering in the formation of such samples. The average loess δ30Si is -0.22 ± 0.07‰ (2 s.d.), identical to average granite and felsic igneous compositions. Therefore, minor chemical weathering does not resolvably affect bulk rock δ30Si, and loess is a good proxy for the Si isotopic composition of unweathered, crystalline, continental crust. The Si isotopic compositions of shales display much more variability (δ30Si = -0.82‰ to 0.00‰). Shale Si isotope compositions do not correlate well with canonical proxies for chemical weathering, such as CIA values, but do correlate negatively with insoluble element concentrations and Al/Si ratios. This implies that more intensive or prolonged chemical weathering of a sedimentary source, with attendant desilicification, is required before resolvable negative Si isotopic fractionation occurs. Shale δ30Si values that are more positive than those of felsic igneous rocks most likely indicate the presence of marine-derived silica in such samples. Using the data gathered in this study, combined with already published granite Si isotope analyses, a weighted average composition of δ30Si = -0.25 ± 0.16‰ (2 s.d.) for the UCC has been calculated.

Heterogenous Oxygen Isotopic Composition of a Complex Wark-Lovering Rim and the Margin of a Refractory Inclusion from Leoville

NASA Technical Reports Server (NTRS)

Simon, J. I.; Matzel, J. E. P.; Simon, S. B.; Weber, P. K.; Grossman, L.; Ross, D. K.; Hutcheon, I. D.

2014-01-01

Wark-Lovering (WL) rims [1] surrounding many refractory inclusions represent marker events in the early evolution of the Solar System in which many inclusions were exposed to changes in pressure [2], temperature [3], and isotopic reservoirs [4-7]. The effects of these events can be complex, not only producing mineralogical variability of WL rims [2], but also leading to mineralogical [8-10] and isotopic [7, 11, 12] changes within inclusion interiors. Extreme oxygen isotopic heterogeneity measured in CAIs has been explained by mixing between distinct oxygen gas reservoirs in the nebula [13]. Some WL rims contain relatively simple mineral layering and/or are isotopically homogeneous [14, 15]. As part of a larger effort to document and understand the modifications observed in some CAIs, an inclusion (L6) with a complex WL rim from Leoville, a member of the reduced CV3 subgroup was studied. Initial study of the textures and mineral chemistry was presented by [16]. Here we present NanoSIMS oxygen isotopic measurements to complement these petrologic observations.

Isotopic excesses of proton-rich nuclei related to space weathering observed in a gas-rich meteorite Kapoeta

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

Hidaka, Hiroshi; Yoneda, Shigekazu, E-mail: hidaka@hiroshima-u.ac.jp, E-mail: s-yoneda@kahaku.go.jp

2014-05-10

The idea that solar system materials were irradiated by solar cosmic rays from the early Sun has long been suggested, but is still questionable. In this study, Sr, Ba, Ce, Nd, Sm, and Gd isotopic compositions of sequential acid leachates from the Kapoeta meteorite (howardite) were determined to find systematic and correlated variations in their isotopic abundances of proton-rich nuclei, leading to an understanding of the irradiation condition by cosmic rays. Significantly large excesses of proton-rich isotopes (p-isotopes), {sup 84}Sr, {sup 130}Ba, {sup 132}Ba, {sup 136}Ce, {sup 138}Ce, and {sup 144}Sm, were observed, particularly in the first chemical separate, whichmore » possibly leached out of the very shallow layer within a few μm from the surface of regolith grains in the sample. The results reveal the production of p-isotopes through the interaction of solar cosmic rays with the superficial region of the regolith grains before the formation of the Kapoeta meteorite parent body, suggesting strong activity in the early Sun.« less

Lead in the Getchell-Turquoise ridge Carlin-type gold deposits from the perspective of potential igneous and sedimentary rock sources in Northern Nevada: Implications for fluid and metal sources

USGS Publications Warehouse

Tosdal, R.M.; Cline, J.S.; Fanning, C.M.; Wooden, J.L.

2003-01-01

Lead isotope compositions of bulk mineral samples (fluorite, orpiment, and realgar) determined using conventional techniques and of ore-stage arsenian pyrite using the Sensitive High Resolution Ion-Microprobe (SHRIMP) in the Getchell and Turquoise Ridge Carlin-type gold deposits (Osgood Mountains) require contribution from two different Pb sources. One Pb source dominates the ore stage. It has a limited Pb isotope range characterized by 208Pb/206Pb values of 2.000 to 2.005 and 207Pb/206Pb values of 0.8031 to 0.8075, as recorded by 10-??m-diameter spot SHRIMP analyses of ore-stage arsenian pyrite. These values approximately correspond to 206Pb/204Pb of 19.3 to 19.6, 207Pb/204Pb of 15.65 to 15.75, and 208Pb/204Pb of 39.2 to 39.5. This Pb source is isotopically similar to that in average Neoproterozoic and Cambrian elastic rocks but not to any potential magmatic sources. Whether those clastic rocks provided Pb to the ore fluid cannot be unequivocally proven because their Pb isotope compositions over the same range as in ore-stage arsenian pyrite are similar to those of Ordovician to Devonian siliciclastic and calcareous rocks. The Pb source in the calcareous rocks most likely is largely detrital minerals, since that detritus was derived from the same sources as the detritus in the Neoproterozoic and Cambrian clastic rocks. The second Pb source is characterized by a large range of 206Pb/204Pb values (18-34) with a limited range of 208Pb/204Pb values (38.1-39.5), indicating low but variable Th/U and high and variable U/Pb values. The second Pb source dominates late and postore-stage minerals but is also found in preore sulfide minerals. These Pb isotope characteristics typify Ordovician to Devonian siliciclastic and calcareous rocks around the Carlin trend in northeast Nevada. Petrologically similar rocks host the Getchell and Turquoise Ridge deposits. Lead from the second source was either contributed from the host sedimentary rock sequences or brought into the hydrothermal system by oxidized ground water as the system collapsed. Late ore- and postore-stage sulfide minerals (pyrite, orpiment, and stibnite) from the Betze-Post and Meikle deposits in the Carlin trend and from the Jerritt Canyon mining district have Pb isotope characteristics similar to those determined in Getchell and Turquoise Ridge. This observation suggests that the Pb isotope compositions of their ore fluids may be similar to those at Getchell and Turquoise Ridge. Two models can explain the Pb isotope compositions of the ore-stage arsenian pyrite versus the late ore or postore sulfide minerals. In either model, Pb from the Ordovician to Devonian siliciclastic and calcareous rock source enters the hydrothermal system late in the ore stage but not to any extent during the main stage of ore deposition. In one model, ore-stage Pb was derived from a source with Pb isotope compositions similar to those of the Neoproterozoic and Cambrian clastic sequence, transported as part of the ore fluid and then deposited in the ore-stage arsenian pyrite and fluorite. The second model is based on the observation that the Pb isotope characteristics of the ore-stage minerals also are found in some Ordovician to Devonian calcareous and siliciclastic rocks. Hence, ore-stage Pb could have been derived locally and simply concentrated during the ore stage. Critical to the second model is the removal of all high 206Pb/204Pb (>20) material during alteration. It Also requires the retention of only the low 206Pb/204Pb component of the Ordovician to Devonian sedimentary rocks. This critical step is possible only if the high 206Pb/204Pb values are contained in readily dissolvable mineral phases, whereas the low 206Pb/204Pb values are found only in refractory minerals that released Pb during a final alteration stage just prior deposition of auriferous arsenian pyrite. Distinguishing between Pb transported with the ore fluid or inherited from the site of mineral deposition is not straightforward

A new method of tree xylem water extraction for isotopic analysis

NASA Astrophysics Data System (ADS)

Gierke, C.; Newton, B. T.

2011-12-01

The Sacramento Mountain Watershed Study in the southern Sacramento Mountains of New Mexico is designed to assess the forest restoration technique of tree thinning in mountain watersheds as an effective method of increasing local and regional groundwater recharge. The project is using a soil water balance approach to quantify the partitioning of local precipitation within this watershed before and after thinning trees. Understanding what sources trees extract their water from (e.g. shallow groundwater, unsaturated fractured bedrock, and soils) is difficult due to a complex hydrologic system and heterogeneous distribution of soil thicknesses. However, in order to accurately quantify the soil water balance and to assess how thinning trees will affect this water balance, it is important determine the sources from which trees extract their water. We plan to use oxygen and hydrogen stable isotopic analysis of various end member waters to identify these different sources. We are in the process of developing a new method of determining the isotopic composition of tree water that has several advantages over conventional methods. Within the tree there is the xylem which transports water from the roots to the leaves and the phloem which transports starches and sugars in a water media throughout the tree. Previous studies have shown that the isotopic composition of xylem water accurately reflects that of source water, while phloem water has undergone isotopic fractionation during photosynthesis and metabolism. The distillation of water from twigs, which is often used to extract tree water for isotopic analysis, is very labor intensive. Other disadvantages to distillation methods include possible fractionation due to phase changes and the possible extraction of fractionated phloem waters. Employing a new mixing method, the composition of the twig water (TW) can be determined by putting twigs of unknown isotopic water composition into waters of known compositions or initial waters (IW), allowing diffusive processes to proceed to equilibrium, measuring the composition of the resulting mixture or final water (FW) then, solving a simple mixing equation. To evaluate this method, we collected several twig samples from Douglas Firs in the Sacramento Mountains. Twig water was prepared for isotopic analysis both by cryogenic distillation and the mixing method. Soil in close proximity to these trees was also sampled and water was extracted by cryogenic distillation. Preliminary results show that the isotopic composition of distilled twig water and soil waters plot to the right of the local meteoric water line (LMWL) suggesting that trees are extracting shallow evaporated soil water. Twig water obtained from the mixing method plot near the LMWL within the range expected for local snow melt, suggesting a possibly deeper non-evaporated source. In general, distillation values are approximately 4% heavier with respect to delta 18O than waters obtained from the mixing method. It is possible that this difference is due to the contribution of the fractionated water of the twig phloem that is released during the distillation process. This difference is quite significant and can lead to very different interpretations. These results are being addressed with additional experiments.

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.

Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method

NASA Astrophysics Data System (ADS)

Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

2018-04-01

Isotope ratio monitoring by 13C NMR spectrometry (irm-13C NMR) provides the complete 13C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13C natural abundance values (50‰), irm-13C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13C NMR. Until now, the conventional strategy to determine the position-specific abundance xi relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1H NMR pulse sequence (named DWET) with a 13C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T1, which forms a serious limitation for irm-13C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T1 variations. Their performance is evaluated on the determination of the 13C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm-13C NMR since it is now possible to perform isotopic analysis with high relaxing agent concentrations, leading to a strong reduction of the overall experiment time.

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.

Assessing the Origins of Aliphatic Amines in the Murchison Meteorite from their Compound-Specific Carbon Isotopic Ratios and Enantiomeric Composition

NASA Technical Reports Server (NTRS)

Aponte, Jose; Dworkin, Jason; Elsila, Jamie E.

2014-01-01

The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of L-enantiomeric excesses for alpha-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are chemically related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with delta C-13 values ranging from +21% to +129%, showing a decrease in C-13 with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an L-enantiomeric excess of 9.7; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential linkage to meteoritic amino acids.

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.

Formation of medical radioisotopes {sup 111}In, {sup 117m}Sn, {sup 124}Sb, and {sup 177}Lu in photonuclear reactions

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

Danagulyan, A. S.; Hovhannisyan, G. H., E-mail: hov-gohar@ysu.am; Bakhshiyan, T. M.

2015-06-15

The possibility of the photonuclear production of radioisotopes {sup 111}In, {sup 117m}Sn, {sup 124}Sb, and {sup 177}Lu is discussed. Reaction yields were measured by the gamma-activation method. The enriched tin isotopes {sup 112,} {sup 118}Sn and Te and HfO{sub 2} of natural isotopic composition were used as targets. The targets were irradiated at the linear electron accelerator of Alikhanian National Science Laboratory (Yerevan) at the energy of 40 MeV. The experimental results obtained in this way reveal that the yield and purity of radioisotopes {sup 111}In and {sup 117}mSn are acceptable for their production via photonuclear reactions. Reactions proceeding onmore » targets from Te and HfO{sub 2} of natural isotopic composition and leading to the formation of {sup 124}Sb and {sup 177}Lu have small yields and are hardly appropriate for the photoproduction of these radioisotopes even in the case of enriched targets.« less

Disequilibrium δ18O values in microbial carbonates as a tracer of metabolic production of dissolved inorganic carbon

NASA Astrophysics Data System (ADS)

Thaler, Caroline; Millo, Christian; Ader, Magali; Chaduteau, Carine; Guyot, François; Ménez, Bénédicte

2017-02-01

Carbon and oxygen stable isotope compositions of carbonates are widely used to retrieve paleoenvironmental information. However, bias may exist in such reconstructions as carbonate precipitation is often associated with biological activity. Several skeleton-forming eukaryotes have been shown to precipitate carbonates with significant offsets from isotopic equilibrium with water. Although poorly understood, the origin of these biologically-induced isotopic shifts in biogenic carbonates, commonly referred to as "vital effects", could be related to metabolic effects that may not be restricted to mineralizing eukaryotes. The aim of our study was to determine whether microbially-mediated carbonate precipitation can also produce offsets from equilibrium for oxygen isotopes. We present here δ18O values of calcium carbonates formed by the activity of Sporosarcina pasteurii, a carbonatogenic bacterium whose ureolytic activity produces ammonia (thus increasing pH) and dissolved inorganic carbon (DIC) that precipitates as solid carbonates in the presence of Ca2+. We show that the 1000 lnαCaCO3-H2O values for these bacterially-precipitated carbonates are up to 24.7‰ smaller than those expected for precipitation at isotopic equilibrium. A similar experiment run in the presence of carbonic anhydrase (an enzyme able to accelerate oxygen isotope equilibration between DIC and water) resulted in δ18O values of microbial carbonates in line with values expected at isotopic equilibrium with water. These results demonstrate for the first time that bacteria can induce calcium carbonate precipitation in strong oxygen isotope disequilibrium with water, similarly to what is observed for eukaryotes. This disequilibrium effect can be unambiguously ascribed to oxygen isotope disequilibrium between DIC and water inherited from the oxygen isotope composition of the ureolytically produced CO2, probably combined with a kinetic isotope effect during CO2 hydration/hydroxylation. The fact that both disequilibrium effects are triggered by the metabolic production of CO2, which is common in many microbially-mediated carbonation processes, leads us to propose that metabolically-induced offsets from isotopic equilibrium in microbial carbonates may be more common than previously considered. Therefore, precaution should be taken when using the oxygen isotope signature of microbial carbonates for diagenetic and paleoenvironmental reconstructions.

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.

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.

Advances in natural stable isotope ratio analysis of human hair to determine nutritional and metabolic status.

PubMed

Petzke, Klaus J; Fuller, Benjamin T; Metges, Cornelia C

2010-09-01

We review the literature on the use of stable isotope ratios at natural abundance to reveal information about dietary habits and specific nutrient intakes in human hair protein (keratin) and amino acids. In particular, we examine whether hair isotopic compositions can be used as unbiased biomarkers to provide information about nutritional status, metabolism, and diseases. Although the majority of research on the stable isotope ratio analysis of hair has focused on bulk protein, methods have been recently employed to examine amino acid-specific isotope ratios using gas chromatography or liquid chromatography coupled to an isotope ratio mass spectrometer. The isotopic measurement of amino acids has the potential to answer research questions on amino acid nutrition, metabolism, and disease processes and can contribute to a better understanding of the variations in bulk protein isotope ratio values. First results suggest that stable isotope ratios are promising as unbiased nutritional biomarkers in epidemiological research. However, variations in stable isotope ratios of human hair are also influenced by nutrition-dependent nitrogen balance, and more controlled clinical research is needed to examine these effects in human hair. Stable isotope ratio analysis at natural abundance in human hair protein offers a noninvasive method to reveal information about long-term nutritional exposure to specific nutrients, nutritional habits, and in the diagnostics of diseases leading to nutritional stress and impaired nitrogen balance.

Metals and metalloids in atmospheric dust: Use of lead isotopic analysis for source apportionment

NASA Astrophysics Data System (ADS)

Felix Villar, Omar I.

Mining activities generate aerosol in a wide range of sizes. Smelting activities produce mainly fine particles (<1 microm). On the other hand, milling, crushing and refining processes, as well tailings management, are significant sources of coarse particles (> 1 microm). The adverse effects of aerosols on human health depend mainly on two key characteristics: size and chemical composition. One of the main objectives of this research is to analyze the size distribution of contaminants in aerosol produced by mining operations. For this purpose, a Micro-Orifice Uniform Deposit Impactor (MOUDI) was utilized. Results from the MOUDI samples show higher concentrations of the toxic elements like lead and arsenic in the fine fraction (<1 microm). Fine particles are more likely to be deposited in the deeper zones of the respiratory system; therefore, they are more dangerous than coarse particles that can be filtered out in the upper respiratory system. Unfortunately, knowing the total concentration of contaminants does not give us enough information to identify the source of contamination. For this reason, lead isotopes have been introduced as fingerprints for source apportionment. Each source of lead has specific isotopic ratios; by knowing these ratios sources can be identified. During this research, lead isotopic ratios were analyzed at different sites and for different aerosol sizes. From these analyses it can be concluded that lead isotopes are a powerful tool to identify sources of lead. Mitigation strategies could be developed if the source of contamination is well defined. Environmental conditions as wind speed, wind direction, relative humidity and precipitation have an important role in the concentration of atmospheric dust. Dry environments with low relative humidity are ideal for the transport of aerosols. Results obtained from this research show the relationship between dust concentrations and meteorological parameters. Dust concentrations are highly correlated with relative humidity and wind speed. With all the data collected on site and the analysis of the meteorological parameters, models can be develop to predict the transport of particles as well as the concentration of contaminants at a specific point. These models were developed and are part of the results shown in this dissertation.

Some Pb and Sr isotopic measurements on eclogites from the Roberts Victor mine, South Africa

USGS Publications Warehouse

Manton, W.I.; Tatsumoto, M.

1971-01-01

Five nodules of eclogite, one nodule of garnet peridotite and one sample of kimberlite from the Roberts Victor mine were analyzed for concentrations of U, Th, Pb, Rb and Sr and isotopic compositions of Pb and Sr. In the eclogites, U content ranges from 0.09 to 0.26 ppm, Th from 0.35 to 1.1 ppm, Pb from 0.79 to 5.5 ppm, Rb from 2.1 to 28 ppm and Sr from 133 to 346 ppm; 206Pb/204Pb ratios range from 14.8 to 18.5, 207Pb/204Pb from 14.9 to 15.7, 208Pb/204Pb from 35.2 to 38.5. The garnet peridotite contains 0.22 ppm U, 0.97 ppm Th, 1.05 ppm Pb, 6.9 ppm Rb and 108 ppm Sr and the kimberlite contains 2.5 ppm U, 30 ppm Th, 37 ppm Pb, 113 ppm Rb and 2040 ppm Sr. The lead in the eclogites has two components, a lead pyroextractable at 1100-1200?? and a non-pyroextractable residual lead. In three of the eclogites, which are to some extent altered, a proportion of the pyroextractable lead may be contaminating lead from the kimberlite, but an altered kyanite eclogite does not appear to be contaminated by this same kimberlite. The pyroextractable lead from a less altered eclogite contains a much larger proportion of 206Pb. Compositions calculated for the residual leads vary greatly. In many of the pyroextraction runs the primary eclogitic phases disappeared and the new phases plagioclase, clinopyroxene and a magnetic iron compound were formed. Why part of the lead should have been retained by these new phases is not understood. ?? 1971.

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.

Pb isotope systematics in volcanic river system: Constraints about weathering processes

NASA Astrophysics Data System (ADS)

Negrel, P. J.; Millot, R.; Petelet-Giraud, E.; Guerrot, C.

2012-12-01

We present a series of lead isotopes in soils and sediments developed on volcanic rocks forming a small watershed flowing through the Massif Central (France). The Massif Central volcanic province is a widespread area of Tertiary to Recent continental alkaline volcanism comprising alkali basalts and basanites. The Allanche watershed has an area of 160 km2, a maximum altitude in the watershed of 1400 m (a.s.l.) and the relief between the extreme sampling points of 340 m The river is 29 km long from headwaters to the outlet and from its origin in the Cézallier area to its mouth in the Allagnon river (a tributary of the Allier river), the Allanche river flows through the volcanic terrains of the lava plateau (11 to 2.5 Ma). Main bedrocks are basanites (nepheline or leucitic basalts), with SiO2 around 41-45%, low Na2O + K2O (<5%), and with modal or normative nepheline or leucite and a ground mass of clinopyroxene and plagioclase. Surrounding rocks are feldspatic basalts with SiO2 close to 46-49%, low Na2O + K2O (<5%). The main phase in these basalts is plagioclase with normative nepheline, hyperstene and olivine. Crustal contamination (e.g. by granite, gneiss or metasedimentary granulite, as stated by Downes, 1987, doi: 10.1144/GSL.SP.1987.030.01.25) has occurred in the differentiated magmas of both series, as witnessed by lead isotopic variations in conjunction with Rb/La ratios and lead contents. Using Pb isotope ratios, major and trace elements (from Négrel and Deschamps, 1996, Aquatic Geochemistry, 2, 1-27) we therefore compare sediments and soils evolution over the Allanche river watershed. K and Ca are considered as mobile reference elements and illustrate the weathering state of soils and sediments relative to parent rocks through a large decrease in K and Ca content when compared to Si; the sediments being less depleted than soils. Lead, with regards to Si shows three behaviour with depleted Si content- same lead content that bedrock, depleted Si content- less lead content and depleted Si content - high lead content that bedrock. The comparison of 1000Pb/K versus Si/K ratio evidenced the evolution line from weathering processes and the lead enrichment from atmospheric deposition as a major contributor to explain the deviation of several points from this line. Lead isotopes decrease from bedrock to sediments-soils without any clear relationship when compared to lead contents. The use of Pb-isotopic compositions showed that most of the lead budget in sediments and soils result from bedrock weathering with an influence of gasoline additive-lead derived inputs and a lack of lead input from agricultural activities.

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

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

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

Assimilation of sediments embedded in the oceanic arc crust: myth or reality?

NASA Astrophysics Data System (ADS)

Bezard, Rachel; Davidson, Jon P.; Turner, Simon; Macpherson, Colin G.; Lindsay, Jan M.; Boyce, Adrian J.

2014-06-01

Arc magmas are commonly assumed to form by melting of sub-arc mantle that has been variably enriched by a component from the subducted slab. Although most magmas that reach the surface are not primitive, the impact of assimilation of the arc crust is often ignored with the consequence that trace element and isotopic compositions are commonly attributed only to varying contributions from different components present in the mantle. This jeopardises the integrity of mass balance recycling calculations. Here we use Sr and O isotope data in minerals from a suite of volcanic rocks from St Lucia, Lesser Antilles arc, to show that assimilation of oceanic arc basement can be significant. Analysis of 87Sr/86Sr in single plagioclase phenocrysts from four Soufrière Volcanic Complex (SVC; St Lucia) hand samples with similar composition (87Sr/86Sr = 0.7089-0.7091) reveals crystal isotopic heterogeneity among hand samples ranging from 0.7083 to 0.7094 with up to 0.0008 difference within a single hand sample. δO18 measurements in the SVC crystals show extreme variation beyond the mantle range with +7.5 to +11.1‰ for plagioclase (n=19), +10.6 to +11.8‰ for quartz (n=10), +9.4 to +9.8‰ for amphibole (n=2) and +9 to +9.5‰ for pyroxene (n=3) while older lavas (Pre-Soufriere Volcanic Complex), with less radiogenic whole rock Sr composition (87Sr/86Sr = 0.7041-0.7062) display values closer to mantle range: +6.4 to +7.9‰ for plagioclase (n=4) and +6 to +6.8‰ for pyroxene (n=5). We argue that the 87Sr/86Sr isotope disequilibrium and extreme δO18 values provide compelling evidence for assimilation of material located within the arc crust. Positive correlations between mineral δO18 and whole rock 87Sr/86Sr, 143Nd/144Nd and 206,207,208Pb/204Pb shows that assimilation seems to be responsible not only for the isotopic heterogeneity observed in St Lucia but also in the whole Lesser Antilles since St Lucia encompasses almost the whole-arc range of isotopic compositions. This highlights the need for detailed mineral-scale investigation of oceanic arc suites to quantify assimilation that could otherwise lead to misinterpretation of source composition and subduction processes.

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.

Compositional variation through time and space in Quaternary magmas of the Chyulu Hills Volcanic Province, Kenya

NASA Astrophysics Data System (ADS)

Widom, E.; Kuentz, D. C.

2017-12-01

The Chyulu Hills Volcanic Province, located in southern Kenya >100 km east of the Kenya Rift Valley, has produced mafic, monogenetic eruptions throughout the Quaternary. The volcanic field is considered to be an off-rift manifestation of the East African Rift System, and is known for the significant compositional variability of its eruptive products, which range from nephelinites to basanites, alkali basalts, hawaiites, and orthopyroxene-normative subalkaline basalts [1]. Notably, erupted compositions vary systematically in time and space: Pleistocene volcanism, occurring in the northern Chyulu Hills, was characterized by highly silica-undersaturated magmas, whereas Holocene volcanism, restricted to the southern Chyulu Hills, is less silica-understaturated, consistent with a progressive decrease in depth and increase in degree of melting with time, from north to south [1]. Pronounced negative K anomalies, and enriched trace element and Sr-Nd-Pb isotope signatures have been attributed to a metasomatized, amphibole-bearing, sub-continental lithospheric mantle (SCLM) source [2]. Seismic evidence for a partially molten zone in the SCLM beneath this region [3] may be consistent with such an interpretation. We have analyzed Chyulu Hills samples for Os, Hf and high precision Pb isotopes to further evaluate the magma sources and petrogenetic processes leading to systematic compositional variation in time and space. Sr-Nd-Pb-Hf isotope systematics and strong negative correlations of 206Pb/204Pb and highly incompatible trace element ratios with SiO2 are consistent with the progression from a deeper, HIMU-type source to a shallower, EM-type source. Os isotope systematics, however, suggest a more complex relationship; although all samples are more radiogenic than primitive mantle, the least radiogenic values (similar to primitive OIB) are found in magmas with intermediate SiO2, and those with lower or higher SiO2 are more radiogenic. This may be explained by interaction between mantle plume-derived magmas and heterogeneous metasomatized SCLM, consistent with the radiogenic Os isotope compositions found in some highly metasomatized mantle xenoliths associated with the Tanzanian craton [4]. [1] Spath et al., 2000; [2] Spath et al., 2001; [3] Ritter & Kasper, 1997; [4] Nelson et al., 2012.

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.

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.

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.

Recording the transition from flare-up to steady-state arc magmatism at the Purico-Chascon volcanic complex, northern Chile

NASA Astrophysics Data System (ADS)

Burns, Dale H.; de Silva, Shanaka L.; Tepley, Frank; Schmitt, Axel K.; Loewen, Matthew W.

2015-07-01

The long-term evolution of continental magmatic arcs is episodic, where a few transient events of high magmatic flux or flare-ups punctuate the low-flux magmatism or "steady state" that makes up most of the arc history. How this duality manifests in terms of differences in crustal architecture, magma dynamics and chemistry, and the time scale over which transitions occur is poorly known. Herein we use multiscale geochemical and isotopic characteristics coupled with geothermobarometry at the Purico-Chascon Volcanic Complex (PCVC) in the Central Andes to identify a transition from flare-up to steady state arc magmatism over ∼800 kyr during which significant changes in upper crustal magmatic dynamics are recorded. The PCVC is one of the youngest volcanic centers related to a 10-1 Ma ignimbrite flare-up in the Altiplano-Puna Volcanic Complex of the Central Andes. Activity at the PCVC initiated 0.98 ± 0.03 Ma with the eruption of a large 80-100 km3 crystal-rich dacite ignimbrite. High, restricted 87Sr/86Sr isotope ratios between 0.7085 and 0.7090 in the bulk rock and plagioclase crystals from the Purico ignimbrite, combined with mineral chemistry and phase relationships indicate the dacite magma accumulated and evolved at relatively low temperatures around 800-850 °C in the upper crust at 4-8 km depth. Minor andesite pumice erupted late in the ignimbrite sequence records a second higher temperature (965 °C), higher pressure environment (17-20 km), but with similar restricted radiogenic bulk rock 87Sr/86Sr = 0.7089-0.7091 to the dacites. The compositional and isotopic characteristics of the Purico ignimbrite implicate an extensive zone of upper crustal mixing, assimilation, storage and homogenization (MASH) between ∼30 and 4 km beneath the PCVC ∼1 Ma. The final eruptions at the PCVC < 0.18 ± 0.02 Ma suggest a change in the magmatic architecture beneath the PCVC. These eruptions produced three small <6 km3 crystal-rich dacite lava domes with radiogenic bulk rock 87Sr/86Sr ratios ranging from 0.7075 to 0.7081, that contain abundant basaltic-andesite inclusions with relatively low bulk rock 87Sr/86Sr ratios of 0.7057-0.7061. Plagioclase and amphibole in the host lava of Cerro Chascon, the largest of the domes, record two distinct magmatic environments; an upper crustal environment identical to that recorded in the Purico ignimbrite, and a second deeper, ∼15-20 km depth, higher temperature (∼922-1001 °C) environment. This deeper environment is recorded in textures and compositions of distinct mineral phases, and in intracrystalline isotope ratios. Plagioclase cores in the host dacite lava and mafic inclusions have in situ87Sr/86Sr isotopic compositions of 0.7083 to 0.7095, broadly similar to plagioclase from the Purico ignimbrite. In contrast, plagioclase rims and microphenocrysts in the mafic inclusions are isotopically distinct with lower 87Sr/86Sr isotope ratios (0.7057 to 0.7065 and 0.7062 to 0.7064, respectively) that overlap with the regional isotopic "baseline" compositions that are parental to the modern arc lavas. The textural and compositional characteristics of the PCVC attest to two distinct stages in its history. At ∼1 Ma the system was broadly homogeneous and dominantly dacitic recording extensive upper crustal magmatism. By ∼0.2 Ma the PCVC had transitioned to a more compositionally heterogeneous, smaller volume, mixed dacite to basaltic-andesite system, coinciding with the appearance of less-enriched "baseline" compositions. The evolution of PCVC is a microcosm of the Central Andean arc in this region where, from 10 to 1 Ma, upper crustal MASH processes resulted in the production and eruption of large volumes of homogeneous crystal-rich dacite during a regional ignimbrite flare-up. Since ∼1 Ma, decreasing explosivity, smaller eruptive volumes, increasing heterogeneity, and the emergence of less isotopically enriched basaltic-andesite to dacite composite volcanoes signal a return to steady-state arc volcanism. We posit that the transition from flare-up to steady state captured at the PCVC tracks the waning of the arc scale "thermal engine". High magmatic fluxes during the flare-up would lead to elevated geothermal gradients and efficient crustal processing leading to a dominantly "crustal" magmatism feeding the large volume Purico ignimbrite. This upper crustal MASH zone would act as an efficient filter to any parental compositions precluding them from the eruption record. As magmatic flux and thermal energy wanes, crustal isotherms would relax leading to greater thermal contrast between parental magmas, upper crust, and remnant felsic magmas stored in the upper crust. These changes are manifested in the preservation of textural and compositional heterogeneity and the survival of less isotopically enriched magmas in the upper crust. The chemical imprint of these arc-scale changes in magma dynamics is recorded at all scales from bulk rock to intra-crystalline. The distinct magma dynamics and chemical signatures of the two modes of arc magmatism detailed here should provide a model for investigations of mature continental arc evolution through time and space.

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.

Lithium elemental and isotopic disequilibrium in minerals from peridotite xenoliths from far-east Russia: Product of recent melt/fluid rock reaction

NASA Astrophysics Data System (ADS)

Rudnick, Roberta L.; Ionov, Dmitri A.

2007-04-01

Lithium concentrations and isotopic compositions of coexisting olivine and clinopyroxene (cpx) in well-characterized peridotite xenoliths from Tok (SE Siberian craton) and samples from two other far-east Russian localities reveal strong elemental and isotopic disequilibria, which correlates with bulk rock composition. Lithium concentrations in cpx from Tok (1-12 ppm) are equal to or significantly greater than those in coexisting olivines (1-5 ppm). The Li-rich cpx show core to rim zoning, indicative of Li infiltration from the grain boundaries. Olivines are generally unzoned, although Li concentrations can vary significantly from grain to grain. ol/cpxD varies from 0.2 to 1.0, which is lower than that expected for equilibrium partitioning ( ol/cpxDeq = 1.1 to 2.0), and reflects preferential Li enrichment in cpx. The Li isotopic compositions of both minerals range far beyond normal mantle δ7Li of ˜ + 4 ± 2. δ7Li cpx (- 0.8 to - 14.6) is systematically lighter than δ7Li of coexisting olivine (- 1.7 to + 11.9), and Δ 7Li ol-cpx varies from 2.8 to 22.9‰. The greatest elemental and isotopic disequilibria occur in the most fertile samples (lherzolites) and may reflect longer equilibration times and/or enhanced melt permeability in the more refractory samples. Collectively, these observations suggest that the peridotite minerals experienced Li addition via diffusion from a grain boundary melt or fluid shortly before or coincident with their entrainment into the host basalt (i.e., within tens of thousands of years, based on published diffusion coefficients for Li in cpx at the temperatures of equilibration). This diffusional ingress of Li generated large kinetic isotopic fractionation, leading to unusually light cpx and heavier olivines. Thus, low δ7Li cpx do not reflect the influence of an exotic mantle component related to crustal recycling.

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.

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

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.

Assessing Precipitation Isotope Variations during Atmospheric River Events to Reveal Dominant Atmospheric/Hydrologic Processes

NASA Astrophysics Data System (ADS)

McCabe-Glynn, S. E.; Johnson, K. R.; Yoshimura, K.; Buenning, N. H.; Welker, J. M.

2015-12-01

Extreme precipitation events across the Western US commonly associated with atmospheric rivers (ARs), whereby extensive fluxes of moisture are transported from the subtropics, can result in major damage and are projected by most climate models to increase in frequency and severity. However, they are difficult to project beyond ~ten days and the location of landfall and topographically induced precipitation is even more uncertain. Water isotopes, often used to reconstruct past rainfall variability, are useful natural tracers of atmospheric hydrologic processes. Because of the typical tropical and sub-tropical origins, ARs can carry unique water isotope (δ18O and δ2H, d-excess) signatures that can be utilized to provide source and process information that can lead to improving AR predictions. Recent analysis of the top 10 weekly precipitation total samples from Sequoia National Park, CA, of which 9 contained AR events, shows a high variability in the isotopic values. NOAA Hysplit back trajectory analyses reveals a variety of trajectories and varying latitudinal source regions contributed to moisture delivered to this site, which may explain part of the high variability (δ2H = -150.03 to -49.52 ‰, δ18O = -19.27 to -7.20 ‰, d-excess = 4.1 to 25.8). Here we examine the top precipitation totals occurring during AR events and the associated isotopic composition of precipitation samples from several sites across the Western US. We utilize IsoGSM, an isotope-enabled atmospheric general circulation model, to characterize the hydrologic processes and physical dynamics contributing to the observed isotopic variations. We investigate isotopic influences from moisture source location, AR speed, condensation height, and associated temperature. We explore the dominant controls on spatial and temporal variations of the isotopic composition of AR precipitation which highlights different physical processes for different AR events.

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.

Fire severity impacts trajectories of vegetative regrowth and δ13C in organic pools and fluxes in Siberian/Alaskan forests

NASA Astrophysics Data System (ADS)

Fessenden, J. E.; Randerson, J. T.; Schuur, E.; Zimov, S.

2002-12-01

Stable carbon isotope ratios of carbon dioxide and leaf organic matter were measured in boreal forests of varying age and fire severity in Siberia and Alaska. This study focused on moderate and extreme severity burn sites in neighboring Alaskan forests ranging from 2 years to 160 years and Siberian forests ranging from 1 year to 200 years. The Alaskan forests were composed primarily of black spruce (Picea Mariana) and quaking aspen (Populus tremuloides) with a shift in species dominance from aspen to spruce approximately 50 years after fire disturbance. The Siberian forests were composed of Dahurian larch (Larix gmelinii). The understory species are the same in both Siberia and Alaska: dwarf birch (Betula nana), willow (Salix alaxensis), blueberry (Vaccinium ovalifolium), cranberry (Vaccinium vitis-idaea), and various moss and lichen species. Our aim was to determine how disturbance influenced local and regional carbon isotopic ratios in organic pools and fluxes. Samples of organic δ13C in whole leaf tissue were collected from the dominant species of each forest. δ13CO2 and [CO2] were measured on soil cuvette- and canopy-CO2 to determine the isotopic ratio of soil and ecosystem respiration, respectively. Plant functional type primarily controlled the organic δ13C composition, and changes in abundance of different plant functional types with time since fire lead to patterns of 13C-enrichment with increased forest age. Successional stage and species composition trajectory dictated the composition of heterotrophic respiration with more 13C-enriched values found in dry/cold coniferous areas. Burn severity and successional state largely determined the distribution and abundance of plant functional types which dictated the δ13C values of organic pools and fluxes in the ecosystems. These results suggest that fire severity and frequency changes the carbon isotope composition of ecosystems and biosphere-atmosphere fluxes in ways that are predictable at local and regional scales by changing species composition and regrowth patterns.

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

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.

Coupled Mo-U abundances and isotopes in a small marine euxinic basin: Constraints on processes in euxinic basins

NASA Astrophysics Data System (ADS)

Bura-Nakić, Elvira; Andersen, Morten B.; Archer, Corey; de Souza, Gregory F.; Marguš, Marija; Vance, Derek

2018-02-01

Sedimentary molybdenum (Mo) and uranium (U) abundances, as well as their isotope systematics, are used to reconstruct the evolution of the oxygenation state of the surface Earth from the geological record. Their utility in this endeavour must be underpinned by a thorough understanding of their behaviour in modern settings. In this study, Mo-U concentrations and their isotope compositions were measured in the water column, sinking particles, sediments and pore waters of the marine euxinic Lake Rogoznica (Adriatic Sea, Croatia) over a two year period, with the aim of shedding light on the specific processes that control Mo-U accumulation and isotope fractionations in anoxic sediment. Lake Rogoznica is a 15 m deep stratified sea-lake that is anoxic and euxinic at depth. The deep euxinic part of the lake generally shows Mo depletions consistent with near-quantitative Mo removal and uptake into sediments, with Mo isotope compositions close to the oceanic composition. The data also, however, show evidence for periodic additions of isotopically light Mo to the lake waters, possibly released from authigenic precipitates formed in the upper oxic layer and subsequently processed through the euxinic layer. The data also show evidence for a small isotopic offset (∼0.3‰ on 98Mo/95Mo) between particulate and dissolved Mo, even at highest sulfide concentrations, suggesting minor Mo isotope fractionation during uptake into euxinic sediments. Uranium concentrations decrease towards the bottom of the lake, where it also becomes isotopically lighter. The U systematics in the lake show clear evidence for a dominant U removal mechanism via diffusion into, and precipitation in, euxinic sediments, though the diffusion profile is mixed away under conditions of increased density stratification between an upper oxic and lower anoxic layer. The U diffusion-driven precipitation is best described with an effective 238U/235U fractionation of +0.6‰, in line with other studied euxinic basins. Combining the Mo and U systematics in Lake Rogoznica and other euxinic basins, it is apparent that the two different uptake mechanisms of U and Mo can lead to spatially and temporally variable Mo/U and Mo-U isotope systematics that depend on the rate of water renewal versus removal to sediment, the sulfide concentration, and the geometry of the basin. This study further emphasises the potential of combining multiple observations, from Mo-U enrichment and isotope systematics, for disentangling the various processes via which redox conditions control the chemistry of modern and ancient sediments.

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.

Fate of Cd in Agricultural Soils: A Stable Isotope Approach to Anthropogenic Impact, Soil Formation, and Soil-Plant Cycling.

PubMed

Imseng, Martin; Wiggenhauser, Matthias; Keller, Armin; Müller, Michael; Rehkämper, Mark; Murphy, Katy; Kreissig, Katharina; Frossard, Emmanuel; Wilcke, Wolfgang; Bigalke, Moritz

2018-02-20

The application of mineral phosphate (P) fertilizers leads to an unintended Cd input into agricultural systems, which might affect soil fertility and quality of crops. The Cd fluxes at three arable sites in Switzerland were determined by a detailed analysis of all inputs (atmospheric deposition, mineral P fertilizers, manure, and weathering) and outputs (seepage water, wheat and barley harvest) during one hydrological year. The most important inputs were mineral P fertilizers (0.49 to 0.57 g Cd ha -1 yr -1 ) and manure (0.20 to 0.91 g Cd ha -1 yr -1 ). Mass balances revealed net Cd losses for cultivation of wheat (-0.01 to -0.49 g Cd ha -1 yr -1 ) but net accumulations for that of barley (+0.18 to +0.71 g Cd ha -1 yr -1 ). To trace Cd sources and redistribution processes in the soils, we used natural variations in the Cd stable isotope compositions. Cadmium in seepage water (δ 114/110 Cd = 0.39 to 0.79‰) and plant harvest (0.27 to 0.94‰) was isotopically heavier than in soil (-0.21 to 0.14‰). Consequently, parent material weathering shifted bulk soil isotope compositions to lighter signals following a Rayleigh fractionation process (ε ≈ 0.16). Furthermore, soil-plant cycling extracted isotopically heavy Cd from the subsoil and moved it to the topsoil. These long-term processes and not anthropogenic inputs determined the Cd distribution in our soils.

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.

Calcium Isotopic Compositions of Forearc Sediments from DSDP Site 144

NASA Astrophysics Data System (ADS)

Zhang, Z.; Zhu, H.; Nan, X.; Li, X.; Huang, F.

2016-12-01

It is important to investigate calcium isotopic compositions of reservoirs of the Earth for better application of Ca isotopes into studies of a variety of geochemical problems. Because Ca isotopic compositions for igneous rocks and carbonates are increasingly reported, this maybe bring new requirements on carefully understanding the isotopic compositions of subducted marine sediments. Marine sediments mainly contains carbonates and clays, controlling the compositions of slab-derived materials which are added to the mantle wedge. Obviously, it could have different elemental and calcium isotopic compositions with marine carbonate. Thus, it could also put biases on calcium isotopic signatures of basalts resulted from recycling oceanic carbonate into the mantle. Here, we report calcium isotopic compositions of 17 sediment samples from Deep Sea Drilling Project (DSDP) site 144 (09°27.23' N, 54°20.52' W) which is located about 400 km north of Surinam on the northern flank of the Demerara Rise with a water depth of 2957 meters. These samples have CaO contents ranging from 14.56 wt.% to 41.46 wt.% with an average of 29.61 ± 18.21 (2SD), δ44/40Ca ranges from 0.19 to 0.58 (relative to SRM915a) with an average of 0.40 ± 0.22 (2SD). These carbonate-rich sediments can be used to represent an endmember with high CaO content and low δ44/40Ca, which could modify chemical composition of the upper mantle and subduction zone lavas if they are recycled to the convective mantle during subduction. The positive linear correlation between CaO and δ44/40Ca in the sediments cannot be explained by a simple mixing between marine carbonate and clay. Instead, δ44/40Ca of these samples roughly increase from the Upper Cretaceous to the Early Oligocene, which might reflect the evolution of calcium isotopic compositions of seawater through time.

Seventh Annual V. M. Goldschmidt Conference

NASA Technical Reports Server (NTRS)

1997-01-01

Topics considered include: Subduction of the Aseismic Cocos Ridge Displaced Magma Sources Beneath the Cordillera de Talamanca, Costa Rica; Topography of Transition Zone Discontinuities: A Measure of 'Olivine' Content and Evidence for Deep Cratonic Roots; Uranium Enrichment in Lithospheric Mantle: Case Studies from French Massif Central; Rare-Earth-Element Anomalies in the Decollement Zone of the nankai Accretionary Prism, Japan: Evidence of Fluid Flow?; Rare Earth Elements in Japanese Mudrocks: The Influence of Provenance; The Evolution of Seawater Strontium Isotopes in the Last Hundred Million Years: Reinterpretation and Consequences for Erosion and Climate Models; From Pat to Tats: The Lead Isotope Legacy in the Studies of the Continental Crust-Upper Mantle System; Geochronology of the Jack Hills Detrital Zircons by Precise Uranium-Lead Isotope-Dilution Analysis of Crystal Fragments; Iridium in the Oceans; The Helium-Heat-Lead Paradox; Control of Distribution Patterns of Heavy Metals in Ganga Plain Around Kanpur Region, India, by Fluvial Geomorphic Domains; Geochemical and Isotopic Features of Ferrar Magmatic Provience (Victoria Land, Antarctica); Rare Earth Elements in Marine Fine-Grained Sediments from the Northwestern Portuguese Shelf (Atlantic); Aspects of Arc Fluxes; General Kinetic Model for Dolomite Precipitation Rate with Application to the Secular History of Seawater Composition; High-Precision Uranium-series Chronology from Speleothems; Trace-Element Modeling of Aqueous Fluid-Peridotite Interaction in the Mantle Wedge of Subduction Zones; Rainfall Variations in Southeastern Australia over the Last 500,000 Years from Speleothem Deposition; The Role of Water in High-Pressure Fluids; The Kinetic Conditions of Metamorphic Minearogenesis: Evidence from Minerals and Assemblages.

Isotope Biogeochemistry of Sulfur in a Cold-Water Carbonate Mound (IODP Site 1317)

NASA Astrophysics Data System (ADS)

Ferdelman, T. G.; Boettcher, M. E.

2007-12-01

To establish a depositional model for cold-water carbonate mounds, Challenger Mound and adjacent continental slope sites were drilled during IODP Expedition 307 in May 2005. Although a role for methane seepage and subsequent anaerobic oxidation was discounted both as a hard-round substrate for mound initiation and as a principal source of carbonate within the mound succession, interstitial water profiles of sulfate, alkalinity, Mg, and Sr indicated a tight coupling between carbonate diagenesis and mircrobial sulfate reduction. The reaction of sulfide with siliciclastic iron-bearing minerals to form pyrite was proposed to account for enhanced diagenetic carbonate precipitation (Ferdelman et al., 2006; Proc. IODP, vol. 307; doi:10.2204/iodp.proc.307.2006). To characterize these geomicrobial sulfur transformations in the carbonate mound sediments, the inorganic and stable isotope geochemical compositions of pore water sulfate and solid phase reduced sulfur compounds were performed. Acid-volatile sulfur (AVS) and pyrite del 34S compositions were usually similar and exhibited an increasing trend of from -40 per mil near surface to -20 per mil at the mound base at 132 mbsf. However, several excursions to more 34S sulfur enriched pyrite to values >0 per mil were observed in the deeper sections of the mound sequence. These excursions may be linked transitory changes in the depth of the methane-sulfate transition zone during mound build-up. The oxygen isotopic composition of residual dissolved sulfate indicates intracellular isotope exchange processes within the cells of SRBs, leading to increasing equilibration between extracellular pore water and sulfate.

Hydroclimate variability of High Arctic Svalbard during the Holocene inferred from hydrogen isotopes of leaf waxes

NASA Astrophysics Data System (ADS)

Balascio, Nicholas L.; D'Andrea, William J.; Gjerde, Marthe; Bakke, Jostein

2018-03-01

The response of the Arctic hydrologic cycle to global warming includes changes in precipitation patterns and moisture availability associated with variable sea ice extent and modes of atmospheric circulation. Reconstructions of past hydroclimate changes help constrain the natural range of these systems, identify the manners in which they respond to different forcing mechanisms, and reveal their connections to other components of the climate system, all of which lead to a better understanding of present and future changes. Here we examine hydroclimate changes during the Holocene in the High Arctic archipelago of Svalbard by reconstructing the isotopic composition of precipitation. We measured the hydrogen isotopic composition (δD values) of leaf wax compounds (n-alkanes; C25-C31) in a sediment core from Lake Hakluytvatnet on the island of Amsterdamøya, northwest Spitsbergen. We interpret δD values of mid-chain (C25) and long-chain (C29, C31) length n-alkanes to represent changes in the isotopic composition of lake water and precipitation over the last 12.9 ka. After deglaciation of the catchment, water supply became restricted and the lake experienced significant evaporative isotopic enrichment indicating warmer conditions from 12.8 to 7.5 ka. The isotope values suggest an increase in the delivery of moisture from warmer sub-polar air masses between 12.8 and 9.5 ka, followed by generally warm, but unstable conditions between 9.5 and 7.5 ka, possibly indicating a response to meltwater forcing. Sedimentary evidence indicates a hiatus in deposition c. 7.5-5.0 ka, likely as a result of desiccation of the lake. At c. 5.0 ka lacustrine sedimentation resumed and over the last 5 ka there was a progressive increase in the influence of polar air masses and colder conditions, which culminated in an abrupt shift to colder conditions at c. 1.8 ka. This late Holocene cooling ended c. 0.18 ka, when isotopic data indicate warmer conditions and greater influence of moisture derived from lower latitudes.

The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

NASA Astrophysics Data System (ADS)

von Sperber, C.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.

2015-07-01

Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (myo-inositol hexakisphosphate, IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields available Pi and less phosphorylated inositol derivates as products. The hydrolysis of organic P compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'-monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as a substrate were prepared. During the hydrolysis of IP6 by phytase, four of the six Pi were released, and one oxygen atom from water was incorporated into each Pi. This incorporation of oxygen from water into Pi was subject to an apparent inverse isotopic fractionation (ϵ ~ 6 to 10 ‰), which was similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ~ 7 ‰), where less than three Pi were released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ~ -12 ‰), similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ϵ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking substrate dependency of the isotopic fractionation could be attributed to a difference in the δ18O values of the C-O-P bridging and non-bridging oxygen atoms in organic phosphate compounds.

The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

NASA Astrophysics Data System (ADS)

Sperber, C. v.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.

2015-03-01

Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields plant available inorganic phosphate (Pi) and less phosphorylated inositol derivates as products. The hydrolysis of organic P-compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as substrate were prepared. During the hydrolysis of IP6 by phytase, four Pi are released, and one oxygen atom from water is incorporated into each Pi. This incorporation of oxygen from water into Pi is subject to an apparent inverse isotopic fractionation (ϵ ∼ 6 to 10‰), which is similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ∼ 7‰) where less than three Pi are released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ∼ -12‰), again similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ɛ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking substrate-dependency of the isotopic fractionation could be attributed to a difference in the δ18O-values of the C-O-P bridging and non-bridging oxygen atoms in organic phosphate compounds.

Stable isotopes reveal spatial variability in the trophic structure of a macro-benthic invertebrate community in a tropical coral reef.

PubMed

Kolasinski, Joanna; Nahon, Sarah; Rogers, Karyne; Chauvin, Anne; Bigot, Lionel; Frouin, Patrick

2016-02-15

Studies of organic matter fluxes in coral reefs are historically based on physical and biogeochemical approaches. It is important to link these approaches to community analysis as the abundance and behaviour of species, populations or trophic groups can have a profound effect on nutrient budgets. We determined the carbon and nitrogen isotopic compositions of coral reef organic matter sources and macro-benthic invertebrate communities using a Europa Geo 20/20 isotope ratio mass spectrometer interfaced to an ANCA-SL elemental analyzer in continuous flow mode. Isotopic ecology metrics and a mixing model were used to analyze and interpret the data. The coral reef macro-invertebrate community principally relies on detrital or recycled food sources. An increased reliance on reef nitrogen-derived sources was observed in the cold-dry season. The community food-web lengths differ noticeably across the coral reef and reflect the characteristics and origin of organic matter reservoirs. Anthropogenic and terrestrial inputs lead to a loss of biological diversity. Exclusive dominance of suspension-feeding species is observed in areas receiving direct surface riverine particulate organic matter. The accumulation of sediment organic matter in eutrophic areas leads to dominance of deposit-feeding species. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Contamination history of lead and other trace metals reconstructed from an urban winter pond in the Eastern Mediterranean coast (Israel).

PubMed

Zohar, I; Bookman, R; Levin, N; de Stigter, H; Teutsch, N

2014-12-02

Pollution history of Pb and other trace metals was reconstructed for the first time for the Eastern Mediterranean, from a small urban winter pond (Dora, Netanya), located at the densely populated coastal plain of Israel. An integrated approach including geochemical, sedimentological, and historical analyses was employed to study sediments from the center of the pond. Profiles of metal concentrations (Pb, Zn, V, Ni, Cu, Cr, Co, Cd, and Hg) and Pb isotopic composition denote two main eras of pre- and post-19th century. The deeper sediment is characterized by low concentrations and relatively constant 206Pb/207Pb (around 1.20), similar to natural Pb sources, with slight indications of ancient anthropogenic activity. The upper sediment displays an upward increase in trace metal concentrations, with the highest enrichment factor for Pb (18.4). Lead fluxes and isotopic composition point to national/regional petrol-Pb emissions as the major contributor to Pb contamination, overwhelming other potential local and transboundary sources. Traffic-related metals are correlated with Pb, emphasizing the polluting inputs of traffic. The Hg profile, however, implies global pollution rather than local sources.

Applying geochemical signatures of atmospheric dust to distinguish current mine emissions from legacy sources

NASA Astrophysics Data System (ADS)

Dong, Chenyin; Taylor, Mark Patrick

2017-07-01

Resolving the source of environmental contamination is the critical first step in remediation and exposure prevention. Australia's oldest silver-zinc-lead mine at Broken Hill (>130 years old) has generated a legacy of contamination and is associated with persistent elevated childhood blood lead (Pb) levels. However, the source of environmental Pb remains in dispute: current mine emissions; remobilized mine-legacy lead in soils and dusts; and natural lead from geological weathering of the gossan ore body. Multiple lines of evidence used to resolve this conundrum at Broken Hill include spatial and temporal variations in dust Pb concentrations and bioaccessibility, Pb isotopic compositions, particle morphology and mineralogy. Total dust Pb loading (mean 255 μg/m2/day) and its bioaccessibility (mean 75% of total Pb) is greatest adjacent to the active mining operations. Unweathered galena (PbS) found in contemporary dust deposits contrast markedly to Pb-bearing particles from mine-tailings and weathered gossan samples. Contemporary dust particles were more angular, had higher sulfur content and had little or no iron and manganese. Dust adjacent to the mine has Pb isotopic compositions (208Pb/207Pb: 2.3197; 206Pb/207Pb: 1.0406) that are a close match (99%) to the ore body with values slightly lower (94%) at the edge of the city. The weight of evidence supports the conclusion that contemporary dust Pb contamination in Broken Hill is sourced primarily from current mining activities and not from weathering or legacy sources.

[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.

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.

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.

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.

Illuminating hydrological processes at the soil-vegetation-atmosphere interface with water stable isotopes

NASA Astrophysics Data System (ADS)

Sprenger, Matthias; Leistert, Hannes; Gimbel, Katharina; Weiler, Markus

2016-09-01

Water stable isotopes (18O and 2H) are widely used as ideal tracers to track water through the soil and to separate evaporation from transpiration. Due to the technical developments in the last two decades, soil water stable isotope data have become easier to collect. Thus, the application of isotope methods in soils is growing rapidly. Studies that make use of soil water stable isotopes often have a multidisciplinary character since an interplay of processes that take place in the vadose zone has to be considered. In this review, we provide an overview of the hydrological processes that alter the soil water stable isotopic composition and present studies utilizing pore water stable isotopes. The processes that are discussed include the water input as precipitation or throughfall, the output as evaporation, transpiration, or recharge, and specific flow and transport processes. Based on the review and supported by additional data and modeling results, we pose a different view on the recently proposed two water world hypothesis. As an alternative to two distinct pools of soil water, where one pool is enriched in heavy isotopes and used by the vegetation and the other pool does not undergo isotopic fractionation and becomes recharge, the water gets successively mixed with newly introduced rainwater during the percolation process. This way, water initially isotopically enriched in the topsoil loses the fractionation signal with increasing infiltration depth, leading to unfractionated isotopic signals in the groundwater.

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.

Development of a Method to Isolate Glutamic Acid from Foodstuffs for a Precise Determination of Their Stable Carbon Isotope Ratio.

PubMed

Kobayashi, Kazuhiro; Tanaka, Masaharu; Yatsukawa, Yoichi; Tanabe, Soichi; Tanaka, Mitsuru; Ohkouchi, Naohiko

2018-01-01

Recent growing health awareness is leading to increasingly conscious decisions by consumers regarding the production and traceability of food. Stable isotopic compositions provide useful information for tracing the origin of foodstuffs and processes of food production. Plants exhibit different ratios of stable carbon isotopes (δ 13 C) because they utilized different photosynthetic (carbon fixation) pathways and grow in various environments. The origins of glutamic acid in foodstuffs can be differentiated on the basis of these photosynthetic characteristics. Here, we have developed a method to isolate glutamic acid in foodstuffs for determining the δ 13 C value by elemental analyzer-isotope-ratio mass spectrometry (EA/IRMS) without unintended isotopic fractionation. Briefly, following acid-hydrolysis, samples were defatted and passed through activated carbon and a cation-exchange column. Then, glutamic acid was isolated using preparative HPLC. This method is applicable to measuring, with a low standard deviation, the δ 13 C values of glutamic acid from foodstuffs derived from C3 and C4 plants and marine algae.

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

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

USGS Publications Warehouse

Ayuso, Robert A.; Foley, Nora K.

2008-01-01

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

Elemental and iron isotopic composition of aerosols collected in a parking structure.

PubMed

Majestic, Brian J; Anbar, Ariel D; Herckes, Pierre

2009-09-01

The trace metal contents and iron isotope composition of size-resolved aerosols were determined in a parking structure in Tempe, AZ, USA. Particulate matter (PM)<2.5 microm in diameter (the fine fraction) and PM>2.5 microm were collected. Several air toxics (e.g., arsenic, cadmium, and antimony) were enriched above the crustal average, implicating automobiles as an important source. Extremely high levels of fine copper (up to 1000 ng m(-3)) were also observed in the parking garage, likely from brake wear. The iron isotope composition of the aerosols were found to be +0.15+/-0.03 per thousand and +0.18+/-0.03 per thousand for the PM<2.5 microm and PM>2.5 microm fractions, respectively. The similarity of isotope composition indicates a common source for each size fraction. To better understand the source of iron in the parking garage, the elemental composition in four brake pads (two semi-metallic and two ceramic), two tire tread samples, and two waste oil samples were determined. Striking differences in the metallic and ceramic brake pads were observed. The ceramic brake pads contained 10-20% copper by mass, while the metallic brake pads contained about 70% iron, with very little copper. Both waste oil samples contained significant amounts of calcium, phosphorous, and zinc, consistent with the composition of some engine oil additives. Differences in iron isotope composition were observed between the source materials; most notably between the tire tread (average=+0.02 per thousand) and the ceramic brake linings (average=+0.65 per thousand). Differences in isotopic composition were also observed between the metallic (average=+0.18 per thousand) and ceramic brake pads, implying that iron isotope composition may be used to resolve these sources. The iron isotope composition of the metallic brake pads was found to be identical to the aerosols, implying that brake dust is the dominant source of iron in a parking garage.

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.

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.

Particular geoscientific perspectives on stable isotope analysis in the arboreal system

NASA Astrophysics Data System (ADS)

Helle, Gerhard; Balting, Daniel; Pauly, Maren; Slotta, Franziska

2017-04-01

In geosciences stable isotopes of carbon, oxygen and hydrogen from the tree ring archive have been used for several decades to trace the course of past environmental and climatological fluctuations. In contrast to ice cores, the tree ring archive is of biological nature (like many other terrestrial archives), but provides the opportunity to establish site networks with very high resolution in space and time. Many of the basic physical mechanisms of isotope shifts are known, but biologically mediated processes may lead to isotope effects that are poorly understood. This implies that the many processes within the arboreal system leading to archived isotope ratios in wood material are governed by a multitude of environmental variables that are not only tied to the isotopic composition of atmospheric source values (precipitation, CO2), but also to seasonally changing metabolic flux rates and pool sizes of photosynthates within the trees. Consequently, the extraction of climate and environmental information is particularly challenging and reconstructions are still of rather qualitative nature. Over the last 10 years or so, monitoring studies have been implemented to investigate stable isotope, climate and environmental signal transfer within the arboreal system to develop transfer or response functions that can translate the relevant isotope values extracted from tree rings into climate or other environmental variables. To what extent have these efforts lead to a better understanding that helps improving the meaningfulness of tree ring isotope signals? For example, do monitoring studies help deciphering the causes for age-related trends in tree ring stable isotope sequences that are published in a growing number of papers. Are existing monitoring studies going into detail enough or is it already too much effort for the outcome? Based on what we know already particularly in mesic habitats, tree ring stable isotopes are much better climate proxies than other tree ring parameters. However, millennial or multi-millennial high quality reconstructions from tree ring isotopes are still rare. This is because of i) methodological constraints related to mass spectrometric analyses and ii) the nature of tree-ring chronologies that are put together by many trees of various individual ages. In view of this: What is the state-of-the-art in high throughput tree ring stable isotope analyses? Is it necessary to advance existing methodologies further to conserve the annual time resolution provided by the tree-ring archive? Other terrestrial archives, like lake sediments and speleothems rarely provide annually resolved stable isotope data. Furthermore, certain tree species from tropical or sub-tropical regions cannot be dated properly by dendrochronology and hence demand specific stable isotope measuring strategies, etc.. Although the points raised here do specifically apply for the tree ring archive, some of them are important for all proxy archives of organic origin.

Influence of accretion on lead in the Earth

NASA Astrophysics Data System (ADS)

Galer, Stephen J. G.; Goldstein, Steven L.

The Pb abundance and isotope composition of the Earth is fundamentally altered from bulk solar system values by the processes occurring during accretion. The most important of the possible processes are volatile element loss and core formation, or some form of inhomogeneous accretion/condensation. The final result is an Earth highly impoverished in 204Pb and other Pb isotopes in primordial abundance. Depending on the exact timing, some radiogenic Pb is also lost either to space or to the core; the degree of loss occurs in the same order as the parent decay constants, namely 207Pb > 206Pb > 208Pb. In this contribution, we explore the likely effects accretion had on the Pb isotope composition of the present day bulk silicate Earth and its secular isotope evolution. This is used to address a number of questions: (1) What can be learned about accretion from the Pb isotope composition of the bulk silicate Earth? (2) Can effects of accretion reconcile the classical "Pb paradox" of a 206Pb-rich bulk silicate Earth? (3) What exactly is the meaning of the "age of the Earth" within the context of Pb isotopes? By consideration of a number of accretion scenarios it is demonstrated that Pb isotopes yield information only on the following two coupled quantities: Firstly, the accretion interval Δ T, the time between initial condensation of the solar nebula (at 4.566Ga) and when accretion-produced U/Pb fractionation (whether loss of Pb to the core or to space) in the silicate Earth ceased. Secondly, the mean 238U/204 Pb ratio μ during accretion—no details of changes in μ during the accretion interval can be resolved. The effects of accretion are thus adequately considered in terms of a simple two-stage model described by μ over ΔT followed by a postaccretion μ. The systematics of μ and ΔT are then examined for the cases of present day terrestrial reservoirs and Archean leads. These estimates of μ and ΔT for the present and past silicate Earth are not compatible with ΔT = 0; rather, they require ΔT ≥ 50Ma and μ ≥ 0 in all instances, with our best estimate of ΔT being 80±40Ma. From a number of lines of argument it can be demonstrated that the U-Pb "age of the Earth" records an endogenous process actively taking place during accretion. Further, this process cannot be volatile loss of Pb, but rather it actually records the termination of Pb partitioning into the core. This does not necessarily date the endpoint of growth of the Earth for two reasons: Firstly, this core formation "age" may itself in part reflect that occurring on bodies later contributing to the Earth; secondly, later infall of bodies may alter μ but leave the U-Pb "age" of the silicate Earth effectively unaltered. Overall, the Earth can be considerably `younger' than previous single-stage model U-Pb ages for the silicate Earth have suggested. In addition, the "lead paradox" is seen to be a natural consequence of the finite time taken for accretion and core formation on the Earth.

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.

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.

Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

USGS Publications Warehouse

Meshoulam, Alexander; Ellis, Geoffrey S.; Ahmad, Ward Said; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

2016-01-01

Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and provide important mechanistic details about the overall TSR process.

Determination of kinetic isotopic fractionation of water during bare soil evaporation

NASA Astrophysics Data System (ADS)

Quade, Maria; Brüggemann, Nicolas; Graf, Alexander; Rothfuss, Youri

2017-04-01

A process-based understanding of the water cycle in the atmosphere is important for improving meteorological and hydrological forecasting models. Usually only net fluxes of evapotranspiration - ET are measured, while land-surface models compute their raw components evaporation -E and transpiration -T. Isotopologues can be used as tracers to partition ET, but this requires knowledge of the isotopic kinetic fractionation factor (αK) which impacts the stable isotopic composition of water pools (e.g., soil and plant waters) during phase change and vapor transport by soil evaporation and plant transpiration. It is defined as a function of the ratio of the transport resistances in air of the less to the most abundant isotopologue. Previous studies determined αK for free evaporating water (Merlivat, 1978) or bare soil evaporation (Braud et al. 2009) at only low temporal resolution. The goal of this study is to provide estimates at higher temporal resolution. We performed a soil evaporation laboratory experiment to determine the αK by applying the Craig and Gordon (1965) model. A 0.7 m high column (0.48 m i.d.) was filled with silt loam (20.1 % sand, 14.9 % loam, 65 % silt) and saturated with water of known isotopic composition. Soil volumetric water content, temperature and the isotopic composition (δ) of the soil water vapor were measured at six different depths. At each depth microporous polypropylene tubing allowed the sampling of soil water vapor and the measurement of its δ in a non-destructive manner with high precision and accuracy as detailed in Rothfuss et al. (2013). In addition, atmospheric water vapor was sampled at seven different heights up to one meter above the surface for isotopic analysis. Results showed that soil and atmospheric δ profiles could be monitored at high temporal and vertical resolutions during the course of the experiment. αK could be calculated by using an inverse modeling approach and the Keeling (1958) plot method at high temporal resolution over a long period. We observed an increasing δ in the evaporating water vapor due to more enriched surface water. This leads to a higher transport resistances and an increasing αK. References Braud, I., Bariac, T., Biron, P., and Vauclin, M.: Isotopic composition of bare soil evaporated water vapor. Part II: Modeling of RUBIC IV experimental results, J. Hydrol., 369, 17-29. Craig, H. et al., 1965. Deuterium and oxygen 18 variations in the ocean and marine atmosphere. In: E. Tongiogi (Editor), Stable Isotopes in Oceanographic Studies and Paleotemperatures. V. Lishi, Spoleto, Italy, pp. 9-130. Keeling, C. D.: The Concentration and Isotopic Abundances of Atmospheric Carbon Dioxide in Rural Areas, Geochim. Cosmochim. Acta, 13, 322-334. Merlivat, L., 1978. Molecular Diffusivities of H216O, HD16O, and H218O in Gases. J Chem Phys, 69, 2864-2871. Rothfuss, Y. et al., 2013. Monitoring water stable isotopic composition in soils using gas-permeable tubing and infrared laser absorption spectroscopy. Water Resour. Res., 49, 1-9.

Laser ionization time of flight mass spectrometer for isotope mass detection and elemental analysis of materials

NASA Astrophysics Data System (ADS)

Ahmed, Nasar; Ahmed, Rizwan; Umar, Z. A.; Aslam Baig, M.

2017-08-01

In this paper we present the construction and modification of a linear time-of-flight mass spectrometer to improve its mass resolution. This system consists of a laser ablation/ionization section based on a Q-switched Nd:YAG laser (532 nm, 500 mJ, 5 ns pulse duration) integrated with a one meter linear time-of-flight mass spectrometer coupled with an electric sector and a magnetic lens and outfitted with a channeltron electron multiplier for ion detection. The resolution of the system has been improved by optimizing the accelerating potential and inserting a magnetic lens after the extraction region. The isotopes of lithium, lead and cadmium samples have been resolved and detected in accordance with their natural abundance. The capability of the system has been further exploited to determine the elemental composition of a brass alloy, having a certified composition of zinc and copper. Our results are in excellent agreement with its certified composition. This setup is found to be extremely efficient and convenient for fast analyses of any solid sample.

Testing and Resilience of the Impact Origin of the Moon

NASA Technical Reports Server (NTRS)

Righter, K.; Canup, R. M.

2016-01-01

The leading hypothesis for the origin of the Moon is the giant impact model, which grew out of the post-Apollo science community. The hypothesis was able to explain the high E-M system angular momentum, the small lunar core, and consistent with the idea that the early Moon melted substantially. The standard hypothesis requires that the Moon be made entirely from the impactor, strangely at odds with the nearly identical oxygen isotopic composition of the Earth and Moon, compositions that might be expected to be different if Moon came from a distinct impactor. Subsequent geochemical research has highlighted the similarity of both geochemical and isotopic composition of the Earth and Moon, and measured small but significant amounts of volatiles in lunar glassy materials, both of which are seemingly at odds with the standard giant impact model. Here we focus on key geochemical measurements and spacecraft observations that have prompted a healthy re-evaluation of the giant impact model, provide an overview of physical models that are either newly proposed or slightly revised from previous ideas, to explain the new datasets.

The lack of potassium-isotopic fractionation in Bishunpur chondrules

USGS Publications Warehouse

Alexander, C.M. O'D.; Grossman, J.N.; Wang, Jingyuan; Zanda, B.; Bourot-Denise, M.; Hewins, R.H.

2000-01-01

In a search for evidence of evaporation during chondrule formation, the mesostases of 11 Bishunpur chondrules and melt inclusions in olivine phenocrysts in 7 of them have been analyzed for their alkali element abundances and K-isotopic compositions. Except for six points, all areas of the chondrules that were analyzed had δ41K compositions that were normal within error (typically ±3%, 2s̀). The six “anomalous” points are probably all artifacts. Experiments have shown that free evaporation of K leads to large 41K enrichments in the evaporation residues, consistent with Rayleigh fractionation. Under Rayleigh conditions, a 3% enrichment in δ41K is produced by ∼12% loss of K. The range of L-chondrite-normalized K/Al ratios (a measure of the K-elemental fractionation) in the areas analyzed vary by almost three orders of magnitude. If all chondrules started out with L-chondrite-like K abundances and the K loss occurred via Rayleigh fractionation, the most K-depleted chondrules would have had compositions of up to δ41K ≅ 200%. Clearly, K fractionation did not occur by evaporation under Rayleigh conditions. Yet experiments and modeling indicate that K should have been lost during chondrule formation under currently accepted formation conditions (peak temperature, cooling rate, etc.). Invoking precursors with variable alkali abundances to produce the range of K/Al fractionation in chondrules does not explain the K-isotopic data because any K that was present should still have experienced sufficient loss during melting for there to have been a measurable isotopic fractionation. If K loss and isotopic fractionation was inevitable during chondrule formation, the absence of K-isotopic fractionation in Bishunpur chondrules requires that they exchanged K with an isotopically normal reservoir during or after formation. There is evidence for alkali exchange between chondrules and rim-matrix in all unequilibrated ordinary chondrites. However, melt inclusions can have alkali abundances that are much lower than the mesostases of the host chondrules, which suggests that they at least remained closed since formation. If it is correct that some or all melt inclusions remained closed since formation, the absence of K-isotopic fractionation in them requires that the K-isotopic exchange took place during chondrule formation, which would probably require gas-chondrule exchange. Potassium evaporated from fine-grained dust and chondrules during chondrule formation may have produced sufficient K-vapor pressure for gas-chondrule isotopic exchange to be complete on the timescales of chondrule formation. Alternatively, our understanding of chondrule formation conditions based on synthesis experiments needs some reevaluation.

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.

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

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.

Uranium-lead isotope systematics of Mars inferred from the basaltic shergottite QUE 94201

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

Gaffney, A M; Borg, L E; Connelly, J N

2006-12-22

Uranium-lead ratios (commonly represented as {sup 238}U/{sup 204}Pb = {mu}) calculated for the sources of martian basalts preserve a record of petrogenetic processes that operated during early planetary differentiation and formation of martian geochemical reservoirs. To better define the range of {mu} values represented by the source regions of martian basalts, we completed U-Pb elemental and isotopic analyses on whole rock, mineral and leachate fractions from the martian meteorite Queen Alexandra Range 94201 (QUE 94201). The whole rock and silicate mineral fractions have unradiogenic Pb isotopic compositions that define a narrow range ({sup 206}Pb/{sup 204}Pb = 11.16-11.61). In contrast, themore » Pb isotopic compositions of weak HCl leachates are more variable and radiogenic. The intersection of the QUE 94201 data array with terrestrial Pb in {sup 206}Pb/{sup 204}Pb-{sup 207}Pb/{sup 204}Pb-{sup 208}Pb/{sup 204}Pb compositional space is consistent with varying amounts of terrestrial contamination in these fractions. We calculate that only 1-7% contamination is present in the purified silicate mineral and whole rock fractions, whereas the HCl leachates contain up to 86% terrestrial contamination. Despite the contamination, we are able to use the U-Pb data to determine the initial {sup 206}Pb/{sup 204}Pb of QUE 94201 (11.086 {+-} 0.008) and calculate the {mu} value of the QUE 94201 mantle source to be 1.823 {+-} 0.008. This is the lowest {mu} value calculated for any martian basalt source, and, when compared to the highest values determined for martian basalt sources, indicates that {mu} values in martian source reservoirs vary by at least 100%. The range of source {mu} values further indicates that the {mu} value of bulk silicate Mars is approximately three. The amount of variation in the {mu} values of the mantle sources ({mu} {approx} 2-4) is greater than can be explained by igneous processes involving silicate phases alone. We suggest the possibility that a small amount of sulfide crystallization may generate large extents of U-Pb fractionation during formation of the mantle sources of martian basalts.« less

Stable isotopes in water vapor and precipitation for a coastal lagoon at mid latitudes

NASA Astrophysics Data System (ADS)

Zannoni, Daniele; Bergamasco, Andrea; Dreossi, Giuliano; Rampazzo, Giancarlo; Stenni, Barbara

2016-04-01

The stable oxygen and hydrogen isotope composition in precipitation can be used in hydrology to describe the signature of local meteoric water. The isotopic composition of water vapor is usually obtained indirectly from measurements of δD and δ18O in precipitation, assuming the isotopic equilibrium between rain and water vapor. Only few studies report isotopic data in both phases for the same area, thus providing a complete Local Meteoric Water Line (LMWL). The goal of this study is to build a complete LMWL for the lagoon of Venice (northern Italy) with observations of both water vapor and precipitation. The sampling campaign has started in March 2015 and will be carried out until the end of 2016. Water vapor is collected once a week with cold traps at low temperatures (-77°C). Precipitation is collected on event and monthly basis with a custom automatic rain sampler and a rain gauge, respectively. Liquid samples are analyzed with a Picarro L1102-i and results are reported vs VSMOW. The main meteorological parameters are continuously recorded in the same area by the campus automatic weather station. Preliminary data show an LMWL close to the Global Meteoric Water Line (GMWL) with lower slope and intercept. An evaporation line is clearly recognizable, considering samples that evaporated between the cloud base and the ground. The deviation from the GMWL parameters, especially intercept, can be attributed to evaporated rain or to the humidity conditions of the water vapor source. Water vapor collected during rainfall shows that rain and vapor are near the isotopic equilibrium, just considering air temperature measured at ground level. Temperature is one of the main factor that controls the isotopic composition of the atmospheric water vapor. Nevertheless, the circulation of air masses is a crucial parameter which has to be considered. Water vapor samples collected in different days but with the same meteorological conditions (air temperature and relative humidity) show differences in terms of δ18O up to 3‰. Isotopic ratios in rain events and water vapor are in fact dominated by a seasonal component but outliers are clearly linked to air parcel origin. The monthly measurements of δD and δ18O in precipitation of August 2015, for instance, are lower than in colder months, considering monthly average temperatures. Single rain events show a small sequence of precipitation, that leads to 40% of total precipitation of August, which lowers δ-values considerably. The sampling on event basis during occasional and discontinuous rain also allows to identify the rainout effect, which leads to lightening water during a rainfall. Statistics based on back trajectories (48 hours) show that the major part of air parcels travels across central Europe and derives from sources located in the north Atlantic, whereas, a smaller fraction of the water vapor can be attributed to Mediterranean sources.

Source discrimination of atmospheric metal deposition by multi-metal isotopes in the Three Gorges Reservoir region, China.

PubMed

Liu, Jinling; Bi, Xiangyang; Li, Fanglin; Wang, Pengcong; Wu, Jin

2018-05-12

Concentrations of heavy metals, as well as isotopic compositions of mercury (Hg) and lead (Pb), in mosses (Bryum argenteum) from the Three Gorges Reservoir (TGR) region were investigated to decipher the sources of atmospheric metals in this region. Higher contents of metals (0.90 ± 0.65 mg/kg of Cd, 24.6 ± 27.4 mg/kg of Cu, and 36.1 ± 51.1 mg/kg of Pb) in the mosses from TGR were found compared with those from pollution-free regions. Principal component analysis (PCA) grouped the moss metals into four main components which were associated with both anthropogenic and natural sources. The ratios of Pb isotopes of the mosses (1.153-1.173 for 206 Pb/ 207 Pb and 2.094-2.129 for 208 Pb/ 206 Pb) fell between those of the traffic emissions and coals. Similarly, the compositions of δ 202 Hg (-4.29∼-2.33‰) and Δ 199 Hg (within ±0.2‰) were comparable to those of the coals and coal combustion emissions from China and India. These joined results of Pb and Hg isotope data give solid evidences that the coal combustion and traffic emissions are the main causes of metal accumulation in the TGR region. Copyright © 2018 Elsevier Ltd. All rights reserved.

Lead Isotope Compositions of Acid Residues from Olivine-Phyric Shergottite Tissint: Implications for Heterogeneous Shergottite Source Reservoirs

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Yokoyama, T.; Simon, J. I.; Jones, J. H.

2015-01-01

Geochemical studies of shergottites suggest that their parental magmas reflect mixtures between at least two distinct geochemical source reservoirs, producing correlations between radiogenic isotope compositions and trace element abundances. These correlations have been interpreted as indicating the presence of a reduced, incompatible element- depleted reservoir and an oxidized, incompatible- element-enriched reservoir. The former is clearly a depleted mantle source, but there is ongoing debate regarding the origin of the enriched reservoir. Two contrasting models have been proposed regarding the location and mixing process of the two geochemical source reservoirs: (1) assimilation of oxidized crust by mantle derived, reduced magmas, or (2) mixing of two distinct mantle reservoirs during melting. The former requires the ancient Martian crust to be the enriched source (crustal assimilation), whereas the latter requires isolation of a long-lived enriched mantle domain that probably originated from residual melts formed during solidification of a magma ocean (heterogeneous mantle model). This study conducts Pb isotope and trace element concentration analyses of sequential acid-leaching fractions (leachates and the final residues) from the geochemically depleted olivine-phyric shergottite Tissint. The results suggest that the Tissint magma is not isotopically uniform and sampled at least two geochemical source reservoirs, implying that either crustal assimilation or magma mixing would have played a role in the Tissint petrogenesis.

Isotope geochemistry of waters affected by acid mine drainage in old labour sites (SE, Spain).

NASA Astrophysics Data System (ADS)

Pérez-Sirvent, Carmen; Martinez-Sanchez, Maria Jose; Garcia-Lorenzo, Maria Luz; Agudo, Ines; Hernandez-Cordoba, Manuel; Recio, Clemente

2015-04-01

The ore deposits of this zone have iron, lead and zinc as the main metal components. Iron is present in oxides, hydroxides, sulfides, sulfates, carbonates, and silicates; lead and zinc occur in sulfides (galena and sphalerite, respectively), carbonates, sulfates, and lead or zinc-bearing (manganese, iron) oxides. Mining started with the Romans and activity peaked in the second half of the 19th century and throughout the 20th century until the 1980's. From 1940 to 1957, mineral concentration was made by froth flotation and, prior to this, by gravimetric techniques. The mining wastes, or tailings, with a very fine particle size were deposited inland (tailings dams) and, since 1957, huge releases were made in directly the sea coast. The objective of this work was to evaluate processes affecting waters from abandoned mine sites by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. Several common chemical and physical processes, such as evaporation, water-rock interaction and mixing could alter water isotopic composition. Evaporation, which causes an enrichment in δD and δ18O in the residual water, is an important process in semiarid areas. The results obtained indicate that, for sites near the coast, waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe3+ was predominant in the surface, and controlled by A. ferrooxidans, while at depth, sulfate reduction occurred.

Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method.

PubMed

Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

2018-04-01

Isotope ratio monitoring by 13 C NMR spectrometry (irm- 13 C NMR) provides the complete 13 C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13 C natural abundance values (50‰), irm- 13 C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13 C NMR. Until now, the conventional strategy to determine the position-specific abundance x i relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13 C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13 C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1 H NMR pulse sequence (named DWET) with a 13 C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T 1 , which forms a serious limitation for irm- 13 C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T 1 variations. Their performance is evaluated on the determination of the 13 C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm- 13 C NMR since it is now possible to perform isotopic analysis with high relaxing agent concentrations, leading to a strong reduction of the overall experiment time. Copyright © 2018 Elsevier Inc. All rights reserved.

Lead Isotopes in Olivine-Phyric Shergottite Tissint: Implications for the Geochemical Evolution of the Shergottite Source Mantle

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Simon, J. I.; Jones, J. H.; Yokoyama, T.

2015-01-01

Geochemically-depleted shergottites are basaltic rocks derived from a martian mantle source reservoir. Geochemical evolution of the martian mantle has been investigated mainly based on the Rb-Sr, Sm-Nd, and Lu-Hf isotope systematics of the shergottites [1]. Although potentially informative, U-Th- Pb isotope systematics have been limited because of difficulties in interpreting the analyses of depleted meteorite samples that are more susceptible to the effects of near-surface processes and terrestrial contamination. This study conducts a 5-step sequential acid leaching experiment of the first witnessed fall of the geochemically-depleted olivinephyric shergottite Tissint to minimize the effect of low temperature distrubence. Trace element analyses of the Tissint acid residue (mostly pyroxene) indicate that Pb isotope compositions of the residue do not contain either a martian surface or terrestrial component, but represent the Tissint magma source [2]. The residue has relatively unradiogenic initial Pb isotopic compositions (e.g., 206Pb/204Pb = 10.8136) that fall within the Pb isotope space of other geochemically-depleted shergottites. An initial µ-value (238U/204Pb = 1.5) of Tissint at the time of crystallization (472 Ma [3]) is similar to a time-integrated mu- value (1.72 at 472 Ma) of the Tissint source mantle calculated based on the two-stage mantle evolution model [1]. On the other hand, the other geochemically-depleted shergottites (e.g., QUE 94201 [4]) have initial µ-values of their parental magmas distinctly lower than those of their modeled source mantle. These results suggest that only Tissint potentially reflects the geochemical signature of the shergottite mantle source that originated from cumulates of the martian magma ocean

Chemical and isotopic evidence for hydrogeochemical processes occurring in the Lincolnshire Limestone

NASA Astrophysics Data System (ADS)

Bishop, Philip K.; Lloyd, John W.

1990-12-01

Over 150 groundwater samples from the Lincolnshire Limestone have been analysed for pH, major ions and δ 13C ratios. Where possible, field E h and iodide concentrations were measured and methane concentrations were determined for 12 samples. Stable isotope ratios were determined for soil and rock carbonate samples. A system of zonation allows the division of hydrogeochemical processes occurring in the aquifer. The use of hydrochemical and isotope data in modelling exercises enables the re-evaluation and possible enhancement of the understanding of hydrogeochemical processes. The carbonate chemistry of outcrop groundwaters is explained by calcite saturation being achieved under open-system conditions in the soil zone. δ 13C ratios in the range - 15.99 to - 10.57‰ may be generated from a stoichiometric reaction with possible additional partial and/or simultaneous exchange with soil CO 2 or carbonate. The isotopic composition of soil carbonate shows the effects of precipitation from soil waters. The incongruent dissolution of primary depositional limestone carbonate results in increasing magnesium and strontium concentrations and increasing δ 13C ratios for the groundwaters with flow down the hydraulic gradient. As a result of incongruent dissolution, secondary calcite may be precipitated onto fissure surfaces. Significant nitrate and sulphate reduction in non-saline groundwaters is not supported by the results of hydrochemical and isotope modelling exercises. However, sulphate reduction and methane fermentation may be affecting the isotopic and chemical compositions of saline groundwaters. Sodium-calcium ion exchange leads to limited calcite dissolution deep in the aquifer, but the evolution of these groundwaters is confused by the uncertain effects of oxidation of organic carbon and mixing with a saline end-member solution.

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.

Isotopic Pu, Am and Cm signatures in environmental samples contaminated by the Fukushima Dai-ichi Nuclear Power Plant accident.

PubMed

Yamamoto, M; Sakaguchi, A; Ochiai, S; Takada, T; Hamataka, K; Murakami, T; Nagao, S

2014-06-01

Dust samples from the sides of roads (black substances) have been collected together with litter and soil samples at more than 100 sites contaminated heavily in the 20-km exclusion zones around Fukushima Dai-ichi Nuclear Power Plant (FDNPP) (Minamisoma City, and Namie, Futaba and Okuma Towns), in Iitate Village located from 25 to 45 km northwest of the plant and in southern areas from the plant. Isotopes of Pu, Am and Cm have been measured in the samples to evaluate their total releases into the environment from the FDNPP and to get the isotopic compositions among these nuclides. For black substances and litter samples, in addition to Pu isotopes, (241)Am, (242)Cm and (243,244)Cm were determined for most of samples examined, while for soil samples, only Pu isotopes were determined. The results provided a coherent data set on (239,240)Pu inventories and isotopic composition among these transuranic nuclides. When these activity ratios were compared with those for fuel core inventories in the FDNPP accident estimated by a group at JAEA, except (239,240)Pu/(137)Cs activity ratios, fairly good agreements were found, indicating that transuranic nuclides, probably in the forms of fine particles, were released into the environment without their large fractionations. The obtained data may lead to more accurate information about the on-site situation (e.g., burn-up, conditions of fuel during the release phase, etc.), which would be difficult to get otherwise, and more detailed information on the dispersion and deposition processes of transuranic nuclides and the behavior of these nuclides in the environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

Oxygen isotope analysis of fossil organic matter by secondary ion mass spectrometry

NASA Astrophysics Data System (ADS)

Tartèse, Romain; Chaussidon, Marc; Gurenko, Andrey; Delarue, Frédéric; Robert, François

2016-06-01

We have developed an analytical procedure for the measurement of oxygen isotope composition of fossil organic matter by secondary ion mass spectrometry (SIMS) at the sub-per mill level, with a spatial resolution of 20-30 μm. The oxygen isotope composition of coal and kerogen samples determined by SIMS are on average consistent with the bulk oxygen isotope compositions determined by temperature conversion elemental analysis - isotope ratio mass spectrometry (TC/EA-IRMS), but display large spreads of δ18O of ∼5-10‰, attributed to mixing of remnants of organic compounds with distinct δ18O signatures. Most of the δ18O values obtained on two kerogen residues extracted from the Eocene Clarno and Early Devonian Rhynie continental chert samples and on two immature coal samples range between ∼10‰ and ∼25‰. Based on the average δ18O values of these samples, and on the O isotope composition of water processed by plants that now constitute the Eocene Clarno kerogen, we estimated δ18Owater values ranging between around -11‰ and -1‰, which overall correspond well within the range of O isotope compositions for present-day continental waters. SIMS analyses of cyanobacteria-derived organic matter from the Silurian Zdanow chert sample yielded δ18O values in the range 12-20‰. Based on the O isotope composition measured on recent cyanobacteria from the hypersaline Lake Natron (Tanzania), and on the O isotope composition of the lake waters in which they lived, we propose that δ18O values of cyanobacteria remnants are enriched by about ∼18 ± 2‰ to 22 ± 2‰ relative to coeval waters. This relationship suggests that deep ocean waters in which the Zdanow cyanobacteria lived during Early Silurian times were characterised by δ18O values of around -5 ± 4‰. This study, establishing the feasibility of micro-analysis of Phanerozoic fossil organic matter samples by SIMS, opens the way for future investigations of kerogens preserved in Archean cherts and of the O isotopic composition of ocean water at that period in time.

High precision tungsten isotope analysis using MC-ICP-MS and application for terrestrial samples

NASA Astrophysics Data System (ADS)

Suzuki, K.; Takamasa, A.

2017-12-01

Tungsten has five isotopes (M = 180, 182, 183, 184, 186), and 182W isotope is a rediogenic isotope produced by b-decay of 182Hf. Its half life is short (8.9 m.y.), and 182W isotope has been investigated to understand the early Earth geochemical evolution. Both Hf and W are highly refractory elements. As Hf is a lithophile and W is a siderophile elements, 182Hf-182W system could give constraints on metal-silicate (core-mantle) differentiation such as especially early Earth system because of its larege fractionation betwenn core-mantle and short half life. Improvement of analytical techniques of W isotope analyses leads to findings of W isotope anomaly (mostly positive) in old komatiites (2.4 - 3.8 Ga) and young volcanic rocks (12 Ma Ontong Java Plateau and 6 Ma Baffin Bay). In our study, high-precision W isotope ratio measurement with MC-ICP-MS (Thermo co. Ltd., NEPTUNE PLUS). We have measured W standard solution (SRM 3163) and obtained the isotopic compositions with an precision of ± 5ppm. However, the standard solution, which separated by cation or anion exchange resin, has systematical 183W/184W drift to -5ppm. These phenomena was also reported by Willbold et al. (2011). Therefore, we used the standard solution for correction of isotopic fractionation of samples which was processed by the same method as that of the samples. We will present the data of terrestrial samples obtained by the technique dveloped in this study.

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.

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.

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.

Time differences in the formation of meteorites as determined from the ratio of lead-207 to lead-206

USGS Publications Warehouse

Tatsumoto, M.; Knight, R.J.; Allegre, C.J.

1973-01-01

Measurements of the lead isotopic composition and the uranium, thorium, and lead concentrations in meteorites were made in order to obtain more precise radiometric ages of these members of the solar system. The newly determined value of the lead isotopic composition of Canyon Diablo troilite is as follows: 206Pb/204Pb = 9.307, 207Pb/204Pb = 10.294, and 208Pb/204Pb = 29.476. The leads of Angra dos Reis, Sioux County, and Nuevo Laredo achondrites are very radiogenic, the 206Pb/204Pb values are about 200, and the uranium-thorium-lead systems are nearly concordant. The ages of the meteorites as calculated from a single-stage 207Pb/206Pb isochron based on the newly determined primordial lead value and the newly reported 235U and 238U decay constants, are 4.528 ?? 10 9 years for Sioux County and Nuevo Laredo and 4.555 ?? 10 9 years for Angra dos Reis. When calculated with the uranium decay constants used by Patterson, these ages are 4.593 ?? 109 years and 4.620 ?? 109 years, respectively, and are therefore 40 to 70 ?? 106 years older than the 4.55 ?? 109 years age Patterson reported. The age difference of 27 ?? 106 years between Angra dos Reis and the other two meteorites is compatible with the difference between the initial 87Sr/86Sr ratio of Angra dos Reis and that of seven basaltic achondrites observed by Papanastassiou and Wasserburg. The time difference is also comparable to that determined by 129I-129Xe chronology. The ages of ordinary chondrites (H5 and L6) range from 4.52 to 4.57 ?? 109 years, and, here too, time differences in the formation of the parent bodies or later metamorphic events are indicated. Carbonaceous chondrites (C2 and C3) appear to contain younger lead components.

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.

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.

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.

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.

[Spatial and temporal variations of hydrological characteristic on the landscape zone scale in alpine cold region].

PubMed

Yang, Yong-Gang; Hu, Jin-Fei; Xiao, Hong-Lang; Zou, Song-Bing; Yin, Zhen-Liang

2013-10-01

There are few studies on the hydrological characteristics on the landscape zone scale in alpine cold region at present. This paper aimed to identify the spatial and temporal variations in the origin and composition of the runoff, and to reveal the hydrological characteristics in each zone, based on the isotopic analysis of glacier, snow, frozen soil, groundwater, etc. The results showed that during the wet season, heavy precipitation and high temperature in the Mafengou River basin caused secondary evaporation which led to isotope fractionation effects. Therefore, the isotope values remained high. Temperature effects were significant. During the dry season, the temperature was low. Precipitation was in the solid state during the cold season and the evaporation was weak. Water vapor came from the evaporation of local water bodies. Therefore, less secondary evaporation and water vapor exchange occurred, leading to negative values of delta18O and deltaD. delta18O and deltaD values of precipitation and various water bodies exhibited strong seasonal variations. Precipitation exhibited altitude effects, delta18O = -0. 005 2H - 8. 951, deltaD = -0.018 5H - 34. 873. Other water bodies did not show altitude effects in the wet season and dry season, because the runoff was not only recharged by precipitation, but also influenced by the freezing and thawing process of the glacier, snow and frozen soil. The mutual transformation of precipitation, melt water, surface water and groundwater led to variations in isotopic composition. Therefore, homogenization and evaporation effect are the main control factors of isotope variations.

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

Isotopic evolution of Mauna Loa volcano

NASA Astrophysics Data System (ADS)

Kurz, Mark D.; Kammer, David P.

1991-04-01

In an effort to understand the temporal helium isotopic variations in Mauna Loa volcano, we have measured helium, strontium and lead isotopes in a suite of Mauna Loa lavas that span most of the subaerial eruptive history of the volcano. The lavas range in age from historical flows to Ninole basalt which are thought to be several hundred thousand years old. Most of the samples younger than 30 ka in age (Kau Basalt) are radiocarbon-dated flows, while the samples older than 30 ka are stratigraphically controlled (Kahuku and Ninole Basalt). The data reveal a striking change in the geochemistry of the lavas approximately 10 ka before present. The lavas older than 10 ka are characterized by high 3He/ 4He ( ˜ 16-20 times atmospheric), higher 206Pb/ 204Pb ( ˜ 18.2), and lower 87Sr/ 86Sr ( ˜ 0.70365) ratios than the younger Kau samples (having He, Pb and Sr ratios of approximately 8.5 × atmospheric, 18.1 and 0.70390, respectively). The historical lavas are distinct in having intermediate Sr and Pb isotopic compositions with 3He/ 4He ratios similar to the other young Kau basalt ( ˜ 8.5 × atmospheric). The isotopic variations are on a shorter time scale (100 to 10,000 years) than has previously been observed for Hawaiian volcanoes, and demonstrate the importance of geochronology and stratigraphy to geochemical studies. The data show consistency between all three isotope systems, which suggests that the variations are not related to magma chamber degassing processes, and that helium is not decoupled from the other isotopes. However, the complex temporal evolution suggests that three distinct mantle sources are required to explain the isotopic data. Most of the Mauna Loa isotopic variations could be explained by mixing between a plume type source, similar to Loihi, and an asthenospheric source with helium isotopic composition close to MORB and elevated Sr isotopic values. An asthenospheric source, or variation within the plume source, is considered more likely than lithospheric sources due to the elevated 87Sr/ 86Sr ratios in the recent Kau Basalts. However, the distinct isotopic characteristics of the historical lavas are inferred to be related to lithospheric involvement in the latest stages of shield-building volcanism.

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

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 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.

Nitrogen isotope record of a perturbed paleoecosystem in the aftermath of the end-Triassic crisis, Doniford section, SW England

NASA Astrophysics Data System (ADS)

Paris, Guillaume; Beaumont, ValéRie; Bartolini, Annachiara; CléMence, Marie-Emilie; Gardin, Silvia; Page, Kevin

2010-08-01

The Triassic-Jurassic transition (TJ) is characterized by successive perturbations of the carbon cycle during a time of biotic disruption as recorded by the carbon isotopic composition of organic matter (δ13Corg). The nitrogen isotopic composition of sedimentary organic matter (δ15Norg) constitutes a key parameter to explore the functioning of the ecosystem during carbon cycle perturbations and biological crises, because it provide information on seawater redox conditions and/or nutrient cycling. Here we report the first continuous δ15Norg record across the TJ transition at the Doniford Bay section (Bristol Channel Basin, UK), combined with δ13Corg, kerogen typology and carbon (δ13Cmin) and oxygen (δ18Omin) isotopic composition of bulk carbonates. The end Triassic is characterized by a major negative excursion both in δ13Corg and δ13Cmin, very low TOC (Total Organic Carbon, wt%) and high δ15Norg values, associated with a sea level lowstand. A second δ13Corg negative excursion occurs during the lower Hettangian. This interval is characterized by phases of carbonate production increase alternated with phases of exceptional accumulations of type I organic matter (up to 12%) associated with lower δ15Norg and δ13Corg. This alternation likely reflects a succession of nutrient input increase to the basin leading to enhanced productivity and eutrophication, which promoted a primary production driven by organic-walled prokaryotic organisms. The following OM export increase generates anaerobic conditions within the basin. These events occur between periods of relatively good seawater column ventilation and nutrient recycling boosting the carbonate producer recovery. Ecosystems remain perturbed in the Bristol Channel Basin during the aftermath of the end-Triassic crisis.

Lead Isotope Characteristics of the Mindyak Gold Deposit, Southern Urals: Evidence for the Source of Metals

NASA Astrophysics Data System (ADS)

Chugaev, A. V.; Znamensky, S. E.

2018-01-01

The isotopic composition of Pb in pyrite of the Mindyak orogenic gold deposit located in the Main Ural Fault Zone, the Southern Urals, has been studied by the high-precision MC-ICP-MS method. Orebodies at the deposit are composed of early pyrite and late polysulfide-carbonate-quartz mineral assemblages. The orebodies are localized in olistostrome with carbonaceous clayey-cherty cement. Pyrites from early and late mineral assemblages are close in Pb isotope ratios. For early pyrite 206Pb/204Pb = 18.250-18.336, 207Pb/204Pb = 15.645-15.653, 208Pb/204Pb = 38.179-38.461; while for late pyrite 206Pb/204Pb = 18.102-18.378, 207Pb/204Pb = 15.635-15.646, 208Pb/204Pb = 38.149-38.320. The model parameters μ2 (238U/204Pb = 9.91 ± 2), ω2 (232Th/204Pb = 38.5 ± 4), and 232Th/238U = 3.88 ± 3 indicate that an upper crustal Pb source played a leading role in ore formation. Carbonaceous shale as an olistostrome cement and syngenetic sulfide mineralization are considered to be the main Pb sources of both early and late mineral assemblages. An additional recept in apparently magmatic lead is suggested for the late veinlet mineralization. The involvement of lead from several sources in ore formation is consistent with the genetic model, which assumes a two-stage formation of orebodies at the Mindyak deposit.

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.

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.

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.

Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis

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

Finkelstein, Myra E., E-mail: myraf@ucsc.edu; Kuspa, Zeka E.; Welch, Alacia

Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot frommore » all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ∼20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events. - Highlights: • We conducted a case-based analysis of illegal shootings of California condors. • Blood and feather Pb isotopes were used to reconstruct the illegal shooting events. • Embedded birdshot from the three condors had the same Pb isotope ratios. • Feather and blood Pb isotopes indicated that the condors were shot in a common event. • Ingested shot causes substantially greater lead exposure compared to embedded shot.« less

Isotopic mass independent signature of black crusts: a proxy for atmospheric aerosols formation in the Paris area (France).

NASA Astrophysics Data System (ADS)

Genot, Isabelle; Martin, Erwan; Yang, David Au; De Rafelis, Marc; Cartigny, Pierre; Wing, Boswell; Le Gendre, Erwann; Bekki, Slimane

2016-04-01

In view of the negative forcing of the sulfate aerosols on climate, a more accurate understanding of the formation of these particles is crucial. Indeed, despite the knowledge of their effects, uncertainties remain regarding the formation of sulfate aerosols, particularly the oxidation processes of S-bearing gases. Since the discovery of oxygen and sulfur mass independent fractionation (O- and S-MIF) processes on Earth, the sulfate isotopic composition became essential to investigate the atmospheric composition evolution and its consequences on the climate and the biosphere. Large amount of S-bearing compounds (SO2 mainly) is released into the atmosphere by anthropogenic and natural sources. Their oxidation in the atmosphere generates sulfate aerosols, H2SO4, which precipitate on the earth surface mainly as acid rain. One consequence of this precipitation is the formation of black crust on buildings made of carbonate stones. Indeed the chemical alteration of CaCO3 by H2SO4 leads to gypsum (CaSO4·2H2O) concretions on building walls. Associated to other particles, gypsum forms black-crusts. Therefore, black crusts acts as 'sulfate aerosol traps', meaning that their isotopic composition reveals the composition and thus the source and formation processes of sulfate aerosols in the atmosphere in a specific region. In this study we collected 37 black crusts on a 300km NW-SE profile centered on Paris (France). In our samples, sulfate represent 40wt.% and other particles 60wt.% of the black crusts. After sulfate extraction from each samples we measured their O- and S-isotopes composition. Variations of about 10‰ in δ18O and δ34S are observed and both O-MIF (Δ17O from 0 to 1.4‰) and S-MIF (Δ33S from 0 to -0.3‰) compositions have been measured. In regards to these compositions we can discuss the source and formation (oxidation pathways) of the sulfate aerosols in troposphere above the Paris region that covers urban, rural and coastal environments. Furthermore, this study shows for the first time O- and S-MIF signature in black crusts. Finally, we demonstrate that black crusts can be considered as a good 'sulfate aerosols traps', which can be widely used to study the sulfate aerosol formation, fate and sink in the troposphere.

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.

Modeling stable isotope transport in metamorphic and hydrothermal systems

NASA Astrophysics Data System (ADS)

Baumgartner, L. P.; Mueller, T.; Skora, S.; Begue, F.

2007-12-01

Stable isotopes are powerful tools for deciphering the fluid flow histories of metamorphic terrains. The nature of fluid flow, fluid sources, and fluid fluxes can be delineated in well constrained studies. Continuum mechanics models for stable isotope fluid-rock exchange were developed and used over the last three decades in an attempt to accurately interpret the signatures left behind by fluid flow in the earths crust. The efforts have been hampered by the realization that the exchange of many stable isotopes, e.g. oxygen and carbon, by intracrystalline diffusion, hence without re-organization of the crystal lattice, appears to be too slow to achieve significant exchange. This should lead to relatively flat isotopic exchange profiles on hand-, outcrop, or aureole scale. Nevertheless, isotopic fronts are typically sharp (sub mm to cm scale), when measured in the field. This has lead to the suggestion that these sharp fronts correspond to the sides of infiltration fronts, implying the data to have been collected at a high angle to the infiltration direction. Nevertheless, the fact that the oxygen and carbon fronts are located at the same place is not explained by this. A review of published carbon and oxygen data reveals that many contact aureoles show linear trends in oxygen-carbon isotope ratio diagrams for carbonate sample suits. This implies that the fluid composition infiltrating the aureoles had essentially an X(CO2) of 0.5. This is in contrast to skarn mineralogy developed, which requires a water-rich fluid, in agreement with the general notion that igneous fluids are water-rich. These and other observations indicate that the mass transport equation used for stable isotope exchange needs to be improved to model appropriately the actual isotope kinetics during fluid-rock exchange. Detailed isotope studies on systems where net transport reactions are driven by mass transport have led us to identify different exchange mechanisms, including: a) the stable isotope exchange is given by instantaneous mass balance written for the isotope during reaction; b) equilibrium precipitation of products, but slow exchange kinetics for reactants. These observations require that the reactive term in the stable isotope reactive transport equation is re-written to include the net transfer reactions, which in turn implies the solution of the transport equation for the elements driving the reaction.

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.

Methane clumped isotopes in the Songliao Basin (China): New insights into abiotic vs. biotic hydrocarbon formation

NASA Astrophysics Data System (ADS)

Shuai, Yanhua; Etiope, Giuseppe; Zhang, Shuichang; Douglas, Peter M. J.; Huang, Ling; Eiler, John M.

2018-01-01

Abiotic hydrocarbon gas, typically generated in serpentinized ultramafic rocks and crystalline shields, has important implications for the deep biosphere, petroleum systems, the carbon cycle and astrobiology. Distinguishing abiotic gas (produced by chemical reactions like Sabatier synthesis) from biotic gas (produced from degradation of organic matter or microbial activity) is sometimes challenging because their isotopic and molecular composition may overlap. Abiotic gas has been recognized in numerous locations on the Earth, although there are no confirmed instances where it is the dominant source of commercially valuable quantities in reservoir rocks. The deep hydrocarbon reservoirs of the Xujiaweizi Depression in the Songliao Basin (China) have been considered to host significant amounts of abiotic methane. Here we report methane clumped-isotope values (Δ18) and the isotopic composition of C1-C3 alkanes, CO2 and helium of five gas samples collected from those Xujiaweizi deep reservoirs. Some geochemical features of these samples resemble previously suggested identifiers of abiotic gas (13C-enriched CH4; decrease in 13C/12C ratio with increasing carbon number for the C1-C4 alkanes; abundant, apparently non-biogenic CO2; and mantle-derived helium). However, combining these constraints with new measurements of the clumped-isotope composition of methane and careful consideration of the geological context, suggests that the Xujiaweizi depression gas is dominantly, if not exclusively, thermogenic and derived from over-mature source rocks, i.e., from catagenesis of buried organic matter at high temperatures. Methane formation temperatures suggested by clumped-isotopes (167-213 °C) are lower than magmatic gas generation processes and consistent with the maturity of local source rocks. Also, there are no geological conditions (e.g., serpentinized ultramafic rocks) that may lead to high production of H2 and thus abiotic production of CH4 via CO2 reduction. We propose that the Songliao gas is representative of an atypical type of thermogenic gas that can be mistaken for abiotic gas. Such gases may be encountered more frequently in future exploration of deep or over-mature petroleum systems.

Tungsten isotopes and the origin of the Moon

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

Kruijer, Thomas S.; Kleine, Thorsten

Here, the giant impact model of lunar origin predicts that the Moon mainly consists of impactor material. As a result, the Moon is expected to be isotopically distinct from the Earth, but it is not. To account for this unexpected isotopic similarity of the Earth and Moon, several solutions have been proposed, including (i) post-giant impact Earth–Moon equilibration, (ii) alternative models that make the Moon predominantly out of proto-Earth mantle, and (iii) formation of the Earth and Moon from an isotopically homogeneous disk reservoir. Here we use W isotope systematics of lunar samples to distinguish between these scenarios. We reportmore » high-precision 182W data for several low-Ti and high-Ti mare basalts, as well as for Mg-suite sample 77215, and lunar meteorite Kalahari 009, which complement data previously obtained for KREEP-rich samples. In addition, we utilize high-precision Hf isotope and Ta/W ratio measurements to empirically quantify the superimposed effects of secondary neutron capture on measured 182W compositions. Our results demonstrate that there are no resolvable radiogenic 182W variations within the Moon, implying that the Moon differentiated later than 70 Ma after Solar System formation. In addition, we find that samples derived from different lunar sources have indistinguishable 182W excesses, confirming that the Moon is characterized by a small, uniform ~+26 parts-per-million excess in 182W over the present-day bulk silicate Earth. This 182W excess is most likely caused by disproportional late accretion to the Earth and Moon, and after considering this effect, the pre-late veneer bulk silicate Earth and the Moon have indistinguishable 182W compositions. Mixing calculations demonstrate that this Earth–Moon 182W similarity is an unlikely outcome of the giant impact, which regardless of the amount of impactor material incorporated into the Moon should have generated a significant 182W excess in the Moon. Consequently, our results imply that post-giant impact processes might have modified 182W, leading to the similar 182W compositions of the pre-late veneer Earth's mantle and the Moon.« less

Tungsten isotopes and the origin of the Moon

DOE PAGES

Kruijer, Thomas S.; Kleine, Thorsten

2017-08-04

Here, the giant impact model of lunar origin predicts that the Moon mainly consists of impactor material. As a result, the Moon is expected to be isotopically distinct from the Earth, but it is not. To account for this unexpected isotopic similarity of the Earth and Moon, several solutions have been proposed, including (i) post-giant impact Earth–Moon equilibration, (ii) alternative models that make the Moon predominantly out of proto-Earth mantle, and (iii) formation of the Earth and Moon from an isotopically homogeneous disk reservoir. Here we use W isotope systematics of lunar samples to distinguish between these scenarios. We reportmore » high-precision 182W data for several low-Ti and high-Ti mare basalts, as well as for Mg-suite sample 77215, and lunar meteorite Kalahari 009, which complement data previously obtained for KREEP-rich samples. In addition, we utilize high-precision Hf isotope and Ta/W ratio measurements to empirically quantify the superimposed effects of secondary neutron capture on measured 182W compositions. Our results demonstrate that there are no resolvable radiogenic 182W variations within the Moon, implying that the Moon differentiated later than 70 Ma after Solar System formation. In addition, we find that samples derived from different lunar sources have indistinguishable 182W excesses, confirming that the Moon is characterized by a small, uniform ~+26 parts-per-million excess in 182W over the present-day bulk silicate Earth. This 182W excess is most likely caused by disproportional late accretion to the Earth and Moon, and after considering this effect, the pre-late veneer bulk silicate Earth and the Moon have indistinguishable 182W compositions. Mixing calculations demonstrate that this Earth–Moon 182W similarity is an unlikely outcome of the giant impact, which regardless of the amount of impactor material incorporated into the Moon should have generated a significant 182W excess in the Moon. Consequently, our results imply that post-giant impact processes might have modified 182W, leading to the similar 182W compositions of the pre-late veneer Earth's mantle and the Moon.« less

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.

Stable carbon and nitrogen isotope enrichment in primate tissues

PubMed Central

Carter, Melinda L.; Karpanty, Sarah M.; Zihlman, Adrienne L.; Koch, Paul L.; Dominy, Nathaniel J.

2010-01-01

Isotopic studies of wild primates have used a wide range of tissues to infer diet and model the foraging ecologies of extinct species. The use of mismatched tissues for such comparisons can be problematic because differences in amino acid compositions can lead to small isotopic differences between tissues. Additionally, physiological and dietary differences among primate species could lead to variable offsets between apatite carbonate and collagen. To improve our understanding of the isotopic chemistry of primates, we explored the apparent enrichment (ε*) between bone collagen and muscle, collagen and fur or hair keratin, muscle and keratin, and collagen and bone carbonate across the primate order. We found that the mean ε* values of proteinaceous tissues were small (≤1‰), and uncorrelated with body size or phylogenetic relatedness. Additionally, ε* values did not vary by habitat, sex, age, or manner of death. The mean ε* value between bone carbonate and collagen (5.6 ± 1.2‰) was consistent with values reported for omnivorous mammals consuming monoisotopic diets. These primate-specific apparent enrichment values will be a valuable tool for cross-species comparisons. Additionally, they will facilitate dietary comparisons between living and fossil primates. Electronic supplementary material The online version of this article (doi:10.1007/s00442-010-1701-6) contains supplementary material, which is available to authorized users. PMID:20628886

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.

Geochemical and isotopic study of soils and waters from an Italian contaminated site: Agro Aversano (Campania)

USGS Publications Warehouse

Bove, M.A.; Ayuso, R.A.; de Vivo, B.; Lima, A.; Albanese, S.

2011-01-01

Lead isotope applications have been widely used in recent years in environmental studies conducted on different kinds of sampled media. In the present paper, Pb isotope ratios have been used to determine the sources of metal pollution in soils and waters in the Agro Aversano area. During three different sampling phases, a total of 113 surface soils (5-20. cm), 20 samples from 2 soil profiles (0-1. m), 11 stream waters and 4 groundwaters were collected. Major element concentrations in sampled media have been analyzed by the ICP-MS technique. Surface soils (20 samples), all soil profiles and all waters have been also analyzed for Pb isotope compositions by thermal ionization (TIMS). The geochemical data were assessed using statistic methods and cartographically elaborated in order to have a clear picture of the level of disturbance of the area. Pb isotopic data were studied to discriminate between anthropogenic and geologic sources. Our results show that As (5.6-25.6. mg/kg), Cu (9-677. mg/kg), Pb (22-193. mg/kg), Tl (0.53-3.62. mg/kg), V (26-142. mg/kg) and Zn (34-215. mg//kg) contents in analyzed soils, exceed the intervention limits fixed by the Italian Environmental Law for residential areas in some of the sampled sites, while intervention limit for industrial areas is exceeded only for Cu concentrations. Lead isotopic data, show that there is a high similarity between the ratios measured in the leached soil samples and those deriving from anthropic activities. This similarity with anthropogenic Pb is also evident in the ratios measured in both groundwater and stream water samples. ?? 2010 Elsevier B.V.

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.

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.

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.

A Sr and Mg isotopic study of soil and stream waters along an erosional gradient, Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Rosen, V. B.; Maher, K.; Kouba, C. M.; Weinman, B. A.; Yoo, K.; Mudd, S. M.

2012-12-01

Since chemical weathering rates are proposed to regulate atmospheric CO2 concentrations and by extension global temperature over geologic timescales, understanding the relationship between chemical weathering rates and physical erosion is crucial to accurately interpreting Earth's climate history. The rate of supply of fresh minerals to the weathering zone is known to be an important control on chemical weathering rates. However, the consequences of physical erosion on the isotopic composition of weathering-derived solutes are more difficult to assess. This study capitalizes on a series of granitic hillslope transects with different erosion rates but similar climate, vegetation, and bedrock, in order to assess the consequences of erosion on the Sr and Mg isotopic composition of solutes. Reactive transport model simulations of varying complexity have been used to complement the field measurements and to analyze the sensitivity of fluid isotopic compositions to changes in key parameters such as erosion rate, flow rate, and biological cycling. The three hillslopes in the Feather River Basin, California reflect different degrees of channel erosion at their bases—BRC is a hillslope with active channel incision (60% average slope, below the knickpoint), FTA is a hillslope reflecting the transition between the relict and modern-day incising areas (50% average slope, at the knickpoint), and POMD is a 30% average hillslope in the relict landscape above the knickpoint. We measured the major element compositions, as well as the Sr and Mg isotopic compositions of soil water leaches (deionized water leaches), lysimeters, stream waters, and groundwaters by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The 87Sr/86Sr values of soil and stream waters show minimal variation (0.7042 to 0.7046) as a function of soil depth, erosion rate, or sampling season despite abundant radiogenic biotite in the profiles. These results agree with the reactive transport model predictions at high erosion rates, and suggest that soil residence times and isotopic equilibrium times are too short for biotite weathering to influence the solute isotopic composition. In contrast, model results for δ26Mg of the soil waters and minerals suggest that the Mg isotopic composition of the solute changes as a function of erosion rate because of shorter isotopic equilibrium length scales at higher erosion rates. The isotopic reactive transport modeling, combined with hillslope depth profiles and stream water analyses, provides a useful approach for linking the isotopic composition of solutes to erosion rates. This study may provide insights into past and present riverine isotopic compositions, and contribute to our understanding of how surface processes have influenced past atmospheric conditions.

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.

Determining provenance of marine metal pollution in French bivalves using Cd, Zn and Pb isotopes

NASA Astrophysics Data System (ADS)

Shiel, Alyssa E.; Weis, Dominique; Cossa, Daniel; Orians, Kristin J.

2013-11-01

Cadmium, Zn and Pb isotopic compositions (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) have been used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from the coastlines of France (English Channel, Atlantic and Mediterranean coasts). The Cd isotopic signatures (δ114Cd = -1.08‰ to -0.52‰) exhibited by bivalves from the coastlines of France, excluding those from NE France, are within the range of those exhibited by bivalves from the USA East coast (δ114Cd = -1.20‰ to -0.54‰). This indicates the high prevalence of industry, as well as the low natural contributions of Cd from North Atlantic waters in both regions. Thus, the significance of anthropogenic Cd sources is similar. These significant anthropogenic contributions are identified for bivalves with a large range in tissue Cd concentrations. Importantly, French bivalves from the Gironde estuary and Marennes-Oléron basin (regions of historic and modern importance for oyster farming, respectively) exhibited the highest Cd levels of the study. Their Cd isotopic signatures indicate historical smelting emissions remain the primary Cd source despite the cessation of local smelting activities in 1986 and subsequent remedial efforts. No significant variability is observed in the δ66Zn values of the French bivalves (∼0.53‰), with the exception of the much heavier compositions exhibited by oysters from the polluted Gironde estuary (1.19-1.27‰). Lead isotopes do not fractionate during processing like Cd and Zn. They can, therefore, be used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as metal sources to French bivalves. Cadmium and Zn isotopes are successfully used here as tracers of anthropogenic processing emissions and are combined with Pb isotope "fingerprinting" techniques to identify metal sources.

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.

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...

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.

Isotopic anomalies - Chemical memory of Galactic evolution

NASA Technical Reports Server (NTRS)

Clayton, Donald D.

1988-01-01

New mechanisms for the chemical memory of isotopic anomalies are proposed which are based on the temporal change during the chemical evolution of the Galaxy of the isotopic composition of the mean ejecta from stars. Because of the differing temporal evolution of primary and secondary products of nucleosynthesis, the isotopic composition of the bulk interstellar medium changes approximately linearly with time, and thus any dust component having an age different from that of average dust will be isotopically anomalous. Special attention is given to C, O, Mg, Si, and isotopically heavy average-stellar condensates of SiC.

Seasonal, synoptic and diurnal variation of atmospheric water-isotopologues in the boundary layer of Southwestern Germany caused by plant transpiration, cold-front passages and dewfall.

NASA Astrophysics Data System (ADS)

Christner, Emanuel; Dyroff, Christoph; Kohler, Martin; Zahn, Andreas; Gonzales, Yenny; Schneider, Matthias

2013-04-01

Atmospheric water is an enormously crucial trace gas. It is responsible for ~70 % of the natural greenhouse effect (Schmidt et al., JGR, 2010) and carries huge amounts of latent heat. The isotopic composition of water vapor is an elegant tracer for a better understanding and quantification of the extremely complex and variable hydrological cycle in Earth's atmosphere (evaporation, cloud condensation, rainout, re-evaporation, snow), which in turn is a prerequisite to improve climate modeling and predictions. As H216O, H218O and HDO differ in vapor pressure and mass, isotope fractionation occurs due to condensation, evaporation and diffusion processes. In contrast to that, plants are able to transpire water with almost no isotope fractionation. For that reason the ratio of isotopologue concentrations in the boundary layer (BL) provides, compared to humidity measurements alone, independent and additional constraints for quantifying the strength of evaporation and transpiration. Furthermore the isotope ratios contain information about transport history of an air mass and microphysical processes, that is not accessible by humidity measurements. Within the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) a commercial Picarro Analyzer L2120-i is operated at Karlsruhe in Southwestern Germany, which is continuously measuring the isotopologues H216O, HDO and H218O of atmospheric water vapor since January 2012. A one year record of H216O, HDO and H218O shows clear seasonal, synoptic and diurnal characteristics and reveals the main driving processes affecting the isotopic composition of water vapor in the Middle European BL. Changes in continental plant transpiration and evaporation throughout the year lead to a slow seasonal HDO/H216O-variation, that cannot be explained by pure Rayleigh condensation. Furthermore, cold-front passages from NW lead to fast and pronounced depletion of the HDO/H216O-ratio within minutes. Superimposed to these variations are local diurnal processes like dewfall, which cause a diurnal pattern captured by the deuterium excess.

Lead Isotopic Source Signatures for Rains and River Waters in Taiwan

NASA Astrophysics Data System (ADS)

You, C.; Cheng, M.; Lee, M.; Lin, F.

2002-12-01

Lead isotopic compositions and Pb contents in rains and river waters are sensitive proxies for air-pollutant sources and their transport processes. We have collected more than 100 wet precipitations between 1998 and 2001 at Peng-Chia Yu, an offshore island in northern Taiwan, and two other cities, Taichung and Tainan, located at central and southern Taiwan. Additional 14 river waters collected along the Er-Ren-Shi River, Tainan were investigated for systematic comparison. All collected samples were analyzed for major ions (i.e., Cl, Na, Mg, Ca, SO4, NO3 and NH4) by ion chromatography, trace elements and Pb isotopes by ICP-MS (Element II) installed at NCKU. The Peng-Chia Yu rains show large seasonal variation in major ions where Na and Cl are much higher in the winter season. Significant industrial contributions of SO4, NH4 and nsCa are detected at Taichung and Tainan. Trace element results display a more complicated picture, suggesting mixing among seasalt, Asia continental dust, and atmospheric pollutant. These chemical data can be understood in terms of seasonal wind direction changes due to the Asian monsoon system. In winter, the northerly cold wind blow materials with high concentration of anthropogenic input (i.e., Pb and SO4) and dust source (i.e., Al and Ca) from the Asia continent. In contrast, the intertropical convergence zone (ITCZ) migrates northward and caused southwest monsoon prevail in the summer. The 208Pb/207Pb ratio shows consistent seasonal trends as that of Pb contents, possibly a result of mixing between Asia atmospheric sources and seasalt. For the Er-ren Shi River waters, Pb and Pb isotopic compositions vary systematically downstream. Pb concentrations decrease rapidly from 5200 ppt at upstream stations to a value of less than 50 ppt near the estuary whereas 208Pb/207Pb varied between 2.087 and 2.124. The 208Pb/206Pb vs. 1/Pb plot demonstrates a mixing trend between anthropogenic sources and seawater. These results demonstrate that Pb and Pb isotopes in rains and river waters can be used as useful tools for tracing air-borne pollutant sources and their transportation processes.

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.

On the Origin of GEMS

NASA Technical Reports Server (NTRS)

Keller, L. P.; Messenger, S.

2004-01-01

GEMS (glass with embedded metal and sulfides) are a major component of anhydrous interplanetary dust particles (IDPs) their physical and chemical characteristics show marked similarities to contemporary interstellar dust. Recent oxygen isotopic measurements confirm that at least a small fraction (less than 5%) of GEMS are demonstrably presolar, while the remainder have ratios that are indistinguishable from solar values. GEMS with solar oxygen isotopic compositions either (1) had their isotopic compositions homogenized through processing in the interstellar medium (ISM), or (2) formed in the early solar system. Isotopic homogenization necessarily implies chemical homogenization, so (interstellar) GEMS compositions should reflect the average composition of dust in the local ISM. We performed a systematic examination of the bulk chemistry of GEMS in primitive IDPs in order to test this hypothesis.

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.

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

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.

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.

Isotopic composition of transpiration and rates of change in leaf water isotopologue storage in response to environmental variables.

PubMed

Simonin, Kevin A; Roddy, Adam B; Link, Percy; Apodaca, Randy; Tu, Kevin P; Hu, Jia; Dawson, Todd E; Barbour, Margaret M

2013-12-01

During daylight hours, the isotope composition of leaf water generally approximates steady-state leaf water isotope enrichment model predictions. However, until very recently there was little direct confirmation that isotopic steady-state (ISS) transpiration in fact exists. Using isotope ratio infrared spectroscopy (IRIS) and leaf gas exchange systems we evaluated the isotope composition of transpiration and the rate of change in leaf water isotopologue storage (isostorage) when leaves were exposed to variable environments. In doing so, we developed a method for controlling the absolute humidity entering the gas exchange cuvette for a wide range of concentrations without changing the isotope composition of water vapour. The measurement system allowed estimation of (18)O enrichment both at the evaporation site and for bulk leaf water, in the steady state and the non-steady state. We show that non-steady-state effects dominate the transpiration isoflux even when leaves are at physiological steady state. Our results suggest that a variable environment likely prevents ISS transpiration from being achieved and that this effect may be exacerbated by lengthy leaf water turnover times due to high leaf water contents. © 2013 John Wiley & Sons Ltd.

Mercury isotope constraints on the source for sediment-hosted lead-zinc deposits in the Changdu area, southwestern China

NASA Astrophysics Data System (ADS)

Xu, Chunxia; Yin, Runsheng; Peng, Jiantang; Hurley, James P.; Lepak, Ryan F.; Gao, Jianfeng; Feng, Xinbin; Hu, Ruizhong; Bi, Xianwu

2018-03-01

The Lanuoma and Cuona sediment-hosted Pb-Zn deposits hosted by Upper Triassic limestone and sandstone, respectively, are located in the Changdu area, SW China. Mercury concentrations and Hg isotopic compositions from sulfide minerals and potential source rocks (e.g., the host sedimentary rocks and the metamorphic basement) were investigated to constrain metal sources and mineralization processes. In both deposits, sulfide minerals have higher mercury (Hg) concentrations (0.35 to 1185 ppm) than the metamorphic basement rocks (0.05 to 0.15 ppm) and sedimentary rocks (0.02 to 0.08 ppm). Large variations of mass-dependent fractionation (3.3‰ in δ202Hg) and mass-independent fractionation (0.3‰ in Δ199Hg) of Hg isotopes were observed. Sulfide minerals have Hg isotope signatures that are similar to the hydrothermal altered rocks around the deposit, and similar to the metamorphic basement, but different from barren sedimentary rocks. The variation of Δ199Hg suggests that Hg in sulfides was mainly derived from the underlying metamorphic basement. Mercury isotopes could be a geochemical tracer in understanding metal sources in hydrothermal ore deposits.

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.

Crystal growth and disequilibrium distribution of oxygen isotopes in an igneous Ca-Al-rich inclusion from the Allende carbonaceous chondrite

NASA Astrophysics Data System (ADS)

Kawasaki, Noriyuki; Simon, Steven B.; Grossman, Lawrence; Sakamoto, Naoya; Yurimoto, Hisayoshi

2018-01-01

TS34 is a Type B1 Ca-Al-rich inclusion (CAI) from the Allende CV3 chondrite, consisting of spinel, melilite, Ti-Al-rich clinopyroxene (fassaite) and minor anorthite in an igneous texture. Oxygen and magnesium isotopic compositions were measured by secondary ion mass spectrometry in spots of known chemical composition in all major minerals in TS34. Using the sequence of formation from dynamic crystallization experiments and from chemical compositions of melilite and fassaite, the oxygen isotopic evolution of the CAI melt was established. Oxygen isotopic compositions of the constituent minerals plot along the carbonaceous chondrite anhydrous mineral line. The spinel grains are uniformly 16O-rich (Δ17O = -22.7 ± 1.7‰, 2SD), while the melilite grains are uniformly 16O-poor (Δ17O = -2.8 ± 1.8‰) irrespective of their åkermanite content and thus their relative time of crystallization. The fassaite crystals exhibit growth zoning overprinting poorly-developed sector zoning; they generally grow from Ti-rich to Ti-poor compositions. The fassaite crystals also show continuous variations in Δ17O along the inferred directions of crystal growth, from 16O-poor (Δ17O ∼ -3‰) to 16O-rich (Δ17O ∼ -23‰), covering the full range of oxygen isotopic compositions observed in TS34. The early-crystallized 16O-poor fassaite and the melilite are in oxygen isotope equilibrium and formed simultaneously. The correlation of oxygen isotopic compositions with Ti content in the fassaite imply that the oxygen isotopic composition of the CAI melt evolved from 16O-poor to 16O-rich during fassaite crystallization, presumably due to oxygen isotope exchange with a surrounding 16O-rich nebular gas. Formation of spinel, the liquidus phase in melts of this composition, predates crystallization of all other phases, so its 16O-rich composition is a relic of an earlier stage. Anorthite exhibits oxygen isotopic compositions between Δ17O ∼ -2‰ and -9‰, within the range of those of fassaite, indicating co-crystallization of these two minerals during the earliest to intermediate stage of fassaite growth. The melilite and fassaite yield an 26Al-26Mg mineral isochron with an initial value of (26Al/27Al)0 = (5.003 ± 0.075) × 10-5, corresponding to a relative age of 0.05 ± 0.02 Myr from the canonical Al-Mg age of CAIs. These data demonstrate that both 16O-rich and 16O-poor reservoirs existed in the solar nebula at least ∼0.05 Myr after the birth of the Solar System.

Oxygen isotope corrections for online δ34S analysis

USGS Publications Warehouse

Fry, B.; Silva, S.R.; Kendall, C.; Anderson, R.K.

2002-01-01

Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the δ34S isotopic composition of plants, animals and soils. We found that the online technology for automated δ34S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO2 produced, and as a result calculated δ34S values were often 1–3‰ too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO2-SiO2 buffering method that minimizes detrimental oxygen isotope variations in SO2.

Early Proterozoic crustal evolution: Geochemical and NdPb isotopic evidence from metasedimentary rocks, southwestern North America

NASA Astrophysics Data System (ADS)

McLennan, S. M.; Hemming, S. R.; Taylor, S. R.; Eriksson, K. A.

1995-03-01

Early Proterozoic (1.8-1.7 Ga) metasedimentary rocks in northern New Mexico and southern Colorado, USA, can be divided into turbidite successions (commonly volcanogenic) associated with mafic/felsic metavolcanic successions (e.g., Irving Fm.) and stable shelf quartzite-pelite successions of shallow marine origin (e.g., Hondo Gp.). Metapelites from the turbidite successions reported here have low K2O/Na2O, low Th/U (<3.0), low to moderate Th/Sc (0.1-0.6), and slight negative Eu-anomalies, although regionally, negative Eu-anomalies in such rocks are common. At the time of sedimentation (ca. 1.7-1.8 Ga), ɛNd values were in the range +3 to +7, indistinguishable from associated metavolcanic and plutonic rocks. Similarly, lead isotopic data scatter about a 1.7 Ga reference isochron. Low κ (232Th/238U) values for the Irving Formation are consistent with derivation from crustal sources similar to the southern Colorado/northern New Mexico lead isotope crustal province. These data are further consistent with a volcanic arc related origin. In contrast, stable shelf metapelites have high K2O/Na2O, variable but commonly high Th/U (2.0-7.0), moderate to high Th/Sc (0.5-1.4), and substantial negative Eu-anomalies. Although compositions are rather variable, they are typical of post-Archean shales. Neodymium isotopes are surprisingly radiogenic with ɛNd(1.7 Ga) in the range -0.2 to +4. Lead isotopic data for the least radiogenic samples also are consistent with a dominantly juvenile source and on a 207Pb/204Pb vs. 206Pb/204Pb diagram, data scatter slightly above the 1.7 Ga reference isochron, suggesting minor components of significantly older material. Lead isotopic systematics suggest that a major component of the provenance was derived from the immediately associated metavolcanic-plutonic terranes, consistent with suggestions of a first-cycle origin, but with an Archean component. Isotopic data restrict the Archean component to about 10%, on average, and no more than 25% in any sample. This older crustal component may be derived either by direct erosion of Archean rocks, such as the Wyoming Province, or indirectly through assimilation into Early Proterozoic igneous rocks. Although the stable shelf sedimentary rocks are derived from a provenance with similar ages as the volcanogenic turbidites, the geochemical characteristics of the provenance are significantly different. Accordingly, these data are consistent with especially rapid and widespread crustal growth and evolution in southwestern North America during the period 1.9-1.7 Ga. Several samples from the Hondo Group and Uncompahgre Formation have REE patterns that are rotated to LREE depletion and perhaps HREE enrichment. The change in REEs correlate with Mo, U, and V abundances and Pb isotopic characteristics suggesting sedimentary processes similar to those operating in black shales affected these REE patterns. REE patterns and Th/U ratios of Early Proterozoic volcanogenic turbidites examined in this and other studies differ on average from turbidites found in Archean greenstone belts. Negative Eu-anomalies are common, HREE-depletion is seen but comparatively rare, and Th/U ratios are commonly below 3.0. Accordingly, these data are consistent with models suggesting that the upper crust had a different composition in the Archean.

Discrimination of bullet types using analysis of lead isotopes deposited in gunshot entry wounds.

PubMed

Wunnapuk, Klintean; Minami, Takeshi; Durongkadech, Piya; Tohno, Setsuko; Ruangyuttikarn, Werawan; Moriwake, Yumi; Vichairat, Karnda; Sribanditmongkol, Pongruk; Tohno, Yoshiyuki

2009-01-01

In order to discriminate bullet types used in firearms, of which the victims died, the authors investigated lead isotope ratios in gunshot entry wounds from nine lead (unjacketed) bullets, 15 semi-jacketed bullets, and 14 full-jacketed bullets by inductively coupled plasma-mass spectrometry. It was found that the lead isotope ratio of 207/206 in gunshot entry wounds was the highest with lead bullets, and it decreased in order from full-jacketed to semi-jacketed bullets. Lead isotope ratios of 208/206 or 208/207 to 207/206 at the gunshot entry wound were able to discriminate semi-jacketed bullets from lead and full-jacketed ones, but it was difficult to discriminate between lead and full-jacketed bullets. However, a combination of element and lead isotope ratio analyses in gunshot entry wounds enabled discrimination between lead, semi-jacketed, and full-jacketed bullets.

Chromium isotope heterogeneity in the mantle

NASA Astrophysics Data System (ADS)

Xia, Jiuxing; Qin, Liping; Shen, Ji; Carlson, Richard W.; Ionov, Dmitri A.; Mock, Timothy D.

2017-04-01

To better constrain the Cr isotopic composition of the silicate Earth and to investigate potential Cr isotopic fractionation during high temperature geological processes, we analyzed the Cr isotopic composition of different types of mantle xenoliths from diverse geologic settings: fertile to refractory off-craton spinel and garnet peridotites, pyroxenite veins, metasomatised spinel lherzolites and associated basalts from central Mongolia, spinel lherzolites and harzburgites from North China, as well as cratonic spinel and garnet peridotites from Siberia and southern Africa. The δ53CrNIST 979 values of the peridotites range from - 0.51 ± 0.04 ‰ (2SD) to + 0.75 ± 0.05 ‰ (2SD). The results show a slight negative correlation between δ53Cr and Al2O3 and CaO contents for most mantle peridotites, which may imply Cr isotopic fractionation during partial melting of mantle peridotites. However, highly variable Cr isotopic compositions measured in Mongolian peridotites cannot be caused by partial melting alone. Instead, the wide range in Cr isotopic composition of these samples most likely reflects kinetic fractionation during melt percolation. Chemical diffusion during melt percolation resulted in light Cr isotopes preferably entering into the melt. Two spinel websterite veins from Mongolia have extremely light δ53Cr values of - 1.36 ± 0.04 ‰ and - 0.77 ± 0.06 ‰, respectively, which are the most negative Cr isotopic compositions yet reported for mantle-derived rocks. These two websterite veins may represent crystallization products from the isotopically light melt that may also metasomatize some peridotites in the area. The δ53Cr values of highly altered garnet peridotites from southern Africa vary from - 0.35 ± 0.04 ‰ (2SD) to + 0.12 ± 0.04 ‰ (2SD) and increase with increasing LOI (Loss on Ignition), reflecting a shift of δ53Cr to more positive values by secondary alteration. The Cr isotopic composition of the pristine, fertile upper mantle is estimated as δ53Cr = - 0.14 ± 0.12 ‰, after corrections for the effects of partial melting and metasomatism. This value is in line with that estimated for the BSE (- 0.12 ± 0.10 ‰) previously.

Reassessment of the NH4 NO3 thermal decomposition technique for calibration of the N2 O isotopic composition.

PubMed

Mohn, Joachim; Gutjahr, Wilhelm; Toyoda, Sakae; Harris, Eliza; Ibraim, Erkan; Geilmann, Heike; Schleppi, Patrick; Kuhn, Thomas; Lehmann, Moritz F; Decock, Charlotte; Werner, Roland A; Yoshida, Naohiro; Brand, Willi A

2016-09-08

In the last few years, the study of N 2 O site-specific nitrogen isotope composition has been established as a powerful technique to disentangle N 2 O emission pathways. This trend has been accelerated by significant analytical progress in the field of isotope-ratio mass-spectrometry (IRMS) and more recently quantum cascade laser absorption spectroscopy (QCLAS). Methods The ammonium nitrate (NH 4 NO 3 ) decomposition technique provides a strategy to scale the 15 N site-specific (SP ≡ δ 15 N α - δ 15 N β ) and bulk (δ 15 N bulk  = (δ 15 N α  + δ 15 N β )/2) isotopic composition of N 2 O against the international standard for the 15 N/ 14 N isotope ratio (AIR-N 2 ). Within the current project 15 N fractionation effects during thermal decomposition of NH 4 NO 3 on the N 2 O site preference were studied using static and dynamic decomposition techniques. The validity of the NH 4 NO 3 decomposition technique to link NH 4 + and NO 3 - moiety-specific δ 15 N analysis by IRMS to the site-specific nitrogen isotopic composition of N 2 O was confirmed. However, the accuracy of this approach for the calibration of δ 15 N α and δ 15 N β values was found to be limited by non-quantitative NH 4 NO 3 decomposition in combination with substantially different isotope enrichment factors for the conversion of the NO 3 - or NH 4 + nitrogen atom into the α or β position of the N 2 O molecule. The study reveals that the completeness and reproducibility of the NH 4 NO 3 decomposition reaction currently confine the anchoring of N 2 O site-specific isotopic composition to the international isotope ratio scale AIR-N 2 . The authors suggest establishing a set of N 2 O isotope reference materials with appropriate site-specific isotopic composition, as community standards, to improve inter-laboratory compatibility. This article is protected by copyright. All rights reserved.

Kinetically Controlled Alteration of the Chemical Record During Diagenesis: An Experimental Study on Hydrothermal Carbonate Replacement

NASA Astrophysics Data System (ADS)

Mueller, T.; Dohmen, R.; Jonas, L.; Immenhauser, A.

2016-12-01

The geological record stored in the geochemical composition of carbonates provides a direct source of information on the Earth systems. However, the robustness and accuracy of these key records can be compromised by post-depositional alteration of sediments, such as dolomitization during diagenesis or low temperature metamorphism. Hence, knowledge on the mechanisms and rates of these processes hold the key to evaluate the robustness of proxies or to evaluate the extent of geochemical alteration. Previously, we presented experimental results of hydrothermal alteration of single calcite crystals and aragonitic coral fragments leading to replacement of the original carbonate by a Ca-Mg carbonate phase of variable composition. The experiments revealed the formation of a multiphase reaction rim with multiple replacement fronts [1]. Here, the reaction rate as well as composition of the reaction products is controlled by element transport in the pore fluid. In this study we focus on the reaction path of the replacement reaction and its effect on the recorded Mg-isotope composition. XRD diffraction patterns suggest the initial precipitation of non-ordered protodolomite that is subsequently continuously recrystallizing over the duration of the experiments to form an ordered, albeit non-stoichiometric dolomite. These observations are in agreement with Mg-isotope composition measured of the bulk reaction rim showing a systematic evolution over time that cannot be explained by simple Rayleigh or equilibrium fractionation. We interpret these findings as additional, but delayed reaction fronts affecting the microstructure and chemical composition of the newly formed carbonate rim that are essentially decoupled from the initial replacement front. Our results highlight the need to quantitatively understand alteration processes during diagenesis in order to accurately interpret the preserved geochemical record stored in element and isotope ratios of carbonates. [1] Jonas L., Mueller T., Dohmen R., Baumgartner L., and Putlitz B. (2015): Transport-controlled hydrothermal replacement of calcite by Mg-carbonates, Geology, 43, 779-782.

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

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

NASA Technical Reports Server (NTRS)

O'D. Alexander, Conel

2003-01-01

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

The Molybdenum Isotope System as a Tracer of Slab Input in Subduction Zones: An Example From Martinique, Lesser Antilles Arc

NASA Astrophysics Data System (ADS)

Gaschnig, Richard M.; Reinhard, Christopher T.; Planavsky, Noah J.; Wang, Xiangli; Asael, Dan; Chauvel, Catherine

2017-12-01

Molybdenum isotopes are fractionated by Earth-surface processes and may provide a tracer for the recycling of crustal material into the mantle. Here, we examined the Mo isotope composition of arc lavas from Martinique in the Lesser Antilles arc, along with Cretaceous and Cenozoic Deep Sea Drilling Project sediments representing potential sedimentary inputs into the subduction zone. Mo stable isotope composition (defined as δ98Mo in ‰ deviation from the NIST 3134 standard) in lavas older than ˜7 million years (Ma) exhibits a narrow range similar to and slightly higher than MORB, whereas those younger than ˜7 Ma show a much greater range and extend to unusually low δ98Mo values. Sediments from DSDP Leg 78A, Site 543 have uniformly low δ98Mo values whereas Leg 14, Site 144 contains both sediments with isotopically light Mo and Mo-enriched black shales with isotopically heavy Mo. When coupled with published radiogenic isotope data, Mo isotope systematics of the lavas can be explained through binary mixing between a MORB-like end-member and different sedimentary compositions identified in the DSDP cores. The lavas older than ˜7 Ma were influenced by incorporation of isotopically heavy black shales into the mantle wedge. The younger lavas are the product of mixing isotopically light sedimentary material into the mantle wedge. The change in Mo isotope composition of the lavas at ˜7 Ma is interpreted to reflect the removal of the Cretaceous black shale component due to the arrival of younger ocean crust where the age-equivalent Cretaceous sediments were deposited in shallower oxic waters. Isotopic fractionation of Mo during its removal from the slab is not required to explain the observed systematics in this system.

Trihalomethanes formed from natural organic matter isolates: Using isotopic and compositional data to help understand sources

USGS Publications Warehouse

Bergamaschi, Brian A.; Fram, Miranda S.; Fujii, Roger; Aiken, George R.; Kendall, Carol; Silva, Steven R.

2000-01-01

Over 20 million people drink water from the Sacramento-San Joaquin Delta despite problematic levels of natural organic matter (NOM) and bromide in Delta water, which can form trihalomethanes (THMs) during the treatment process. It is widely believed that NOM released from Delta peat islands is a substantial contributor to the pool of THM precursors present in Delta waters. Dissolved NOM was isolated from samples collected at five channel sites within the Sacramento-San Joaquin Rivers and Delta, California, USA, and from a peat island agricultural drain. To help understand the sources of THM precursors, samples were analyzed to determine their chemical and isotopic composition, their propensity to form THMs, and the isotopic composition of the THMs.The chemical composition of the isolates was quite variable, as indicated by significant differences in carbon-13 nuclear magnetic resonance spectra and carbon-to-nitrogen concentration ratios. The lowest propensity to form THMs per unit of dissolved organic carbon was observed in the peat island agricultural drain isolate, even though it possessed the highest fraction of aromatic material and the highest specific ultraviolet absorbance. Changes in the chemical and isotopic composition of the isolates and the isotopic composition of the THMs suggest that the source of the THMs precursors was different between samples and between isolates. The pattern of variability in compositional and isotopic data for these samples was not consistent with simple mixing of river- and peat-derived organic material.

Coordinated Petrography and Oxygen Isotopic Compositions of Al-Rich Chondrules from CV3 Chondrites

NASA Astrophysics Data System (ADS)

Zhang, M. M.; Lin, Y. T.; Tang, G. Q.; Li, X. H.

2017-07-01

In this study, we coordinated the petrology, bulk compositions and oxygen isotope compositions of 12 ARCs from Allende and Leoville and Ningqiang chondrites in order to elucidate any potential genetic relationships between ARCs, CAIs and FMCs.

Paleoclimate Reconstruction at Lamanai, Belize Using Oxygen-Isotope Tropical Dendrochronology

NASA Astrophysics Data System (ADS)

Prentice, A.; Webb, E. A.; White, C. D.; Graham, E.

2009-05-01

Tropical dendrochronology can be complicated because many trees growing in these areas lack distinct visible annual rings. However, the oxygen-isotope composition of wood growing in tropical regions can provide a record of seasonal fluctuations in the amount of precipitation even when visible rings are absent. Variations in the oxygen-isotope compositions of cellulose as the trees grow can be related to the relative timing of wet and dry seasons and used to identify periods of drought. In this study, the oxygen-isotope composition was determined for cellulose extracted from living trees at the site of Lamanai, Belize to assess the variation in oxygen-isotope values that result from heterogeneity within individual tree rings and seasonal fluctuations in amount of precipitation. In temperate regions, the latewood rings that form during periods of reduced growth are traditionally selected for oxygen-isotope analysis of cellulose because their oxygen-isotope compositions are more directly influenced by climate and precipitation during the growing season. However, in tropical isotope dendrochronology, when visible rings are present, detailed sampling of both the light coloured earlywood and the denser latewood is required. At Lamanai, a seasonal signal was evident in the oxygen- isotope composition of the cellulose when tree rings were sectioned in very small increments (approximately every mm), sub-sampling both earlywood and latewood. However, the visible rings did not always correspond with minimum or maximum oxygen-isotope values. As a result, the amplitude of the oxygen-isotope signal obtained by considering only latewood samples is smaller than that obtained from fine-increment sampling. Hence, the oxygen-isotope values of latewood samples alone did not provide accurate data for climate reconstruction. Multiple series of latewood samples extracted from different cross-sections of the same tree did not consistently show the same trends in oxygen isotope values, which can differ by up to 2 permil around the circumference of the same ring. This indicates that even when visible rings are present in tropical trees, the rings may not be annual or continuous. However, the amplitude of variation in the oxygen-isotope values of cellulose from both early and latewood can be related to seasonal signals across the modern tree rings. These signals will be compared to the oxygen-isotope composition of tree ring cellulose extracted from a wood sample excavated from an ancient tomb at the site of Lamanai to assess the preservation of the cellulose- isotope signal in this artefact. If similar oxygen-isotope patterns are preserved in ancient cellulose they can be used as a proxy to determine past climate conditions, such as those experienced by the ancient Maya populations in Belize.

Boron Isotopic Composition Correlates with Ultra-Structure in a - Sea Coral Lophelia Pertusa: Implications for Biomineralization and - PH

NASA Astrophysics Data System (ADS)

Blamart, D.; Rollion-Bard, C.; Meibom, A.; Cuif, J.; Juillet-Leclerc, A.; Dauphin, Y.; Douarin, M.

2007-12-01

The geochemistry (stable isotopes and trace elements) of biogenic carbonates has been widely used for more than fifty years to reconstruct past climatic variability. During this time, the studies were mainly based on bulk sampling limiting sometimes the interpretations of the geochemical data as paleoclimatic proxies. Recently, high spatial resolution sampling techniques, such as micro-mill and SIMS, have been employed in the study of C, O and B isotopic compositions and trace elements (Mg, Sr) in the skeletons of a variety of (deep-sea) coral species. These studies have documented dramatic 'vital effects' and uncovered a systematic relationship between skeletal ultra-structure and stable isotopic composition. The formation of skeleton corals follows a universal two-step growth process. At the tips of the skeletal structures, the mineralizing cell layer produces centers of calcification (COC) or, equivalently, Early Mineralization Zone (EMZ). These EMZ are subsequently overgrown by fibrous aragonite(FA) consisting of cyclically added layers. The EMZ are characterized by systematically lighter C and O isotopic compositions compared with the adjacent FA. A number of geochemical models have been proposed, in which this systematic stable isotopic difference between EMZ and FA is ascribed to a biologically induced variation in the pH of a proposed Extra-cytoplasmic Calcifying Fluid (ECF) reservoir. In these models, relatively high pH conditions during the formation of EMZ result in relatively light C and O isotopic compositions compared with FA, which form under generally lower pH conditions. A direct test of such models would be possible if the Boron isotopic composition, which is pH sensitive, of EMZ and FA could be measured. We performed ion microprobe d11B measurements for EMZ and FA in Lophelia pertusa, a deep-sea coral common in the North-East Atlantic Ocean. We observe a systematic difference in B isotopic composition between the EMZ and FA skeleton. In EMZ, the measured δ11B values are consistently low. Fibrous aragonite is characterized by systematically higher d11B values, but also display B isotopic heterogeneity associated with specific growth bands in the calyx wall. The magnitude of the observed B isotopic variations cannot be explained by changes in environmental conditions and are likely caused by biological processes involved in the biomineralization of new skeleton; i.e. 'vital' effects. The observed B isotopic variations are opposite to the predictions of geochemical models for vital effects. Our data indicate that pH variations are not responsible for the observed stable isotopic fractionations. Geochemical models therefore do not provide an adequate framework within which to understand coral skeletal formation. Without a better understanding of these processes, which require experiments, the use of B isotopic composition to reconstruct paleo-pH variations in the oceans must be considered problematic - at least as far as Lophelia pertusa is concerned.

Chapter 16Tracing Nitrogen Sources and Cycling in Catchments

USGS Publications Warehouse

Kendall, Carol

1998-01-01

This chapter focuses on the uses of isotopes to understand water chemistry.I Isotopic compositions generally cannot be interpreted successfully in the absence of other chemical and hydrologic data. The chapter focusses on uses of isotopes in tracing sources and cycling of nitrogen in the water-component of forested catchment, and on dissolved nitrate in shallow waters, nutrient uptake studies in agricultural areas, large-scale tracer experiments, groundwater contamination studies, food-web investigations, and uses of compound-specific stable isotope techniques. Shallow waters moving along a flowpath through a relatively uniform material and reacting with minerals probably do not achieve equilibrium but gradually approach some steady-state composition. The chapter also discusses the use of isotopic techniques to assess impacts of changes in land-management practices and land use on water quality. The analysis of individual molecular components for isotopic composition has much potential as a method for tracing the source, biogeochemistry, and degradation of organic liquids and gases because different materials have characteristic isotope spectrums or biomarkers.

Tracing fluid transfer across subduction zones using iron and zinc stable isotopes

NASA Astrophysics Data System (ADS)

Williams, H. M.; Debret, B.; Pons, M. L.; Bouilhol, P.

2016-12-01

In subduction zones, serpentinite devolatilization within the downgoing slab and the fluids released play a fundamental role in volatile transfer as well as the redox evolution of the sub-arc mantle. Constraining subduction-related serpentinite devolatilisation is essential in order to better understand of the nature and composition of slab-derived fluids and fluid/rock interactions. Fe and Zn stable isotopes can trace fluid composition and speciation as isotope partitioning is driven by changes in oxidation state, coordination, and bonding environment. In the case of serpentinite devolatilisation, Fe isotope fractionation should reflect changes in Fe redox state and the formation of Fe-Cl- and SO42- complexes (Hill et al., GCA 2010); Zn isotope fractionation should be sensitive to complexation with CO32-, HS- and SO42- anions (Fujii et al., GCA 2011). We targeted samples from Western Alps ophiolite complexes, interpreted as remnants of serpentinized oceanic lithosphere metamorphosed and devolatilized during subduction (Hattori and Guillot, G3 2007; Debret et al., Chem. Geol. 2013). A striking negative correlation is present between bulk serpentinite Fe isotope composition and Fe3+/Fetot, with the highest grade samples displaying the heaviest Fe isotope compositions and lowest Fe3+/Fetot (Debret et al., Geology, 2016). The same samples also display a corresponding variation in Zn isotopes, with the highest grade samples displaying isotopically light compositions (Pons et al., in revision). The negative correlation between Fe and Zn isotopes and decrease in Fe3+/Fetot can explained by serpentinite sulfide breakdown and the release of fluids enriched in isotopically light Fe and heavy Zn sulphate complexes. The migration of these SOX-bearing fluids from the slab to the slab-mantle interface or mantle wedge has important implications for the redox evolution of the sub-arc mantle and the transport of metals from the subducting slab.

Improvement of 2,4-dinitrophenylhydrazine derivatization method for carbon isotope analysis of atmospheric acetone.

PubMed

Wen, Sheng; Yu, Yingxin; Guo, Songjun; Feng, Yanli; Sheng, Guoying; Wang, Xinming; Bi, Xinhui; Fu, Jiamo; Jia, Wanglu

2006-01-01

Through simulation experiments of atmospheric sampling, a method via 2,4-dinitrophenylhydrazine (DNPH) derivatization was developed to measure the carbon isotopic composition of atmospheric acetone. Using acetone and a DNPH reagent of known carbon isotopic compositions, the simulation experiments were performed to show that no carbon isotope fractionation occurred during the processes: the differences between the predicted and measured data of acetone-DNPH derivatives were all less than 0.5 per thousand. The results permitted the calculation of the carbon isotopic compositions of atmospheric acetone using a mass balance equation. In this method, the atmospheric acetone was collected by a DNPH-coated silica cartridge, washed out as acetone-DNPH derivatives, and then analyzed by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using this method, the first available delta13C data of atmospheric acetone are presented. Copyright 2006 John Wiley & Sons, Ltd.

Determination of chemical purity and isotopic composition of natural and carbon-13-labeled arsenobetaine bromide standards by quantitative(1)H-NMR.

PubMed

Le, Phuong-Mai; Ding, Jianfu; Leek, Donald M; Mester, Zoltan; Robertson, Gilles; Windust, Anthony; Meija, Juris

2016-10-01

In this study, we report the characterization of three arsenobetaine-certified reference materials by quantitative NMR. We have synthesized an arsenobetaine bromide high-purity standard of natural isotopic composition (ABET-1) and two carbon-13-labeled isotopic standards (BBET-1 and CBET-1). Assignments of the chemical purity and isotopic composition are not trivial in the case of arsenobetaine, and in this study we utilized quantitative(1)H-NMR techniques for the determination of the mass fractions (chemical purity). The isotopic purity of all three standards was also assessed by NMR from the carbon-13 satellite signals. The standards are non-hygroscopic, high-purity (ca. 0.99 g/g), and the carbon-13 enrichment for both isotopic standards is x((13)C)≈0.99. These standards are designed for use as primary calibrators for mass spectrometric determination of arsenobetaine in environmental samples.

Isotopic Analysis of Fingernails as a USGS Open House Demonstration of the Use of Stable Isotopes in Foodweb Studies

NASA Astrophysics Data System (ADS)

Silva, S. R.; Kendall, C.; Young, M. B.; Choy, D.

2011-12-01

The USGS Isotope Tracers Project uses stable isotopes and tritium to add a unique dimension of chemical information to a wide range of environmental investigations. The use and application of isotopes is usually an unfamiliar and even esoteric topic to the general public. Therefore during three USGS open house events, as a public outreach effort, we demonstrated the use of stable isotopes by analyzing nitrogen and carbon isotopes from very small fragments of fingernail from willing participants. We titled the exhibit "You Are What You Eat". The results from all participants were plotted on a graph indicating the general influence of different food groups on the composition of body tissues as represented by fingernails. All participants were assigned a number and no personal-identification information was collected. A subset of participants provided us with an estimate of the number of days a week various foods were eaten and if they were vegetarians, vegans or non-vegetarians. Volunteers from our research group were on hand to explain and discuss fundamental concepts such as how foods attain their isotopic composition, the difference between C3 and C4 plants, the effects of assimilation, trophic enrichment, and the various uses of stable isotopes in environmental studies. The results of the fingernail analyses showed the variation of the range of isotopic compositions among about 400 people at each event, the distinct influence of C4 plants (mainly corn and cane sugar) on our carbon isotopic composition, and the isotopic differences between vegetarians and non vegetarians among other details (http://wwwrcamnl.wr.usgs.gov/isoig/projects/fingernails/). A poll of visitors attending the open house event in 2006 indicated that "You Are What You Eat" was among the most popular exhibits. Following the first two open house events we were contacted by a group of researchers from Brazil who had completed a very similar study. Our collaboration resulted in a publication in the American Journal of Physical Anthropology (Nardoto et al., 2006). This study found that despite global trends toward dietary homogenization, regional differences in food resources and dietary preferences were recorded in the carbon and nitrogen isotopic compositions of fingernails.

Sea surface salinity of the Eocene Arctic Azolla event using innovative isotope modeling

NASA Astrophysics Data System (ADS)

Speelman, E. N.; Sewall, J. O.; Noone, D.; Huber, M.; Sinninghe Damste, J. S.; Reichart, G. J.

2009-04-01

With the realization that the Eocene Arctic Ocean was covered with enormous quantities of the free floating freshwater fern Azolla, new questions regarding Eocene conditions facilitating these blooms arose. Our present research focuses on constraining the actual salinity of, and water sources for, the Eocene Arctic basin through the application of stable water isotope tracers. Precipitation pathways potentially strongly affect the final isotopic composition of water entering the Arctic Basin. Therefore we use the Community Atmosphere Model (CAM3), developed by NCAR, combined with a recently developed integrated isotope tracer code to reconstruct the isotopic composition of global Eocene precipitation and run-off patterns. We further addressed the sensitivity of the modeled hydrological cycle to changes in boundary conditions, such as pCO2, sea surface temperatures (SSTs) and sea ice formation. In this way it is possible to assess the effect of uncertainties in proxy estimates of these parameters. Overall, results of all runs with Eocene boundary conditions, including Eocene topography, bathymetry, vegetation patterns, TEX86 derived SSTs and pCO2 estimates, show the presence of an intensified hydrological cycle with precipitation exceeding evaporation in the Arctic region. Enriched, precipitation weighted, isotopic values of around -120‰ are reported for the Arctic region. Combining new results obtained from compound specific isotope analyses (δD) on terrestrially derived n-alkanes extracted from Eocene sediments, and model outcomes make it possible to verify climate reconstructions for the middle Eocene Arctic. Furthermore, recently, characteristic long-chain mid-chain ω20 hydroxy wax constituents of Azolla were found in ACEX sediments. δD values of these C32 - C36 diols provide insight into the isotopic composition of the Eocene Arctic surface water. As the isotopic signature of the runoff entering the Arctic is modelled, and the final isotopic composition of the surface waters can be deduced from the isotopic composition of the diols, we can calculate the degree of mixing between freshwater (isotopically light) and seawater (isotopically heavy) in the surface waters. This way we quantify Eocene Arctic surface water salinity, which in turn will shed light on the degree of (seasonal) mixing and stratification.

Carbon isotopic composition of forest soil respiration in the decade following bark beetle and stem girdling disturbances in the Rocky Mountains: Carbon isotopes of soil respiration following disturbance

DOE PAGES

Maurer, Gregory E.; Chan, Allison M.; Trahan, Nicole A.; ...

2016-04-26

Bark beetle outbreaks are widespread in western North American forests, reducing primary productivity and transpiration, leading to forest mortality across large areas and altering ecosystem carbon cycling. Here the carbon isotope composition (δ13C) of soil respiration (δJ) was monitored in the decade after disturbance for forests affected naturally by mountain pine beetle infestation and artificially by stem girdling. The seasonal mean δJ changed along both chronosequences. We found (a) enrichment of δJ relative to controls (<1 ‰) in near-surface soils in the first 2 years after disturbance; (b) depletion (1‰ or no change) during years 3–7; and (c) a secondmore » period of enrichment (1–2‰) in years 8–10. Results were consistent with isotopic patterns associated with the gradual death and decomposition of rhizosphere organisms, fine roots, conifer needles and woody roots and debris over the course of a decade after mortality. Finally, δJ was progressively more 13C-depleted deeper in the soil than near the surface, while the bulk soil followed the well-established pattern of 13C-enrichment at depth. Overall, differences in δJ between mortality classes (<1‰) and soil depths (<3‰) were smaller than variability within a class or depth over a season (up to 6‰).« less

Return to the Strangelove Ocean?: Preliminary results of carbon and oxygenisotope compositions of post-impact sediments, IODP Expedition 364 "Chicxulub Impact Crater"

NASA Astrophysics Data System (ADS)

Yamaguchi, K. E.; Ikehara, M.; Hayama, H.; Takiguchi, S.; Masuda, S.; Ogura, C.; Fujita, S.; Kurihara, E.; Matsumoto, T.; Oshio, S.; Ishihata, K.; Fuchizawa, Y.; Noda, H.; Sakurai, U.; Yamane, T.; Morgan, J. V.; Gulick, S. P. S.

2017-12-01

The Chicxulub crater in the northern Yucatan Peninsula, Mexico was formed by the asteroid impact at the Cretaceous-Paleogene boundary (66.0 Ma). In early 2016 the IODP Exp. 364 successfully drilled the materials from the topographic peak ring within the crater that was previously identified by seismological observations. A continuous core was recovered. The 112m-thick uppermost part of the continuous core (505.7-1334.7 mbsf) is post-impact sediments, including the PETM, that are mainly composed of carbonate with intercalation of siliciclastics and variable contents of organic carbon. More than 300 samples from the post-impact section were finely powdered for a variety of geochemical analysis. Here we report their carbon and oxygen isotope compositions of the carbonate fraction (mostly in the lower part of the analyzed section) and carbon and nitrogen isotope compositions of organic matter (mostly in the middle-upper part of the analyzed section). Isotope mass spectrometer Isoprime was used for the former analysis, and EA-irMS (elemental analyzer - isotope ratio mass spectrometer) was used for the latter analysis, both at CMCR, Kochi Univ. Depth profile of oxygen isotope compositions of carbonate fraction is variable and somewhat similar to those of Zachos et al. (2001; Science). Carbon isotope compositions of carbonate and organic carbon in the lower part of the analyzed section exhibit some excursions that could correspond to the hyperthemals in the early Paleogene. Their variable nitrogen isotope compositions reflect temporal changes in the style of biogeochemical cycles involving denitrification and nitrogen fixation. Coupled temporal changes in the carbon isotope compositions of organic and carbonate carbon immediately after the K-Pg boundary might support a Strangelove ocean (Kump, 1991; Geology), however high export production (Ba/Ti, nannoplankton and calcisphere blooms, high planktic foram richness, and diverse and abundant micro- and macrobenthic organisms) at the base of the Danian limestone cored during Exp. 364 contradict a Strangelove Ocean.

Nickel isotopic composition of the mantle

NASA Astrophysics Data System (ADS)

Gall, Louise; Williams, Helen M.; Halliday, Alex N.; Kerr, Andrew C.

2017-02-01

This paper presents a detailed high-precision study of Ni isotope variations in mantle peridotites and their minerals, komatiites as well as chondritic and iron meteorites. Ultramafic rocks display a relatively large range in δ60 Ni (permil deviation in 60 Ni /58 Ni relative to the NIST SRM 986 Ni isotope standard) for this environment, from 0.15 ± 0.07‰ to 0.36 ± 0.08‰, with olivine-rich rocks such as dunite and olivine cumulates showing lighter isotope compositions than komatiite, lherzolite and pyroxenite samples. The data for the mineral separates shed light on the origin of these variations. Olivine and orthopyroxene display light δ60 Ni whereas clinopyroxene and garnet are isotopically heavy. This indicates that peridotite whole-rock δ60 Ni may be controlled by variations in modal mineralogy, with the prediction that mantle melts will display variable δ60 Ni values due to variations in residual mantle and cumulate mineralogy. Based on fertile peridotite xenoliths and Phanerozoic komatiite samples it is concluded that the upper mantle has a relatively homogeneous Ni isotope composition, with the best estimate of δ60Nimantle being 0.23 ± 0.06‰ (2 s.d.). Given that >99% of the Ni in the silicate Earth is located in the mantle, this also defines the Ni isotope composition of the Bulk Silicate Earth (BSE). This value is nearly identical to the results obtained for a suite of chondrites and iron meteorites (mean δ60 Ni 0.26 ± 0.12‰ and 0.29 ± 0.10‰, respectively) showing that the BSE is chondritic with respect to its Ni isotope composition, with little to no Ni mass-dependent isotope fractionation resulting from core formation.

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.

Compound-specific Isotope Analysis of Cyanobacterial Pure cultures and Microbial Mats: Effects of Photorespiration?

NASA Technical Reports Server (NTRS)

Jahnke, L. L.; Summons, R. E.

2006-01-01

Microbial mats are considered modern homologs of Precambrian stromatolites. The carbon isotopic compositions of organic matter and biomarker lipids provide clues to the depositional environments of ancient mat ecosystems. As the source of primary carbon fixation for over two billion years, an understanding of cyanobacterial lipid biosynthesis, associated isotopic discriminations, and the influence of physiological factors on growth and isotope expression is essential to help us compare modern microbial ecosystems to their ancient counterparts. Here, we report on the effects of photorespiration (PR) on the isotopic composition of cyanobacteria and biomarker lipids, and on potential PR effects associated with the composition of various microbial mats. The high light, high O2 and limiting CO2 conditions often present at the surface of microbial mats are known to support PR in cyanobacteria. The oxygenase function of ribulose bisphosphate carboxylase/oxygenase can result in photoexcretion of glycolate and subsequent degration by heterotrophic bacteria. We have found evidence which supports an isotopic depletion (increased apparent E) scaled to O2 level associated with growth of Phormidium luridum at low CO2 concentrations (less than 0.04%). Similar to previous studies, isotopic differences between biomass and lipid biomarkers, and between lipid classes were positively correlated with overall fractionation, and should provide a means of estimating the influence of PR on overall isotopic composition of microbial mats. Several examples of microbial mats growing in the hydrothermal waters of Yellowstone National Park and the hypersaline marine evaporation ponds at Guerrero Negro, Baja Sur Mexico will be compared with a view to PR as a possible explanation of the relatively heavy C-isotope composition of hypersaline mats.

What is the iron isotope composition of the Moon?

NASA Astrophysics Data System (ADS)

Poitrasson, F.; Zambardi, T.; Magna, T.; Neal, C. R.

2016-12-01

It is difficult to estimate the bulk chemical and isotopic composition of the Moon because of severe limitations in our sampling. As a result, there is currently a debate on the bulk Fe isotope composition of the Moon despite the constraints on the lunar accretion modes or differentiation processes it may provide. For this, a proper mass balance estimation of essential planetary reservoirs is required. For instance, the dichotomy in δ57Fe between low- and high-Ti mare basalt varieties as a consequence of differences in degree of fractional crystallization of their respective lunar mantle sources should be rigorously tested. To investigate this, we performed new iron isotope measurements of 33 bulk lunar mare basalts and highland rocks, including KREEP-related materials. The new data show significant Fe isotope differences between high-Ti and low-Ti mare basalts, yielding mean δ57FeIRMM-014=0.277±0.020‰ and δ57FeIRMM-014=0.127±0.020‰, respectively. Assuming that lunar basalts mirror the iron isotope composition of their respective mantle protoliths, the estimated relative proportion of the low-Ti and high-Ti mantle source suggests that the lunar upper mantle should be close to δ57Fe=0.14±0.03‰. At present, it is unclear whether the bulk lunar Fe isotope composition is indistinguishable from that of the Earth (δ57FeIRMM-014=0.10±0.03‰), when estimated solely from mare basalts data, or if it is twice as heavy relative to chondrites, as initially proposed. A large scatter at δ57Fe=0.08±0.19‰ for ferroan anorthosites, Mg-suite rocks and a KREEP basalt imparts more complexities for global isotopic view of the Moon. A better understanding of the cause of Fe isotope heterogeneity among the lunar highland rocks will likely allow to better estimate the bulk Moon composition, and possibly to improve our knowledge about the genesis of the lunar crust itself.

Riverine dissolved lithium isotopic signatures in low-relief central Africa and their link to weathering regimes

NASA Astrophysics Data System (ADS)

Henchiri, Soufian; Gaillardet, Jérôme; Dellinger, Mathieu; Bouchez, Julien; Spencer, Robert G. M.

2016-05-01

The isotopic composition of dissolved lithium (δ7Li) near the Congo River mouth varied from 14‰ to 22‰ in 2010 and was negatively correlated to discharge. From the relationship between dissolved δ7Li and strontium isotopes, we suggest that this large variation is due to mixing of waters from two contrasting continental weathering regimes. One end-member (high δ7Li ≈ 25‰) represents waters sourced from active lateritic soils covering the periphery of the basin (Li highly sequestered into secondary mineral products) and another representing blackwater rivers (low δ7Li ≈ 5.7‰) derived from the swampy central depression where high organic matter content in water leads to congruent dissolution of the Tertiary sedimentary bedrock. This suggests that the lithium isotopic signature of tropical low-relief surfaces is not unique and traces the long-term, large-scale vertical motions of the continental crust that control geomorphological settings. This evolution should be recorded in the oceanic secular δ7Li curve.

Isotope and trace element insights into heterogeneity of subridge mantle

NASA Astrophysics Data System (ADS)

Mallick, Soumen; Dick, Henry J. B.; Sachi-Kocher, Afi; Salters, Vincent J. M.

2014-06-01

Geochemical data for abyssal peridotites are used to determine the relationship to mid-ocean ridge basalts from several locations at ridge segments on the SW Indian Ridge (SWIR), the Mid-Cayman-Rise (MCR), and the Mid-Atlantic Ridge (MAR). Based on chemical and petrological criteria peridotites are categorized as being either dominantly impregnated with melt or being residual after recent melting. Those that are considered impregnated with melt also have isotopic compositions similar to the basalts indicating impregnation by an aggregate MORB melt. A SWIR and MCR residual peridotite Nd-isotopic compositions partly overlap the Nd-isotopic compositions of the basalts but extend to more radiogenic compositions. The differences between peridotite and basalt Nd-isotopic compositions can be explained by incorporating a low-solidus component with enriched isotopic signature in the subridge mantle: a component that is preferentially sampled by the basalts. At the MAR, peridotites and associated basalts have overlapping Nd-isotopic compositions, suggesting a more homogeneous MORB mantle. The combined chemistry and petrography indicates a complex history with several depletion and enrichment events. The MCR data indicate that a low-solidus component can be a ubiquitous component of the asthenosphere. Residual abyssal peridotites from limited geographic areas also show significant chemical variations that could be associated with initial mantle heterogeneities related to events predating the ridge-melting event. Sm-Nd model ages for possible earlier depletion events suggest these could be as old as 2.4 Ga. This article was corrected on 9 JULY 2014. See the end of the full text for details.

Impact of topography, climate and moisture sources on isotopic composition (δ18O &δD) of rivers in the Pyrenees: Implications for topographic reconstructions in small orogens

NASA Astrophysics Data System (ADS)

Huyghe, Damien; Mouthereau, Frédéric; Sébilo, Mathieu; Vacherat, Arnaud; Ségalen, Loïc; Richard, Patricia; Biron, Philippe; Bariac, Thierry

2018-02-01

Understanding how orogenic topography controls the spatial distribution and isotopic composition of precipitation is critical for paleoaltitudinal reconstructions. Here, we determine the isotopic composition (δ18O and δD) of 82 small rivers and springs from small catchments in the Pyrenees. Calculation of the deuterium excess (d-excess) parameter allows the distinction of four distinct isotopic provinces with d-excess values of between 15 and 22‰ in the northwest, between 7 and 14‰ in the central northern Pyrenees and between 3 and 11‰ in the northeast. The southern Pyrenees have a homogenous d-excess signature ranging from 7 to 14‰. Our results show significant local moisture recycling and/or rain amount effect in the northwestern Pyrenees, and control by evaporation processes during rainfall events in the southern Pyrenees and for low elevated samples of the northeast of the range. Based on the distribution of d-excess values, we estimate contrasting isotope lapse rates of -2.9/-21.4‰/km (δ18O/δD) in the northwest, -2.7/-21.4‰/km (δ18O/δD) in the north central and -3.7/-31.7‰/km (δ18O/δD) in the northeastern Pyrenees. The southern Pyrenees show distinctly higher lapse rates of -9.5/-77.5‰/km (δ18O/δD), indicating that in this area the altitudinal effect in not the only parameter driving isotopic composition of rivers. Despite their relatively low topographic gradient, the Pyrenees exert a direct control on the isotopic composition of river waters, especially on their northern side. The variations in isotopic composition-elevation relationships documented along the strike of the range are interpreted to reflect an increasing continentality effect driven by wind trajectories parallel to the range, and mixing with Mediterranean air masses. Despite these effects, the measurable orographic effect on precipitation in the Pyrenees proves that the isotopic composition approach for reconstructing past topography is applicable to low-elevation orogens.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

NASA Technical Reports Server (NTRS)

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

2011-01-01

One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. 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 hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique 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 separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Isotopic coherence of refractory inclusions from CV and CK meteorites: Evidence from multiple isotope systems

NASA Astrophysics Data System (ADS)

Shollenberger, Quinn R.; Borg, Lars E.; Render, Jan; Ebert, Samuel; Bischoff, Addi; Russell, Sara S.; Brennecka, Gregory A.

2018-05-01

Calcium-aluminum-rich inclusions (CAIs) are the oldest dated materials in the Solar System and numerous previous studies have revealed nucleosynthetic anomalies relative to terrestrial rock standards in many isotopic systems. However, most of the isotopic data from CAIs has been limited to the Allende meteorite and a handful of other CV3 chondrites. To better constrain the isotopic composition of the CAI-forming region, we report the first Sr, Mo, Ba, Nd, and Sm isotopic compositions of two CAIs hosted in the CK3 desert meteorites NWA 4964 and NWA 6254 along with two CAIs from the CV3 desert meteorites NWA 6619 and NWA 6991. After consideration of neutron capture processes and the effects of hot-desert weathering, the Sr, Mo, Ba, Nd, and Sm stable isotopic compositions of the samples show clearly resolvable nucleosynthetic anomalies that are in agreement with previous results from Allende and other CV meteorites. The extent of neutron capture, as manifested by shifts in the observed 149Sm-150Sm isotopic composition of the CAIs is used to estimate the neutron fluence experienced by some of these samples and ranges from 8.40 × 1013 to 2.11 × 1015 n/cm2. Overall, regardless of CAI type or host meteorite, CAIs from CV and CK chondrites have similar nucleosynthetic anomalies within analytical uncertainty. We suggest the region that CV and CK CAIs formed was largely uniform with respect to Sr, Mo, Ba, Nd, and Sm isotopes when CAIs condensed and that CAIs hosted in CV and CK meteorites are derived from the same isotopic reservoir.

Large Carbonate Associated Sulfate isotopic variability between brachiopods, micrite, and other sedimentary components in Late Ordovician strata

NASA Astrophysics Data System (ADS)

Present, Theodore M.; Paris, Guillaume; Burke, Andrea; Fischer, Woodward W.; Adkins, Jess F.

2015-12-01

Carbonate Associated Sulfate (CAS) is trace sulfate incorporated into carbonate minerals during their precipitation. Its sulfur isotopic composition is often assumed to track that of seawater sulfate and inform global carbon and oxygen budgets through Earth's history. However, many CAS sulfur isotope records based on bulk-rock samples are noisy. To determine the source of bulk-rock CAS variability, we extracted CAS from different internal sedimentary components micro-drilled from well-preserved Late Ordovician and early Silurian-age limestones from Anticosti Island, Quebec, Canada. Mixtures of these components, whose sulfur isotopic compositions vary by nearly 25‰, can explain the bulk-rock CAS range. Large isotopic variability of sedimentary micrite CAS (34S-depleted from seawater by up to 15‰) is consistent with pore fluid sulfide oxidation during early diagenesis. Specimens recrystallized during burial diagenesis have CAS 34S-enriched by up to 9‰ from Hirnantian seawater, consistent with microbial sulfate reduction in a confined aquifer. In contrast to the other variable components, brachiopods with well-preserved secondary-layer fibrous calcite-a phase independently known to be the best-preserved sedimentary component in these strata-have a more homogeneous isotopic composition. These specimens indicate that seawater sulfate remained close to about 25‰ (V-CDT) through Hirnantian (end-Ordovician) events, including glaciation, mass extinction, carbon isotope excursion, and pyrite-sulfur isotope excursion. The textural relationships between our samples and their CAS isotope ratios highlight the role of diagenetic biogeochemical processes in setting the isotopic composition of CAS.

Three centuries of heavy metal pollution in Paris (France) recorded by urban speleothems.

PubMed

Pons-Branchu, Edwige; Ayrault, Sophie; Roy-Barman, Matthieu; Bordier, Louise; Borst, Wolfgang; Branchu, Philippe; Douville, Eric; Dumont, Emmanuel

2015-06-15

The first record of urban speleothems used to reconstruct the history of heavy metal pollution of shallow groundwaters is presented. Two speleothems grew during the last 300 years in an underground aqueduct in the north-eastern part of Paris. They display high Pb, Mn V, Cu, Cd and Al concentrations since 1900 due to the urbanization of the site which triggered anthropogenic contamination of the water feeding the speleothems. Surprisingly, these heavy metal concentrations are also high in the oldest part. This early pollution could come from the use of Parisian waste as fertilizers in the orchards and vineyards cultivated above the aqueduct before urbanization. Lead isotopes were measured in these carbonates as well as in lead artifacts from the 17th-18th centuries ((206)Pb/(207)Pb=1.180+/-0.003). The mean (206)Pb/(207)Pb ratio, for one of the speleothems is 1.181+/-0.003 unvarying with time. These lead signatures are close to those of coal and old lead from northern European mines, lower than the natural background signature. It confirms that the high metal concentrations found come from anthropogenic pollution. Conversely, the lead isotopic composition of the second speleothem presents two temporal trends: for the oldest levels, the mean value (1.183+/-0.003) is similar to the first speleothem. For the youngest part, a lower value (1.172+/-0.005) is recorded, evidencing the contribution of a new lead source at the beginning of the industrial revolution. Pb isotopes were also measured in recent samples from a nearby superficial site. The first sample is a recent (AD 1975+/-15 years) deposit ((206)Pb/(207)Pb=1.148+/-0.003), and the second, a thin subactual layer ((206)Pb/(207)Pb=1.181+/-0.002). These data are compatible with the adding of anthropogenic sources (leaded gasoline and industrial lead from Rio Tinto ore). Copyright © 2015 Elsevier B.V. All rights reserved.

Isotope geochemistry of early Kilauea magmas from the submarine Hilina bench: The nature of the Hilina mantle component

USGS Publications Warehouse

Kimura, Jun-Ichi; Sisson, Thomas W.; Nakano, Natsuko; Coombs, Michelle L.; Lipman, Peter W.

2006-01-01

Submarine lavas recovered from the Hilina bench region, offshore Kilauea, Hawaii Island provide information on ancient Kilauea volcano and the geochemical components of the Hawaiian hotspot. Alkalic lavas, including nephelinite, basanite, hawaiite, and alkali basalt, dominate the earliest stage of Kilauea magmatism. Transitional basalt pillow lavas are an intermediate phase, preceding development of the voluminous tholeiitic subaerial shield and submarine Puna Ridge. Most alkalic through transitional lavas are quite uniform in Sr–Nd–Pb isotopes, supporting the interpretation that variable extent partial melting of a relatively homogeneous source was responsible for much of the geochemical diversity of early Kilauea magmas (Sisson et al., 2002). These samples are among the highest 206Pb/204Pb known from Hawaii and may represent melts from a distinct geochemical and isotopic end-member involved in the generation of most Hawaiian tholeiites. This end-member is similar to the postulated literature Kea component, but we propose that it should be renamed Hilina, to avoid confusion with the geographically defined Kea-trend volcanoes. Isotopic compositions of some shield-stage Kilauea tholeiites overlap the Hilina end-member but most deviate far into the interior of the isotopic field defined by magmas from other Hawaiian volcanoes, reflecting the introduction of melt contributions from both “Koolau” (high 87Sr/86Sr, low 206Pb/204Pb) and depleted (low 87Sr/86Sr, intermediate 206Pb/204Pb) source materials. This shift in isotopic character from nearly uniform, end-member, and alkalic, to diverse and tholeiitic corresponds with the major increase in Kilauea's magmatic productivity. Two popular geodynamic models can account for these relations: (1) The upwelling mantle source could be concentrically zoned in both chemical/isotopic composition, and in speed/extent of upwelling, with Hilina (and Loihi) components situated in the weakly ascending margins and the Koolau component in the interior. The depleted component could be refractory and spread throughout or scavenged from the overlying lithosphere. (2) The Hilina (and Loihi) components could be a more fertile material (lower melting temperature) spread irregularly throughout the Hawaiian source in a matrix of more refractory depleted and Koolau compositions. Modest upwelling along the leading hotspot margin melts the fertile domains predominantly, while the refractory matrix also partially melts in the more vigorously upwelling hotspot interior, diluting the Hilina and Loihi components and yielding voluminous isotopically diverse tholeiitic magmas.

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.

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.

Noble gases in the moon

NASA Technical Reports Server (NTRS)

Manuel, O. K.; Srinivasan, B.; Hennecke, E. W.; Sinclair, D. E.

1972-01-01

The abundance and isotopic composition of helium, neon, argon, krypton, and xenon which were released by stepwise heating of lunar fines (15601.64) and (15271.65) were measured spectrometrically. The results of a composition of noble gases released from the lunar fines with noble gases in meteorites and in the earth are presented along with the isotopic composition of noble gases in lunar fines, in meteorites, and in the atmosphere. A study of two isotopically distinct components of trapped xenon in carbonaceous chondrites is also included.

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

NASA Technical Reports Server (NTRS)

Earl, Lyndsey D.

2005-01-01

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

Hydrogenetic Ferromanganese Crusts of the California Continental Margin

NASA Astrophysics Data System (ADS)

Conrad, Tracey A.

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

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.

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

PubMed

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

2013-12-17

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

Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

NASA Astrophysics Data System (ADS)

Meshoulam, Alexander; Ellis, Geoffrey S.; Said Ahmad, Ward; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

2016-09-01

The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n-hexadecane (n-C16) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H2S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H2S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4‰ for H2S and as much as 22.2‰ for BT. The fractionations decrease as the H2S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H2S and sulfate (∼17‰). Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4 dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and provide important mechanistic details about the overall TSR process.

Isotope effects in photo dissociation of ozone with visible light

NASA Astrophysics Data System (ADS)

Früchtl, Marion; Janssen, Christof; Röckmann, Thomas

2014-05-01

Ozone (O3) plays a key role for many chemical oxidation processes in the Earth's atmosphere. In these chemical reactions, ozone can transfer oxygen to other trace gases. This is particularly interesting, since O3 has a very peculiar isotope composition. Following the mass dependent fractionation equation δ17O = 0.52 * δ18O, most fractionation processes depend directly on mass. However, O3 shows an offset to the mass dependent fractionation line. Processes, which show such anomalies, are termed mass independent fractionations (MIF). A very well studied example for a chemical reaction that leads to mass independent fractionation is the O3 formation reaction. To what degree O3 destruction reactions need to be considered in order to understand the isotope composition of atmospheric O3 is still not fully understood and an open question within scientific community. We set up new experiments to investigate the isotope effect resulting from photo dissociation of O3 in the Chappuis band (R1). Initial O3 is produced by an electric discharge. After photolysis O3 is collected in a cold trap at the triple point temperature of nitrogen (63K). O3 is then converted to O2 in order to measure the oxygen isotopes of O3 using isotope ratio mass spectrometry. To isolate O3 photo dissociation (R1) from O3 decomposition (R2) and secondary O3 formation (R3), we use varying amounts of carbon monoxide (CO) as O atom quencher (R4). In this way we suppress the O + O3 reaction (R3) and determine the isotope fractionation in R1 and R2 separately. We present first results on the isotope effects in O3 photo dissociation with visible light in the presence of different bath gases. Results are interpreted based on chemical kinetics modeling. (R1) O3 + hυ → O (3P) + O2 (R2) O3 + O (3P) → 2 O2 (R3) O + O2 + M → O3 + M (R4) O (3P) + CO + M → CO2 + M

Revealing magma degassing below closed-conduit active volcanoes: Geochemical features of volcanic rocks versus fumarolic fluids at Vulcano (Aeolian Islands, Italy)

NASA Astrophysics Data System (ADS)

Mandarano, Michela; Paonita, Antonio; Martelli, Mauro; Viccaro, Marco; Nicotra, Eugenio; Millar, Ian L.

2016-04-01

The elemental and isotopic compositions of noble gases (He, Ne, and Ar) in olivine- and clinopyroxene-hosted fluid inclusions have been measured for rocks at various degrees of evolution and belonging to high-K calcalkaline-shoshonitic and shoshonitic-potassic series in order to cover the entire volcanological history of Vulcano Island (Italy). The major- and trace-element concentrations and the Sr- and Pb-isotope compositions for whole rocks were integrated with data obtained from the fluid inclusions. 3He/4He in fluid inclusions is within the range of 3.30 and 5.94 R/Ra, being lower than the theoretical value for the deep magmatic source expected for Vulcano Island (6.0-6.2 R/Ra). 3He/4He of the magmatic source is almost constant throughout the volcanic history of Vulcano. Integration of the He- and Sr-isotope systematics leads to the conclusion that a decrease in the He-isotope ratio of the rocks is mainly due to the assimilation of 10-25% of a crustal component similar to the Calabrian basement. 3He/4He shows a negative correlation with Sr isotopes except for the last-erupted Vulcanello latites (Punta del Roveto), which have anomalously high He isotope ratios. This anomaly has been attributed to a flushing process by fluids coming from the deepest reservoirs, since an input of deep magmatic volatiles with high 3He/4He values increases the He-isotope ratio without changing 87Sr/86Sr. A comparison of the He-isotope ratios between fluid inclusions and fumarolic gases shows that only the basalts of La Sommata and the latites of Vulcanello have comparable values. Taking into account that the latites of Vulcanello relate to one of the most-recent eruptions at Vulcano (in the 17th century), we infer that the most probable magma which actually feeds the fumarolic emissions is a latitic body that ponded at about 3-3.5 km of depth and is flushed by fluids coming from a deeper and basic magma.

Revealing the magmas degassing below closed-conduit active volcanoes: noble gases in volcanic rocks versus fumarolic fluids at Vulcano (Aeolian Islands, Italy)

NASA Astrophysics Data System (ADS)

Mandarano, Michela; Paonita, Antonio; Martelli, Mauro; Viccaro, Marco; Nicotra, Eugenio; Millar, Ian L.

2016-04-01

With the aim to constrain the nature of magma currently feeding the fumarolic field of Vulcano, we measured the elemental and isotopic compositions of noble gases (He, Ne, and Ar) in olivine- and clinopyroxene-hosted fluid inclusions in high-K calcalcaline-shoshonitic and shoshonitic-potassic series so as to cover the entire volcanological history of Vulcano Island (Italy). The major and trace-element concentrations and the Sr- and Pb-isotope compositions for whole rocks were integrated with data obtained from the fluid inclusions. 3He/4He in fluid inclusions is within the range of 3.30 and 5.94 R/Ra, being lower than the value for the deep magmatic source expected for Vulcano Island (6.0-6.2 R/Ra). 3He/4He of the magmatic source is almost constant throughout the volcanic record of Vulcano. Integration of the He- and Sr-isotope systematics leads to the conclusion that a decrease in the He-isotope ratio of the rocks is mainly due to the assimilation of 10-25% of a crustal component similar to the Calabrian basement. 3He/4He shows a negative correlation with Sr isotopes except for the last-emitted Vulcanello latites (Punta del Roveto), which have high He- and Sr-isotope ratios. This anomaly has been attributed to a flushing process by fluids coming from the deepest reservoirs. Indeed, an input of deep magmatic volatiles with high 3He/4He values increases the He-isotope ratio without changing 87Sr/86Sr. A comparison of the He isotope ratios between fluid inclusions and fumarolic gases showed that only the basalts of La Sommata and the latites of Vulcanello have comparable values. Taking into account that the latites of Vulcanello relate to one of the most-recent eruptions at Vulcano (in the 17th century), we infer that that the most probable magma which actually feeds the fumarolic emissions is a latitic body ponding at about 3-3.5 km of depth and flushed by fluids coming from a deeper and basic magma.

On the equilibrium isotopic composition of the thorium-uranium-plutonium fuel cycle

NASA Astrophysics Data System (ADS)

Marshalkin, V. Ye.; Povyshev, V. M.

2016-12-01

The equilibrium isotopic compositions and the times to equilibrium in the process of thorium-uranium-plutonium oxide fuel recycling in VVER-type reactors using heavy water mixed with light water are estimated. It is demonstrated thEhfat such reactors have a capacity to operate with self-reproduction of active isotopes in the equilibrium mode.

On the equilibrium isotopic composition of the thorium–uranium–plutonium fuel cycle

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

Marshalkin, V. Ye., E-mail: marshalkin@vniief.ru; Povyshev, V. M.

2016-12-15

The equilibrium isotopic compositions and the times to equilibrium in the process of thorium–uranium–plutonium oxide fuel recycling in VVER-type reactors using heavy water mixed with light water are estimated. It is demonstrated thEhfat such reactors have a capacity to operate with self-reproduction of active isotopes in the equilibrium mode.

Molybdenum isotope fractionation in the mantle

NASA Astrophysics Data System (ADS)

Liang, Yu-Hsuan; Halliday, Alex N.; Siebert, Chris; Fitton, J. Godfrey; Burton, Kevin W.; Wang, Kuo-Lung; Harvey, Jason

2017-02-01

We report double-spike molybdenum (Mo) isotope data for forty-two mafic and fifteen ultramafic rocks from diverse locations and compare these with results for five chondrites. The δ98/95Mo values (normalized to NIST SRM 3134) range from -0.59 ± 0.04 to +0.10 ± 0.08‰. The compositions of one carbonaceous (CI) and four ordinary chondrites are relatively uniform (-0.14 ± 0.01‰, 95% ci (confidence interval)) in excellent agreement with previous data. These values are just resolvable from the mean of 10 mid-ocean ridge basalts (MORBs) (0.00 ± 0.02‰, 95% ci). The compositions of 13 mantle-derived ultramafic xenoliths from Kilbourne Hole, Tariat and Vitim are more diverse (-0.39 to -0.07‰) with a mean of -0.22 ± 0.06‰ (95% ci). On this basis, the isotopic composition of the bulk silicate Earth (BSE or Primitive Mantle) is within error identical to chondrites. The mean Mo concentration of the ultramafic xenoliths (0.19 ± 0.07 ppm, 95% ci) is similar in magnitude to that of MORB (0.48 ± 0.13 ppm, 95% ci), providing evidence, either for a more compatible behaviour than previously thought or for selective Mo enrichment of the subcontinental lithospheric mantle. Intraplate and ocean island basalts (OIBs) display significant isotopic variability within a single locality from MORB-like to strongly negative (-0.59 ± 0.04‰). The most extreme values measured are for nephelinites from the Cameroon Line and Trinidade, which also have anomalously high Ce/Pb and low Mo/Ce relative to normal oceanic basalts. δ98/95Mo correlates negatively with Ce/Pb and U/Pb, and positively with Mo/Ce, explicable if a phase such as an oxide or a sulphide liquid selectively retains isotopically heavy Mo in the mantle and fractionates its isotopic composition in low degree partial melts. If residual phases retain Mo during partial melting, it is possible that the [Mo] for the BSE may be misrepresented by values estimated from basalts. This would be consistent with the high Mo concentrations of all the ultramafic xenoliths of 40-400 ppb, similar to or, significantly higher than, current estimates for the BSE (39 ppb). On this basis a revised best estimate of the Mo content in the BSE based on these concentrations would be in the range 113-180 ppb, significantly higher than previously assumed. These values are similar to the levels of depletion in the other refractory moderately siderophile elements W, Ni and Co. A simpler explanation may be that the subcontinental lithospheric mantle has been selectively enriched in Mo leading to the higher concentrations observed. Cryptic melt metasomatism would be difficult to reconcile with the high Mo/Ce of the most LREE depleted xenoliths. Ancient Mo-enriched subducted components would be expected to have heavy δ98/95Mo, which is not observed. The Mo isotope composition of the BSE, cannot be reliably resolved from that of chondrites at this time despite experimental evidence for metal-silicate fractionation. An identical isotopic composition might result from core-mantle differentiation under very high temperatures such as were associated with the Moon-forming Giant Impact, or from the BSE inventory reflecting addition of moderately siderophile elements from an oxidised Moon-forming impactor (O'Neill, 1991). However, the latter would be inconsistent with the non-chondritic radiogenic W isotopic composition of the BSE. Based on mantle fertility arguments, Mo in the BSE could even be lighter (lower 98/95Mo) than that in chondrites, which might be explained by loss of S rich liquids from the BSE during core formation (Wade et al., 2012). Such a late removal model is no longer required to explain the Mo concentration of the BSE if its abundance is in fact much higher, and similar to the values for ultramafic xenoliths.

Methane transport mechanisms and isotopic fractionation in emergent macrophytes of an Alaskan tundra lake

NASA Technical Reports Server (NTRS)

Chanton, Jeffrey P.; Martens, Christopher S.; Kelley, Cheryl A.; Crill, Patrick M.; Showers, William J.

1992-01-01

The stable carbon isotopic composition of methane associated with and emitted by the two dominant emergent macrophytes abundant in the many Alaskan tundra lakes, Carex rostrata and Arctophila fulva, is determined. The carbon isotopic composition of the methane was -58.6 +/- 0.5 (n=2) for Arctophila and -66.6 +/- 2.5 (n=6) for Carex. The methane emitted by these species is depleted in C-13 by 12 per mil for Arctophila and 18 per mil for Carex relative to methane withdrawn from plant stems 1-2 cm below the waterline. The results suggest more rapid transport of (C-12)H4 relative to (C-13)H4 through plants to the atmosphere. Plant stem methane concentrations ranged from 0.2 to 4.0 percent in Arctophila, with an isotopic composition of -46.1 +/- 4.3 percent (n=8). Carex stem methane concentrations ranged from 150 to 1200 ppm, with an isotopic composition of -48.3 +/- 1.4 per mil (n=3).

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

2016-01-01

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. However, the current models for the Moon’s formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes, using NanoSIMS (Nanoscale Secondary Ion Mass Spectrometry) of lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

Hydrogen isotope fractionation during lipid biosynthesis by Haloarcula marismortui

NASA Astrophysics Data System (ADS)

Dirghangi, Sitindra S.; Pagani, Mark

2013-10-01

We studied the controls on the fractionation of hydrogen isotopes during lipid biosynthesis by Haloarcula marismortui, a halophilic archaea, in pure culture experiments by varying organic substrate, the hydrogen isotope composition (D/H) of water, temperature, and salinity. Cultures were grown on three substrates: succinate, pyruvate and glycerol with known hydrogen isotope compositions, and in water with different hydrogen isotopic compositions. All culture series grown on a particular substrate show strong correlations between δDarchaeol and δDwater. However, correlations are distinctly different for cultures grown on different substrates. Our results indicate that the metabolic pathway of substrate exerts a fundamental influence on the δD value of lipids, likely by influencing the D/H composition of NADPH (nicotinamide adenine dinucleotide phosphate), the reducing agent that contributes hydrogen to carbon atoms during lipid biosynthesis. Temperature and salinity have smaller, but similar effects on δDlipid, primarily due to the way temperature and salinity influence growth rate, as well as temperature effects on the activity of enzymes.

Fe isotope composition of bulk chondrules from Murchison (CM2): Constraints for parent body alteration, nebula processes and chondrule-matrix complementarity

NASA Astrophysics Data System (ADS)

Hezel, Dominik C.; Wilden, Johanna S.; Becker, Daniel; Steinbach, Sonja; Wombacher, Frank; Harak, Markus

2018-05-01

Chondrules are a major constituent of primitive meteorites. The formation of chondrules is one of the most elusive problems in cosmochemistry. We use Fe isotope compositions of chondrules and bulk chondrites to constrain the conditions of chondrule formation. Iron isotope compositions of bulk chondrules are so far only known from few studies on CV and some ordinary chondrites. We studied 37 chondrules from the CM chondrite Murchison. This is particularly challenging, as CM chondrites contain the smallest chondrules of all chondrite groups, except for CH chondrites. Bulk chondrules have δ56Fe between -0.62 and +0.24‰ relative to the IRMM-014 standard. Bulk Murchison has as all chondrites a δ56Fe of 0.00‰ within error. The δ56Fe distribution of the Murchison chondrule population is continuous and close to normal. The width of the δ56Fe distribution is narrower than that of the Allende chondrule population. Opaque modal abundances in Murchison chondrules is in about 67% of the chondrules close to 0 vol.%, and in 33% typically up to 6.5 vol.%. Chondrule Al/Mg and Fe/Mg ratios are sub-chondritic, while bulk Murchison has chondritic ratios. We suggest that the variable bulk chondrule Fe isotope compositions were established during evaporation and recondensation prior to accretion in the Murchison parent body. This range in isotope composition was likely reduced during aqueous alteration on the parent body. Murchison has a chondritic Fe isotope composition and a number of chondritic element ratios. Chondrules, however, have variable Fe isotope compositions and chondrules and matrix have complementary Al/Mg and Fe/Mg ratios. In combination, this supports the idea that chondrules and matrix formed from a single reservoir and were then accreted in the parent body. The formation in a single region also explains the compositional distribution of the chondrule population in Murchison.

Historical reconstruction of atmospheric lead pollution in central Yunnan province, southwest China: an analysis based on lacustrine sedimentary records.

PubMed

Liu, Enfeng; Zhang, Enlou; Li, Kai; Nath, Bibhash; Li, Yanling; Shen, Ji

2013-12-01

Atmospheric lead (Pb) pollution during the last century in central Yunnan province, one of the largest non-ferrous metal production centers in China, was reconstructed using sediment cores collected from Fuxian and Qingshui Lakes. Lead concentrations and isotopic ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb) were measured in sediment cores from both lakes. The operationally defined chemical fractions of Pb in sediment core from Fuxian Lake were determined by the optimized BCR procedure. The chronology of the cores was reconstructed using (210)Pb and (137)Cs dating methods. Similar three-phase variations in isotopic ratios and enrichment factors of Pb were observed in the sediment cores from both lakes. Before the 1950s, the sediment data showed low (207)Pb/(206)Pb and (208)Pb/(206)Pb ratios and enrichment factors (EFs=~1), indicating that the sedimentary Pb was predominantly of lithogenic origin. However, these indices were increased gradually between the 1950s and the mid-1980s, implying an atmospheric Pb deposition. The EFs and isotopic ratios of Pb reached their peak during recent years, indicating aggravating atmospheric Pb pollution. The average anthropogenic Pb fluxes since the mid-1980s were estimated to be 0.032 and 0.053 g m(-2) year(-1) recorded in Fuxian and Qingshui cores, respectively. The anthropogenic Pb was primarily concentrated in the reducible fraction. Combining the results of Pb isotopic compositions and chemical speciations in the sediment cores and in potential sources, we deduced that recent aggravating atmospheric Pb pollution in central Yunnan province should primarily be attributed to regional emissions from non-ferrous metal production industries.

Isotope Geochemistry for Comparative Planetology of Exoplanets

NASA Technical Reports Server (NTRS)

Mandt, K. E.; Atreya, S.; Luspay-Kuti, A.; Mousis, O.; Simon, A.; Hofstadter, M. D.

2017-01-01

Isotope geochemistry has played a critical role in understanding processes at work in and the history of solar system bodies. Application of these techniques to exoplanets would be revolutionary and would allow comparative planetology with the formation and evolution of exoplanet systems. The roadmap for comparative planetology of the origins and workings of exoplanets involves isotopic geochemistry efforts in three areas: (1) technology development to expand observations of the isotopic composition of solar system bodies and expand observations to isotopic composition of exoplanet atmospheres; (2) theoretical modeling of how isotopes fractionate and the role they play in evolution of exoplanetary systems, atmospheres, surfaces and interiors; and (3) laboratory studies to constrain isotopic fractionation due to processes at work throughout the solar system.

Stable-isotope fingerprints of biological agents as forensic tools.

PubMed

Horita, Juske; Vass, Arpad A

2003-01-01

Naturally occurring stable isotopes of light elements in chemical and biological agents may possess unique "stable-isotope fingerprints" depending on their sources and manufacturing processes. To test this hypothesis, two strains of bacteria (Bacillus globigii and Erwinia agglomerans) were grown under controlled laboratory conditions. We observed that cultured bacteria cells faithfully inherited the isotopic composition (hydrogen, carbon, and nitrogen) of media waters and substrates in predictable manners in terms of bacterial metabolism and that even bacterial cells of the same strain, which grew in media water and substrates of different isotopic compositions, have readily distinguishable isotopic signatures. These "stable-isotopic fingerprints" of chemical and biological agents can be used as forensic tools in the event of biochemical terrorist attacks.

Detection of diagenetic processes in bones: the case of Arkoudospilia cave, N. Greece

NASA Astrophysics Data System (ADS)

Zisi, Nikoleta; Dotsika, Elissavet; Tsoukala, Evangelia; Psomiadis, David

2010-05-01

Diagenesis of bone material over geological time is a highly complex phenomenon involving the physical, chemical, histological and mechanical alterations that occur at different time scales from the time of death to present and depend on the local geochemical conditions. The significance of diagenesis and the information that can provide its decoding, led to its study by a variety of physicochemical techniques. Despite serious research efforts, a detailed scenario of bone diagenesis remains elusive. The δ18O of the carbonate material of hydroxyapatite of the bones is though to be a good indicator of the δ18O of the local water precipitation and therefore can be used for palaeoclimatic reconstraction, while δ13C is used for definition of palaeodiet habits. The study of isotopic composition requires the detection of the diagenetic degree, because both δ18O and δ13C can be contaminated by these processes. Stable carbon and oxygen isotope values (δ13C, δ18O) were obtained for structural carbonate in the hydroxy-apatite of bear bones from Arkoudospilia Cave, Pella, N. Greece. The age range of the fossil layers is from 32ka BP to a maximum of 38ka BP (radiocarbon dating). The findings belong to Ursus ingressus, an extinct cave bear. The difficulty in studying an extinct species lies to the fact that it cannot be easily correlated with a present one, so it is impossible to determine the diagenesis by the analytical deviation. However, in order to include the environmental and climatic differences of the past and modern bear habitats, the isotopic composition of the water should be also included in the study. Cave bears are considered to be endemic in Europe. The shortage of data in literature concerning cave bears isotopic analyses in combination with the burden of the difficulties in spotting and sampling such rare materials makes difficult to compare the results of a study. The diet and the physiology of this species are not well known. However the morphology of teeth, skull and mandible indicate a basically herbivorous regime and the metabolism of this species is usually considered similar to this of the American black bear (Ursus americanus) or of the brown bear (Ursus arctos). Structural carbonate is considered to be less resistant than phosphate to post - depositional alteration because P-O chemical bonds in apatite are stronger than the C-O bonds, however phosphate is susceptible to microbial activity. For the needs of the present study isotopic composition of fossil bones where correlated with the isotopic composition of modern bears that live in the area of the findings. Moreover both fossil and modern bones were examined with X-ray diffraction for minelalogical alterations. The comparison of the isotopic composition and mineralogical characteristics of fossil and modern bones indicated possible diagenetic effects that may lead to exclude specific samples from palaeoclimatic archives.

Magnesium isotope compositions of Solar System materials determined by double spiking

NASA Astrophysics Data System (ADS)

Hin, R.; Lai, Y. J.; Coath, C.; Elliott, T.

2015-12-01

As a major element, magnesium is of interest for investigating large scale processes governing the formation and evolution of rocky planetary bodies. Determining the Mg isotope composition of the Earth and other planetary bodies has hence been a topic of interest ever since mass-dependent fractionation of 'non-traditional' stable isotopes has been used to study high-temperature processes. Published results, however, suffer from disagreement on the Mg isotope compositions of the Earth and chondrites [1-5], which is attributed to residual matrix effects. Nonetheless, most recent studied have converged towards a homogeneous (chondritic) Mg isotope composition in the Solar System [2-5]. However, in several of the recent studies there is a hint of a systematic difference of about 0.02-0.06‰ in the 26Mg/24Mg isotope compositions of chondrites and Earth. Such difference, however, is only resolvable by taking standard errors, which assumes robust data for homogenous sample sets. The discrepancies between various studies unfortunately undermine the confidence in such robustness and homogeneity. The issues with matrix effects during isotopic analyses can be overcome by using a double spike approach. Such methodology generally requires three isotope ratios to solve for three unknowns, a requirement that cannot be met for Mg. However, using a newly developed approach, we present Mg isotope compositions obtained by critical mixture double spiking. This new approach should allow greater confidence in the robustness of the data and hence enable improvement of. Preliminary data indicate that chondrites have a resolvable ~0.04‰ lighter 26Mg/24Mg than (ultra)mafic rocks from Earth, Mars and the eucrite parent body, which appear indistinguishable from each other. It seems implausible that this difference is caused by magmatic process such as partial melting or crystallisation. More likely, Mg isotopes are fractionated by a non-magmatic process during the formation of planets, e.g. by vapour-condensate fractionation. [1] Wiechert and Halliday, 2007. EPSL 256, 360-371. [2] Bourdon et al., 2010. GCA 74, 5069-5083. [3] Teng et al., 2010. GCA 74, 4150-4166. [4] Chakrabarti and Jacobsen, 2010. EPSl 293, 349-358. [5] Von Strandmann, 2011. GCA 75, 5247-5268.

Evaluating climate model performance in the tropics with retrievals of water isotopic composition from Aura TES

NASA Astrophysics Data System (ADS)

Field, Robert; Kim, Daehyun; Kelley, Max; LeGrande, Allegra; Worden, John; Schmidt, Gavin

2014-05-01

Observational and theoretical arguments suggest that satellite retrievals of the stable isotope composition of water vapor could be useful for climate model evaluation. The isotopic composition of water vapor is controlled by the same processes that control water vapor amount, but the observed distribution of isotopic composition is distinct from amount itself . This is due to the fractionation that occurs between the abundant H216O isotopes (isotopologues) and the rare and heavy H218O and HDO isotopes during evaporation and condensation. The fractionation physics are much simpler than the underlying moist physics; discrepancies between observed and modeled isotopic fields are more likely due to problems in the latter. Isotopic measurements therefore have the potential for identifying problems that might not be apparent from more conventional measurements. Isotopic tracers have existed in climate models since the 1980s but it is only since the mid 2000s that there have been enough data for meaningful model evaluation in this sense, in the troposphere at least. We have evaluated the NASA GISS ModelE2 general circulation model over the tropics against water isotope (HDO/H2O) retrievals from the Aura Tropospheric Emission Spectrometer (TES), alongside more conventional measurements. A small ensemble of experiments was performed with physics perturbations to the cumulus and planetary boundary layer schemes, done in the context of the normal model development process. We examined the degree to which model-data agreement could be used to constrain a select group of internal processes in the model, namely condensate evaporation, entrainment strength, and moist convective air mass flux. All are difficult to parameterize, but exert strong influence over model performance. We found that the water isotope composition was significantly more sensitive to physics changes than precipitation, temperature or relative humidity through the depth of the tropical troposphere. Among the processes considered, this was most closely, and fairly exclusively, related to mid-tropospheric entrainment strength. This demonstrates that water isotope retrievals have considerable potential alongside more conventional measurements for climate model evaluation and development.

Tracing metal-silicate segregation and late veneer in the Earth and the ureilite parent body with palladium stable isotopes

NASA Astrophysics Data System (ADS)

Creech, J. B.; Moynier, F.; Bizzarro, M.

2017-11-01

Stable isotope studies of highly siderophile elements (HSE) have the potential to yield valuable insights into a range of geological processes. In particular, the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal-silicate segregation, making them sensitive tracers of planetary differentiation processes. We present the first techniques for the precise determination of palladium stable isotopes by MC-ICPMS using a 106Pd-110Pd double-spike to correct for instrumental mass fractionation. Results are expressed as the per mil (‰) difference in the 106Pd/105Pd ratio (δ106Pd) relative to an in-house solution standard (Pd_IPGP) in the absence of a certified Pd isotopic standard. Repeated analyses of the Pd isotopic composition of the chondrite Allende demonstrate the external reproducibility of the technique of ±0.032‰ on δ106Pd. Using these techniques, we have analysed Pd stable isotopes from a range of terrestrial and extraterrestrial samples. We find that chondrites define a mean δ106Pdchondrite = -0.19 ± 0.05‰. Ureilites reveal a weak trend towards heavier δ106Pd with decreasing Pd content, similar to recent findings based on Pt stable isotopes (Creech et al., 2017), although fractionation of Pd isotopes is significantly less than for Pt, possibly related to its weaker metal-silicate partitioning behaviour and the limited field shift effect. Terrestrial mantle samples have a mean δ106Pdmantle = -0.182 ± 0.130‰, which is consistent with a late-veneer of chondritic material after core formation.

Triple oxygen isotope composition of photosynthetic oxygen

NASA Astrophysics Data System (ADS)

van der Meer, Anne; Kaiser, Jan

2013-04-01

The measurement of biological production rates is essential for our understanding how marine ecosystems are sustained and how much CO2 is taken up through aquatic photosynthesis. Traditional techniques to measure marine production are laborious and subject to systematic errors. A biogeochemical approach based on triple oxygen isotope measurements in dissolved oxygen (O2) has been developed over the last few years, which allows the derivation of gross productivity integrated over the depth of the mixed layer and the time-scale of O2 gas exchange (Luz and Barkan, 2000). This approach exploits the relative 17O/16O and 18O/16O isotope ratio differences of dissolved O2 compared to atmospheric O2 to work out the rate of biological production. Two parameters are key for this calculation: the isotopic composition of dissolved O2 in equilibrium with air and the isotopic composition of photosynthetic oxygen. Recently, a controversy has emerged in the literature over these parameters (Kaiser, 2011) and one of the goals of this research is to provide additional data to resolve this controversy. In order to obtain more information on the isotopic signature of biological oxygen, laboratory experiments have been conducted to determine the isotopic composition of oxygen produced by different phytoplankton cultures.

Magnesium Isotopes as a Tracer of Crustal Materials in Volcanic Arc Magmas in the Northern Cascade Arc

NASA Astrophysics Data System (ADS)

Brewer, Aaron W.; Teng, Fang-Zhen; Mullen, Emily

2018-03-01

Fifteen North Cascade Arc basalts and andesites were analyzed for Mg isotopes to investigate the extent and manner of crustal contributions to this magmatic system. The δ26Mg of these samples vary from within the range of ocean island basalts (the lightest being -0.33 ± 0.07‰) to heavier compositions (as heavy as -0.15 ± 0.06‰). The observed range in chemical and isotopic composition is similar to that of other volcanic arcs that have been assessed to date in the circum-pacific subduction zones and in the Caribbean. The heavy Mg isotope compositions are best explained by assimilation and fractional crystallization within the deep continental crust with a possible minor contribution from the addition of subducting slab-derived fluids to the primitive magma. The bulk mixing of sediment into the primitive magma or mantle source and the partial melting of garnet-rich peridotite are unlikely to have produced the observed range of Mg isotope compositions. The results show that Mg isotopes may be a useful tracer of crustal input into a magma, supplementing traditional methods such as radiogenic isotopic and trace element data, particularly in cases in which a high fraction of crustal material has been added.

Silurian shale origin for light oil, condensate, and gas in Algeria and the Middle East

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

Zumberge, J.E.; Macko, S.

1996-01-01

Two of the largest gas fields in the world, Hasi R'Mel, Algeria and North Dome, Qatar, also contain substantial condensate and light oil reserves. Gas to source rock geochemical correlation is difficult due to the paucity of molecular parameters in the former although stable isotope composition is invaluable. However, by correlating source rocks with light oils and condensates associated with gas production using traditional geochemical parameters such as biomarkers and isotopes, a better understanding of the origin of the gas is achieved. Much of the crude oil in the Ghadames/Illizi Basins of Algeria has long been thought to have beenmore » generated from Silurian shales. New light oil discoveries in Saudi Arabia have also been shown to originate in basal euxinic Silurian shales. Key sterane and terpane biomarkers as well as the stable carbon isotopic compositions of the C15+ saturate and aromatic hydrocarbon fractions allow for the typing of Silurian-sourced, thermally mature light oils in Algeria and the Middle East. Even though biomarkers are often absent due to advanced thermal maturity, condensates can be correlated to the light oils using (1) carbon isotopes of the residual heavy hydrocarbon fractions, (2) light hydrocarbon distributions (e.g., C7 composition), and (3) compound specific carbon isotopic composition of the light hydrocarbons. The carbon isotopes of the C2-C4 gas components ran then be compared to the associated condensate and light oil isotopic composition.« less

Silurian shale origin for light oil, condensate, and gas in Algeria and the Middle East

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

Zumberge, J.E.; Macko, S.

Two of the largest gas fields in the world, Hasi R`Mel, Algeria and North Dome, Qatar, also contain substantial condensate and light oil reserves. Gas to source rock geochemical correlation is difficult due to the paucity of molecular parameters in the former although stable isotope composition is invaluable. However, by correlating source rocks with light oils and condensates associated with gas production using traditional geochemical parameters such as biomarkers and isotopes, a better understanding of the origin of the gas is achieved. Much of the crude oil in the Ghadames/Illizi Basins of Algeria has long been thought to have beenmore » generated from Silurian shales. New light oil discoveries in Saudi Arabia have also been shown to originate in basal euxinic Silurian shales. Key sterane and terpane biomarkers as well as the stable carbon isotopic compositions of the C15+ saturate and aromatic hydrocarbon fractions allow for the typing of Silurian-sourced, thermally mature light oils in Algeria and the Middle East. Even though biomarkers are often absent due to advanced thermal maturity, condensates can be correlated to the light oils using (1) carbon isotopes of the residual heavy hydrocarbon fractions, (2) light hydrocarbon distributions (e.g., C7 composition), and (3) compound specific carbon isotopic composition of the light hydrocarbons. The carbon isotopes of the C2-C4 gas components ran then be compared to the associated condensate and light oil isotopic composition.« less

The use of lead isotope analysis to identify potential sources of lead toxicosis in a juvenile bald eagle (Haliaeetus leucocephalus) with ventricular foreign bodies

USGS Publications Warehouse

Franzen-Klein, Dana; McRuer, David; Slabe, Vincent; Katzner, Todd

2018-01-01

A male juvenile bald eagle (Haliaeetus leucocephalus) was admitted to the Wildlife Center of Virginia with a left humeral fracture a large quantity of anthropogenic debris in the ventriculus, a blood lead level of 0.616 ppm, and clinical signs consistent with chronic lead toxicosis. Because of the poor prognosis for recovery and release, the eagle was euthanatized. Lead isotope analysis was performed to identify potential anthropogenic sources of lead in this bird. The lead isotope ratios in the eagle's femur (0.8773), liver (0.8761), and kidneys (0.8686) were most closely related to lead paint (0.8925), leaded gasoline (0.8450), and zinc smelting (0.8240). The lead isotope ratios were dissimilar to lead ammunition (0.8179) and the anthropogenic debris in the ventriculus. This case report documents foreign body ingestion in a free-ranging bald eagle and demonstrates the clinical utility of lead isotope analysis to potentially identify or exclude anthropogenic sources of lead poisoning in wildlife patients.

Interactions between surface waters in King George Island, Antarctica - a stable isotope perspective

NASA Astrophysics Data System (ADS)

Perşoiu, Aurel; Bădăluşă, Carmen

2017-04-01

In this paper we present a first study of the isotopic composition of surface waters in the southern peninsulas (Barton, Fildes, Weaver and Potter) of King George Island, Antarctica. We have collected > 200 samples of snow and snowmelt, water (lake, river and spring), ice (glacier ice and permafrost) from the four peninsulas in February 2016 and analyzed them for their oxygen and hydrogen stable isotopic composition. Samples from lake water (50+) indicate a clear west-east depletion trend, suggesting a rain-out process as air masses are moving westward (and are progressively depleted in heavy isotopes) from their origin in the Drake Passage. In both Fildes and Barton Peninsulas, permafrost samples have the heaviest isotopic composition, most probably due to preferential incorporation of heavy isotopes in the ice during freezing (and no fractionation during melting). As permafrost melts, the resulting water mixes with isotopically lighter infiltrated snowmelt, and thus the groundwater has a lower isotopic composition. Further, lake and river (the later fed by lakes) water has the lightest isotopic composition, being derived mostly from the melting of light snow and glacier ice. It seems feasible to separate isotopically water in lakes/rivers (largely fed by melting multi-year glaciers and snow) and water from melting of snow/ground ice This preliminary study suggests that it is possible to separate various water sources in the southern peninsulas of King George Island, and this separation could be used to study permafrost degradation, as well as feeding and migration patterns in the bird fauna, with implications for protection purposes. Acknowledgments. The National Institute of Research and Development for Biological Sciences (Bucharest, Romania) and the Korean polar institute financially supported fieldwork in King George Island. We thank the personal at King Sejong (South Korea), Belingshaussen (Russia) and Carlini (Argentina) stations in King George Island for logistic supports.

PALOMA : an isotope analyzer using static mass spectrometry, coupled with cryogenic and chemical trapping, for the MSL mission to Mars

NASA Astrophysics Data System (ADS)

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Goulpeau, G.; Leblanc, F.; Montmessin, F.; Sarda, P.; Agrinier, P.; Fouchet, T.; Waite, H.

The technique of GCMS analysis has to be completed by static mass spectrometry for precise in-situ measurements of the isotopic composition of planetary atmospheres (noble gases, stable isotopes), and volatile outgassed products from solid sample pyrolysis. Static mass spectrometry, coupled with gas separation by cryo-separation and gettering, is commonly used in the laboratory to study volatiles extracted from terrestrial and meteoritic samples. Such an instrument (PALOMA) is presently developed in our laboratories, and it will be coupled with a Pyr-GCMS analyzer (MACE), built by a US consortium of science laboratories and industrials (University of Michigan, Southwest Research Institute, JPL, Ball Aerospace). The MACE/PALOMA experiment will be proposed on the NASA Mars Science Laboratory mission, planned to be launched in 2009. The scientific objectives of PALOMA, coupled with MACE, may be listed as follows : (i) search for isotopic signatures of past life in atmosphere, rock, dust and ice samples, with emphasis on carbon, nitrogen and hydrogen; (ii) accurately measure isotopic composition of atmospheric noble gases, and stable isotopes, in order to better constrain past escape, surface interaction, outgassing history and climate evolution; (iii) precisely measure diurnal/ seasonal variations of isotopic ratios of H2O, CO2, and N2, for improving our understanding of present and past climate, and of the role of water cycle. Main measurement objectives are : (i) C, H, O, N isotopic composition in both organic evolved samples (provided by MACE pyrolysis system) and atmosphere with high accuracy (a few per mil at 1-s level); (ii) noble gas (He, Ne, Ar, Kr, Xe) and stable (C, H, O, N) isotope composition in atmosphere with high accuracy (a few per mil at 1-s level); (iii) molecular and isotopic composition of inorganic evolved samples (salts, hydrates, nitrates, {ldots}), including ices; (iv) diurnal and seasonal monitoring of D/H in water vapor, and water ice.

Spatiotemporal patterns of plant water isotope values from a continental-scale sample network in Europe as a tool to improve hydroclimate proxies

NASA Astrophysics Data System (ADS)

Nelson, D. B.; Kahmen, A.

2016-12-01

The hydrogen and oxygen isotopic composition of water available for biosynthetic processes in vascular plants plays an important role in shaping the isotopic composition of organic compounds that these organisms produce, including leaf waxes and cellulose in leaves and tree rings. Characterizing changes in large scale spatial patterns of precipitation, soil water, stem water, and leaf water isotope values over time is therefore useful for evaluating how plants reflect changes in the isotopic composition of these source waters in different environments. This information can, in turn, provide improved calibration targets for understanding the environmental signals that plants preserve. The pathway of water through this continuum can include several isotopic fractionations, but the extent to which the isotopic composition of each of these water pools varies under normal field conditions and over space and time has not been systematically and concurrently evaluated at large spatial scales. Two season-long sampling campaigns were conducted at nineteen sites throughout Europe over the 2014 and 2015 growing seasons to track changes in the isotopic composition of plant-relevant waters. Samples of precipitation, soil water, stem water, and leaf water were collected over more than 200 field days and include more than 500 samples from each water pool. Measurements were used to validate continent-wide gridded estimates of leaf water isotope values derived from a combination of mechanistic and statistical modeling conducted with temperature, precipitation, and relative humidity data. Data-model comparison shows good agreement for summer leaf waters, and substantiates the incorporation of modeled leaf waters in evaluating how plants respond to hydroclimate changes at large spatial scales. These results also suggest that modeled leaf water isotope values might be used in future studies in similar ecosystems to improve the coverage density of spatial or temporal data.

The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar

2016-06-01

The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate differentiation processes, such as partial mantle melting and crystal fractionation, can cause stable Cr isotopic fractionation on Earth and other planetary bodies.

Absolute Isotopic Abundance Ratios and the Accuracy of Δ47 Measurements

NASA Astrophysics Data System (ADS)

Daeron, M.; Blamart, D.; Peral, M.; Affek, H. P.

2016-12-01

Conversion from raw IRMS data to clumped isotope anomalies in CO2 (Δ47) relies on four external parameters: the (13C/12C) ratio of VPDB, the (17O/16O) and (18O/16O) ratios of VSMOW (or VPDB-CO2), and the slope of the triple oxygen isotope line (λ). Here we investigate the influence that these isotopic parameters exert on measured Δ47 values, using real-world data corresponding to 7 months of measurements; simulations based on randomly generated data; precise comparisons between water-equilibrated CO2 samples and between carbonate standards believed to share quasi-identical Δ47 values; reprocessing of two carbonate calibration data sets with different slopes of Δ47 versus T. Using different sets of isotopic parameters generally produces systematic offsets as large as 0.04 ‰ in final Δ47 values. What's more, even using a single set of isotopic parameters can produce intra- and inter-laboratory discrepancies in final Δ47 values, if some of these parameters are inaccurate. Depending on the isotopic compositions of the standards used for conversion to "absolute" values, these errors should correlate strongly with either δ13C or δ18O, or more weakly with both. Based on measurements of samples expected to display identical Δ47 values, such as 25°C water-equilibrated CO2 with different carbon and oxygen isotope compositions, or high-temperature standards ETH-1 and ETH-2, we conclude that the isotopic parameters used so far in most clumped isotope studies produces large, systematic errors controlled by the relative bulk isotopic compositions of samples and standards, which should be one of the key factors responsible for current inter-laboratory discrepancies. By contrast, the isotopic parameters of Brand et al. [2010] appear to yield accurate Δ47 values regardless of bulk isotopic composition. References:Brand, Assonov and Coplen [2010] http://dx.doi.org/10.1351/PAC-REP-09-01-05

Mass dependent fractionation of stable chromium isotopes in mare basalts: Implications for the formation and the differentiation of the Moon

NASA Astrophysics Data System (ADS)

Bonnand, Pierre; Parkinson, Ian J.; Anand, Mahesh

2016-02-01

We present the first stable chromium isotopic data from mare basalts in order to investigate the similarity between the Moon and the Earth's mantle. A double spike technique coupled with MC-ICP-MS measurements was used to analyse 19 mare basalts, comprising high-Ti, low-Ti and KREEP-rich varieties. Chromium isotope ratios (δ53Cr) for mare basalts are positively correlated with indices of magmatic differentiation such as Mg# and Cr concentration which suggests that Cr isotopes were fractionated during magmatic differentiation. Modelling of the results provides evidence that spinel and pyroxene are the main phases controlling the Cr isotopic composition during fractional crystallisation. The most evolved samples have the lightest isotopic compositions, complemented by cumulates that are isotopically heavy. Two hypotheses are proposed to explain this fractionation: (i) equilibrium fractionation where heavy isotopes are preferentially incorporated into the spinel lattice and (ii) a difference in isotopic composition between Cr2+ and Cr3+ in the melt. However, both processes require magmatic temperatures below 1200 °C for appreciable Cr3+ to be present at the low oxygen fugacities found in the Moon (IW -1 to -2 log units). There is no isotopic difference between the most primitive high-Ti, low-Ti and KREEP basalts, which suggest that the sources of these basalts were homogeneous in terms of stable Cr isotopes. The least differentiated sample in our sample set is the low-Ti basalt 12016, characterised by a Cr isotopic composition of -0.222 ± 0.025‰, which is within error of the current BSE value (-0.124 ± 0.101‰). The similarity between the mantles of the Moon and Earth is consistent with a terrestrial origin for a major fraction of the lunar Cr. This similarity also suggests that Cr isotopes were not fractionated by core formation on the Moon.

Using semi-continuous, in-situ measurements of nitrous oxide isotopic composition at a suburban site to track emission processes

NASA Astrophysics Data System (ADS)

Harris, Eliza; Henne, Stephan; Christoph, Hüglin; Christoph, Zellweger; Béla, Tuzson; Erkan, Ibraim; Lukas, Emmenegger; Joachim, Mohn

2017-04-01

Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance emitted this century. The atmospheric N2O mole fraction has been increasing at a rate of 0.2-0.3% per year over the past decades due to anthropogenic emissions; in addition, recent results suggest that the rate of increase is rising - therefore effective mitigation of N2O emissions is a critical point for environmental policy. However, N2O sources are poorly defined and disperse, complicating the development of targeted mitigation strategies. Online isotopic measurements using preconcentration and laser spectroscopy [1,2,3] have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of trace gases such as N2O. Semi-continuous, real-time measurements of N2O isotopic composition (δ18O, site preference [SP = 14N15N16O - 15N14N16O] and δ15Nbulk) were performed at the suburban site of Dübendorf, Switzerland, for 19 months between July 2014 and February 2016. The data precision reached 0.1‰ in the final months, thus the results could clearly identify nocturnal build-up of N2O, with a corresponding decrease in δ18O, SP and δ15Nbulk due to isotopically depleted anthropogenic sources. Daily mean source isotopic composition was calculated by considering the measured and the background mole fraction and isotopic composition. Delta values of the mean emission source were highest in winter, with a seasonal cycle of 12, 8 and 5‰ for δ18O, SP and δ15Nbulk respectively. The chemical and meteorological parameters controlling source isotopic composition were considered using data from the Swiss National Air Pollution Monitoring Network (NABEL) as well as a transport regime cluster analysis. A clear spatial distribution for source isotopic composition was observed for δ18O, as well as a significant relationship with the level of urban pollution, indicating δ18O may be a strong indicator of combustion/industrial vs. agricultural N2O. In contrast, δ15Nbulk and particularly SP appear to vary too strongly in response to other factors affecting emission processes to provide a useful distinction between source categories on a regional scale - these isotopocules may however be useful to distinguish emission pathways on a local scale. For comparison, FLEXPART-COSMO transport simulations [4] were combined with emissions from the EDGAR inventory and estimates of source isotopic composition from literature, to simulate N2O isotopic composition at the sampling site. The model was able to capture variability in N2O mole fraction adequately (R2 = 0.34; p <<0.01). However, the measured variability in source isotopic composition was 1-2 orders of magnitude larger than simulated, illustrating that our knowledge of isotopic source signatures - in particular technical N2O sources - is still too limited to successfully model variations in ambient N2O isotopic composition. [1] Mohn et al. (2012) Atmospheric Measurement Techniques, doi:10.5194/amt-5-1601-2012 [2] Harris et al. (2014) Analytical Chemistry, doi: 10.1021/ac403606u. [3] Röckmann et al. (2016) Atmospheric Chemistry and Physics, doi:10.5194/acp-16-10469-2016. [4] Henne et al. (2016) Atmospheric Chemistry and Physics, doi:10.5194/acp-16-3683-2016.

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.

Osmium uptake, distribution, and 187Os/188Os and 187Re/188Os compositions in Phaeophyceae macroalgae, Fucus vesiculosus: Implications for determining the 187Os/188Os composition of seawater

NASA Astrophysics Data System (ADS)

Racionero-Gómez, B.; Sproson, A. D.; Selby, D.; Gannoun, A.; Gröcke, D. R.; Greenwell, H. C.; Burton, K. W.

2017-02-01

The osmium isotopic composition (187Os/188Os) of seawater reflects the balance of input from mantle-, continental- and anthropogenic-derived sources. This study utilizes the Phaeophyceae, Fucus vesiculosus, to analyse its Os abundance and uptake, as well as to assess if macroalgae records the Os isotope composition of the seawater in which it lives. The data demonstrates that Os is not located in one specific biological structure within macroalgae, but is found throughout the organism. Osmium uptake was measured by culturing F. vesiculosus non-fertile tips with different concentrations of Os with a known 187Os/188Os composition (∼0.16), which is significantly different from the background isotopic composition of local seawater (∼0.94). The Os abundance of cultured non-fertile tips show a positive correlation to the concentration of the Os doped seawater. Moreover, the 187Os/188Os composition of the seaweed equalled that of the culture medium, strongly confirming the possible use of macroalgae as a biological proxy for the Os isotopic composition of the seawater.

Optimizing isotope substitution in graphene for thermal conductivity minimization by genetic algorithm driven molecular simulations

NASA Astrophysics Data System (ADS)

Davies, Michael; Ganapathysubramanian, Baskar; Balasubramanian, Ganesh

2017-03-01

We present results from a computational framework integrating genetic algorithm and molecular dynamics simulations to systematically design isotope engineered graphene structures for reduced thermal conductivity. In addition to the effect of mass disorder, our results reveal the importance of atomic distribution on thermal conductivity for the same isotopic concentration. Distinct groups of isotope-substituted graphene sheets are identified based on the atomic composition and distribution. Our results show that in structures with equiatomic compositions, the enhanced scattering by lattice vibrations results in lower thermal conductivities due to the absence of isotopic clusters.

Revising Estimates of the Methane Production Pathway in Peatland Porewater Using Intramolecular Isotopic Analyses of Acetate

NASA Astrophysics Data System (ADS)

Thomas, B.; Arthur, M. A.; Freeman, K. H.

2007-12-01

Stable isotopic measurements of methane and carbon dioxide are routinely applied to environmental samples to assess the relative importance of methane production by either aceticlastic or hydrogenotrophic methanogenesis. Such estimates rely upon assumptions about isotopic fractionation during methane production and oxidation. Rigorous isotope-based pathway estimates require knowledge of the carbon isotopic composition of both carbon dioxide and acetate. In practice, technical barriers have limited measurements of the isotopic composition of whole acetate in natural samples. Yet, the estimate of whole acetate isotopic values, even when available, may not represent accurately the composition of the methyl carbon, which is, in fact, the precursor to methane. It is exceedingly rare to find carbon isotopic measurements of acetate-methyl in the literature, and, to our knowledge, the d13C of the acetate-methyl precursor to methane has never before been reported from peatland porewater samples. Extremely 13C-depleted methane, -70 permil VPDB, and 13C-enriched carbon dioxide from acidic northern peat bogs are typically interpreted as signatures of hydrogenotrophic methanogenesis. The hypothesized dominance of methane production from hydrogen in acidic bogs contrasts with the vast majority of freshwater wetlands in which aceticlastic methanogenesis dominates. Using a new technique for the online analysis of the intramolecular carbon isotopic composition of acetate in natural samples, we find the acetate-methyl in peat porewaters can be significantly depleted relative to bulk organic matter. In porewater profiles from both winter and summer, acetate is as much as 15 permil depleted relative to bulk carbon. We hypothesize that acetate- methyl isotopic depletion results from conditions that favor autotrophic acetogenesis and subsequent acetate consumption by aceticlastic methanogens. Porewater depth profiles during winter and summer illustrate depth- dependent increases in the fraction of methane derived from carbon dioxide, with deeper peat dominated by hydrogenotrophic methanogenesis, but shallow peat dominated by aceticlastic methanogens. Significant aceticlastic methane production from autotrophically produced acetate challenges the ability of hydrogen isotopic measurements of methane to represent the pathway of methanogenesis. Supplementing our field observations, intramolecular acetate measurements of incubation experiments confirm that an aceticlastic methanogen can facilitate significant acetate-carboxyl exchange with DIC. This novel technique confirms two caveats associated with whole acetate carbon isotopic data: 1, the carboxyl carbon isotopic composition may not accurately reflect the composition of the parent molecule, and 2, the acetate methyl may be derived from inorganic carbon or the fractionation effect of fermentation in acidic porewaters may be significant.

Methane clumped isotopes: Progress and potential for a new isotopic tracer

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

Douglas, Peter M. J.; Stolper, Daniel A.; Eiler, John M.

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding hydrocarbon systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a potentially valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here wemore » present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. We review different processes affecting methane clumped isotope compositions, describe the relationships between conventional isotope and clumped isotope data, and summarize the types of information that this measurement can provide in different Earth and planetary environments.« less

Oxygen-isotope, X-ray-diffraction and scanning-electron-microscope examinations of authigenic-layer-silicate minerals from Mississippian and Pennsylvanian sandstones in the Michigan Basin

USGS Publications Warehouse

Zacharias, K.F.; Sibley, D.F.; Westjohn, D.B.; Weaver, T. L.

1993-01-01

Oxygen-isotope compositions of authigenic-layer silicates (<2-micrometer fraction) extracted from Mississippian and Pennsylvanian sandstones in the Lower Peninsula of Michigan were determined. Petrographic and scanning-electron-microscope examinations, and X-ray diffractograms show that chlorite and kaolinite are the most common authigenic-layer silicates in Mississippian sandstones. The range of oxygen-isotope compositions of chlorite and kaolinite are +10.3 to +11.9 and +12.9 to +19.3 pars per thousand (per mil) (relative to Standard Mean Ocean Water), respectively. Kaolinite is the only authigenic-isotopic compositions of kaolinite range from +16.8 to +19.0 per mil.

Development of particle induced gamma-ray emission methods for nondestructive determination of isotopic composition of boron and its total concentration in natural and enriched samples.

PubMed

Chhillar, Sumit; Acharya, Raghunath; Sodaye, Suparna; Pujari, Pradeep K

2014-11-18

We report simple particle induced gamma-ray emission (PIGE) methods using a 4 MeV proton beam for simultaneous and nondestructive determination of the isotopic composition of boron ((10)B/(11)B atom ratio) and total boron concentrations in various solid samples with natural isotopic composition and enriched with (10)B. It involves measurement of prompt gamma-rays at 429, 718, and 2125 keV from (10)B(p,αγ)(7)Be, (10)B(p, p'γ)(10)B, and (11)B(p, p'γ)(11)B reactions, respectively. The isotopic composition of boron in natural and enriched samples was determined by comparing peak area ratios corresponding to (10)B and (11)B of samples to natural boric acid standard. An in situ current normalized PIGE method, using F or Al, was standardized for total B concentration determination. The methods were validated by analyzing stoichiometric boron compounds and applied to samples such as boron carbide, boric acid, carborane, and borosilicate glass. Isotopic compositions of boron in the range of 0.247-2.0 corresponding to (10)B in the range of 19.8-67.0 atom % and total B concentrations in the range of 5-78 wt % were determined. It has been demonstrated that PIGE offers a simple and alternate method for total boron as well as isotopic composition determination in boron based solid samples, including neutron absorbers that are important in nuclear technology.

Stalagmite geochemistry and the timing of the last interglacial-glacial transition in Central Europe (NE Hungary)

NASA Astrophysics Data System (ADS)

Siklosy, Z.; Demeny, A.; Pilet, S.; Leel-Ossy, Sz.; Lin, K.; Shen, C.-C.

2009-04-01

Speleothems can provide accurate chronologies for reconstructions of climate change by combination of U/Th dating and climate-related geochemical compositions. Geochemical studies of speleothems from Central Europe are mostly based on stable C and O isotope analyses, thus, complex geochemical studies combining isotope and trace element measurements are needed for more reliable climate models for this transitional area between oceanic and continental regions. We present stable H-C-O isotope and trace element records obtained on speleothems covering the Last Interglacial (MIS 5e) and the transition to MIS 5d. A stalagmite from Baradla Cave grew from 127.5 to 110 ka. Accelerated growth rates have been detected by U/Th age data in the 127 to 126 ka and 119 to 117 ka parts. Trace element compositions and 230Th/232Th ratios suggest changes in the hydrological regime, whereby early calcite precipitates formed in fissures during the dry and cold glacial period were dissolved by the starting flux of infiltrating meteoric water (producing elevated dissolved ion concentration but low detrital Th component), then the increasing amount of dripwater during the interglacial period resulted in trace element dilution. Temperature and precipitation amount variations are also reflected by the stable isotope compositions. Oxygen isotope composition shows a continuous increase from 127.5 ka until about 118 ka most probably related to temperature rise, whereas C isotope values are shifted in negative direction suggesting increasing humidity in accordance with trace element contents. The presumably warmest period at ca. 118 ka is associated with rather arid climate as indicated by peak d18O values coinciding with the highest dD values of fluid inclusion water. This is followed by a pronounced negative shift in both O and H isotope values, similarly to recent Alpine studies (Meyer et al., 2008), most probably related to cooling. Hydrogen isotope compositions of fluid inclusion water evaluated together with calculated oxygen isotope compositions of water indicate warming and increasing significance of summer precipitation at the latest period of the last interglacial, then increasing importance of winter precipitation and/or changes in oceanic source composition during the cooling phase. The good agreement with other (Alpine and marine) records indicate a synchronous climate change. However, after a negative shift in the wet/warm phase (increasing soil activity), C isotope values start to increase already at about 119 ky BP, warning to the use of the two isotope systems as event correlation tools. In conclusion, our combined isotope and trace element study indicate a complex pattern of temperature and humidity variations during and right after the Last Interglacial. Acknowledgements — This study was financially supported by the Hungarian Scientific Research Fund (OTKA T 049713). Measurements of U-Th isotopic compositions and and 230Th dates were supported by the National Science Council grants (94-2116-M002-012, 97-2752-M002-004-PAE & -005-PAE to C.C.S.). [Meyer, M.; Spötl, C.; Mangini, A. (2008): The demise of the Last Interglacial recorded in isotopically dated speleothems from the Alps. Quaternary Science Reviews, 27, 476-496.

Carbon isotope geochemistry and geobiology

NASA Technical Reports Server (NTRS)

Desmarais, D.

1985-01-01

Carbon isotope fractionation values were used to understand the history of the biosphere. For example, plankton analyses confirmed that marine extinctions at the end of the Cretaceous period were indeed severe (see Hsu's article in Sundquist and Broeker, 1984). Variations in the isotopic compositions of carbonates and evaporitic sulfates during the Paleozoic reflect the relative abundances of euxinic (anoxic) marine environments and organic deposits from terrestrial flora. The carbon isotopic composition of Precambrian sediments suggest that the enzyme ribulose bisphosphate carboxylase has existed for perhaps 3.5 billion years.

The identification of lead ammunition as a source of lead exposure in First Nations: the use of lead isotope ratios.

PubMed

Tsuji, Leonard J S; Wainman, Bruce C; Martin, Ian D; Sutherland, Celine; Weber, Jean-Philippe; Dumas, Pierre; Nieboer, Evert

2008-04-15

The use of lead shotshell to hunt water birds has been associated with lead-contamination in game meat. However, evidence illustrating that lead shotshell is a source of lead exposure in subsistence hunting groups cannot be deemed definitive. This study seeks to determine whether lead shotshell constitutes a source of lead exposure using lead isotope ratios. We examined stable lead isotope ratios for lichens, lead shotshell and bullets, and blood from residents of Fort Albany and Kashechewan First Nations, and the City of Hamilton, Ontario, Canada. Data were analyzed using ANOVA and regression analyses. ANOVA of isotope ratios for blood revealed significant differences with respect to location, but not sex. Hamilton differed from both Kashechewan and Fort Albany; however, the First Nations did not differ from each other. ANOVA of the isotope ratios for lead ammunition and lichens revealed no significant differences between lichen groups (north and south) and for the lead ammunition sources (pellets and bullets). A plot of (206)Pb/(204)Pb and (206)Pb/(207)Pb values illustrated that lichens and lead ammunition were distinct groupings and only the 95% confidence ellipse of the First Nations group overlapped that of lead ammunition. In addition, partial correlations between blood-lead levels (adjusted for age) and isotope ratios revealed significant (p<0.05) positive correlations for (206)Pb/(204)Pb and (206)Pb/(207)Pb, and a significant negative correlation for (208)Pb/(206)Pb, as predicted if leaded ammunition were the source of lead exposure. In conclusion, lead ammunition was identified as a source of lead exposure for First Nations people; however, the isotope ratios for lead shotshell pellets and bullets were indistinguishable. Thus, lead-contaminated meat from game harvested with lead bullets may also be contributing to the lead body burden.

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

Yogodzinski, Gene; Vervoort, Jeffery; Brown, Shaun Tyler

The Hf and Nd isotopic compositions of 71 Quaternary lavas collected from locations along the full length of the Aleutian island arc are used to constrain the sources of Aleutian magmas and to provide insight into the geochemical behavior of Nd and Hf and related elements in the Aleutian subduction-magmatic system. Isotopic compositions of Aleutian lavas fall approximately at the center of, and form a trend parallel to, the terrestrial Hf-Nd isotopic array with {var_epsilon}{sub Hf} of +12.0 to +15.5 and {var_epsilon}{sub Nd} of +6.5 to +10.5. Basalts, andesites, and dacites within volcanic centers or in nearby volcanoes generally allmore » have similar isotopic compositions, indicating that there is little measurable effect of crustal or other lithospheric assimilation within the volcanic plumbing systems of Aleutian volcanoes. Hafnium isotopic compositions have a clear pattern of along-arc increase that is continuous from the eastern-most locations near Cold Bay to Piip Seamount in the western-most part of the arc. This pattern is interpreted to reflect a westward decrease in the subducted sediment component present in Aleutian lavas, reflecting progressively lower rates of subduction westward as well as decreasing availability of trench sediment. Binary bulk mixing models (sediment + peridotite) demonstrate that 1-2% of the Hf in Aleutian lavas is derived from subducted sediment, indicating that Hf is mobilized out of the subducted sediment with an efficiency that is similar to that of Sr, Pb and Nd. Low published solubility for Hf and Nd in aqueous subduction fluids lead us to conclude that these elements are mobilized out of the subducted component and transferred to the mantle wedge as bulk sediment or as a silicate melt. Neodymium isotopes also generally increase from east to west, but the pattern is absent in the eastern third of the arc, where the sediment flux is high and increases from east to west, due to the presence of abundant terrigenous sediment in the trench east of the Amlia Fracture Zone, which is being subducting beneath the arc at Seguam Island. Mixing trends between mantle wedge and sediment end members become flatter in Hf-Nd isotope space at locations further west along the arc, indicating that the sediment end member in the west has either higher Nd/Hf or is more radiogenic in Hf compared to Nd. This pattern is interpreted to reflect an increase in pelagic clay relative to the terrigenous subducted sedimentary component westward along the arc. Results of this study imply that Hf does not behave as a conservative element in the Aleutian subduction system, as has been proposed for some other arcs.« less

Metasomatic Evolution in Tectonically Mixed Zones (Mélange) and Significance for Geochemical Evolution of the Slab-Mantle Interface

NASA Astrophysics Data System (ADS)

Bebout, G. E.; King, R. L.

2012-12-01

Fluid flow focused in highly deformed zones (shear zones), and the physical juxtaposition of chemically disparate rocks (via mechanical mixing) in such zones, can lead to extensive metasomatism, including volume strain, and result in rocks with hybridized compositions little resembling the compositions of the incorporated rock types [1-5]. In the Catalina Schist (California), lawsonite-albite, lawsonite-blueschist, and amphibolite-facies units contain shear zones at scales of meters to kilometers, each containing "blocks" (with more spherical or more tabular dimensions) co-facial in grade with the "matrix" surrounding these blocks [1-3]. Oxygen isotope data for these "mélange" units, and adjacent more "coherent" expanses, indicate enhanced fluid flow in the more strongly deforming mélange zones while fluid flow in coherent domains was dominantly fracture-controlled and episodic. The amphibolite-facies mélange unit shows evidence for km-scale equilibration of varying mineral assemblages with H2O-rich fluids with uniform O and H isotope compositions consistent with a lower-grade metasedimentary source. This unit is believed to have formed largely by mechanical mixing of mafic and ultramafic compositions, partly because of the scarcity of sedimentary blocks. However, the mélange matrix in this unit preserves a number of sedimentary chemical/isotopic characteristics (e.g., Pb isotope compositions [3]) that could reflect the incorporation of sedimentary rocks, with or without fluid-related fractionation, and possibly fluid-mediated additions. Tectonically mixed zones such as these, if volumetrically significant at the slab-mantle interface, could exert disproportionate control on the compositions of hydrous fluids or silicate melts emanating from subducting slabs and entering the forearc to backarc mantle wedge, including those contributing to arc magmatism [1-5]. Geochemical studies of arc lavas should consider the possibility that the "fluids" contributed from slabs to arc source regions bear chemical/isotopic signatures reflecting their interaction with these hybridized zones produced by mixing of varying proportions of sedimentary, mafic, and ultramafic compositions. Also, the high-variance hydrous mineral assemblages created by these coeval mechanical and metasomatic processes (e.g., nearly monomineralic chlorite, talc, and amphibole schists) could play an important role in the volatiles budgets at subduction zones (i.e., having stabilities to P and T significantly higher than those for mineral assemblages in metabasaltic and metasedimentary rocks containing the same mineral phases [1,4]). Field, petrologic/geochemical, theoretical, and geophysical studies should work toward assessment of the volumetric significance, physical properties, and devolatilization histories of these hybridized compositions. [1] Bebout and Barton (2002) Chem. Geol. 187:79-106 [2] King et al. (2006) Ear. Planet. Sci. Lett. 246:288-304 [3] King et al. (2007) Chem. Geol. 239:305-322 [4] Spandler et al. (2008) Contrib. Mineral. Petrol. 155:181-198 [5] Miller et al. (2009) Lithos 107:53-67

Spatial, seasonal, and source variability in the stable oxygen and hydrogen isotopic composition of tap waters throughout the USA

USGS Publications Warehouse

Landwehr, Jurate M.; Coplen, Tyler B.; Stewart, David W.

2013-01-01

To assess spatial, seasonal, and source variability in stable isotopic composition of human drinking waters throughout the entire USA, we have constructed a database of δ18O and δ2H of US tap waters. An additional purpose was to create a publicly available dataset useful for evaluating the forensic applicability of these isotopes for human tissue source geolocation. Samples were obtained at 349 sites, from diverse population centres, grouped by surface hydrologic units for regional comparisons. Samples were taken concurrently during two contrasting seasons, summer and winter. Source supply (surface, groundwater, mixed, and cistern) and system (public and private) types were noted. The isotopic composition of tap waters exhibits large spatial and regional variation within each season as well as significant at-site differences between seasons at many locations, consistent with patterns found in environmental (river and precipitation) waters deriving from hydrologic processes influenced by geographic factors. However, anthropogenic factors, such as the population of a tap’s surrounding community and local availability from diverse sources, also influence the isotopic composition of tap waters. Even within a locale as small as a single metropolitan area, tap waters with greatly differing isotopic compositions can be found, so that tap water within a region may not exhibit the spatial or temporal coherence predicted for environmental water. Such heterogeneities can be confounding factors when attempting forensic inference of source water location, and they underscore the necessity of measurements, not just predictions, with which to characterize the isotopic composition of regional tap waters. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

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

NASA Astrophysics Data System (ADS)

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

2014-11-01

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

Multiple enrichment of the Carpathian-Pannonian mantle: Pb-Sr-Nd isotope and trace element constraints

NASA Astrophysics Data System (ADS)

Rosenbaum, Jeffrey M.; Wilson, Marjorie; Downes, Hilary

1997-07-01

Pb isotope compositions of acid-leached clinopyroxene and amphibole mineral separates from spinel peridotite mantle xenoliths entrained in Tertiary-Quaternary alkali basalts from the Carpathian-Pannonian Region of eastern Europe provide important constraints on the processes of metasomatic enrichment of the mantle lithosphere in an extensional tectonic setting associated with recent subduction. Principal component analysis of Pb-Sr-Nd isotope and rare earth element compositions of the pyroxenes is used to identify the geochemical characteristics of the original lithospheric mantle protolith and a spectrum of infiltrating metasomatic agents including subduction-related aqueous fluids and silicate melts derived from a subduction-modified mantle wedge which contains a St. Helena-type (HIMU) plume component. The mantle protolith is highly depleted relative to mid-ocean ridge basalt-source mantle with Pb-Nd-Sr isotope compositions consistent with an ancient depletion event. Silicate melt infiltration into the protolith accounts for the primary variance in the Pb-Sr-Nd isotope compositions of the xenoliths and has locally generated metasomatic amphibole. Infiltration of aqueous fluids has introduced radiogenic Pb and Sr without significantly perturbing the rare earth element signature of the protolith. The Pb isotope compositions of the fluid-modified xenoliths suggest that they reacted with aqueous fluids released from a subduction zone which had equilibrated with sediment derived from an ancient basement terrain. We propose a model for mantle lithosphere evolution consistent with available textural and geochemical data for the xenolith population. The Pb-Sr-Nd isotope compositions of both alkaline mafic magmas and rare, subduction-related, calc-alkaline basaltic andesites from the region provide important constraints for the nature of the asthenospheric mantle wedge and confirm the presence of a HIMU plume component. These silicate melts contribute to the metasomatism of the mantle lithosphere rather than being derived therefrom.

Stable Isotopes as Indicators of Groundwater Recharge Mechanisms in Arid and Semi-arid Australia

NASA Astrophysics Data System (ADS)

Harrington, G. A.; Herczeg, A. L.

2001-05-01

The isotopic compositions of soil water and groundwaters in arid and semi-arid zones are always different from the mean composition of rainfall. Although evaporative processes always remove the lighter isotopes (1H and 16O) to the vapour phase, arid zone groundwaters are invariably depleted in the heavy isotopes (2H and 18O) relative to mean present day rainfall. We compare two sites, one in semi-arid South Australia and the other in arid Central Australia that have a similar mean annual rainfall (250 to 300 mm/a), very high potential evapotranspiration (2500 and 3500 mm/a respectively) but very different rainfall patterns (winter dominated versus summer monsoonal). We aim to evaluate whether inferences from groundwater \\delta2H and \\delta18O reveal information about palaeorecharge, or recharge mechanisms or a combination of both. Recharge to the unconfined limestone aquifer in the Mallee area of South Australia occurs annually via widespread (diffuse) infiltration of winter dominant rainfall. This process is reflected in soil and groundwater isotopic compositions that plot relatively close to both the Local Meteoric Water Line and the volume-weighted mean composition of winter rainfall, and have a deuterium excess (\\delta2H-8.\\delta18O) of between +2 and +8 for the freshest samples. Groundwater recharge to the arid Ti-Tree Basin occurs predominantly by inputs of partially-evaporated surface water from ephemeral rivers and flood-plains following rare, high-intensity storms that are derived from monsoonal activity to the north of Australia. These extreme events result in groundwater and soil water stable isotope compositions being significantly depleted in the heavy isotopes relative to the mean composition of rainfall and a deuterium excess of between minus 8 and +3 in the freshest groundwaters.

Large-scale drivers of Caucasus climate variability in meteorological records and Mt El'brus ice cores

NASA Astrophysics Data System (ADS)

Kozachek, Anna; Mikhalenko, Vladimir; Masson-Delmotte, Valérie; Ekaykin, Alexey; Ginot, Patrick; Kutuzov, Stanislav; Legrand, Michel; Lipenkov, Vladimir; Preunkert, Susanne

2017-05-01

A 181.8 m ice core was recovered from a borehole drilled into bedrock on the western plateau of Mt El'brus (43°20'53.9'' N, 42°25'36.0'' E; 5115 m a.s.l.) in the Caucasus, Russia, in 2009 (Mikhalenko et al., 2015). Here, we report on the results of the water stable isotope composition from this ice core with additional data from the shallow cores. The distinct seasonal cycle of the isotopic composition allows dating by annual layer counting. Dating has been performed for the upper 126 m of the deep core combined with 20 m from the shallow cores. The whole record covers 100 years, from 2013 back to 1914. Due to the high accumulation rate (1380 mm w.e. year-1) and limited melting, we obtained isotopic composition and accumulation rate records with seasonal resolution. These values were compared with available meteorological data from 13 weather stations in the region and also with atmosphere circulation indices, back-trajectory calculations, and Global Network of Isotopes in Precipitation (GNIP) data in order to decipher the drivers of accumulation and ice core isotopic composition in the Caucasus region. In the warm season (May-October) the isotopic composition depends on local temperatures, but the correlation is not persistent over time, while in the cold season (November-April), atmospheric circulation is the predominant driver of the ice core's isotopic composition. The snow accumulation rate correlates well with the precipitation rate in the region all year round, which made it possible to reconstruct and expand the precipitation record at the Caucasus highlands from 1914 until 1966, when reliable meteorological observations of precipitation at high elevation began.

[Effect of microorganisms and seasonal factors on the isotope composition of organic carbon from Black Sea suspensions].

PubMed

Ivanov, M V; Lein, A Iu; Miller, Iu M; Iusunov, S K; Pimenov, N V; Wehrli, B; Rusanov, I I; Zehnder, A

2000-01-01

The isotopic composition of particulate organic carbon (POC) from the Black Sea deep-water zone was studied during a Russian-Swiss expedition in May 1998. POC from the upper part of the hydrogen sulfide zone (the C-layer) was found to be considerably enriched with the 12C isotope, as compared to the POC of the oxycline and anaerobic zone. In the C-layer waters, the concurrent presence of dissolved oxygen and hydrogen sulfide and an increased rate of dark CO2 fixation were recorded, suggesting that the change in the POC isotopic composition occurs at the expense of newly formed isotopically light organic matter of the biomass of autotrophic bacteria involved in the sulfur cycle. In the anaerobic waters below the C-layer, the organic matter of the biomass of autotrophs is consumed by the community of heterotrophic microorganisms; this results in weighting of the POC isotopic composition. Analysis of the data obtained and data available in the literature allows an inference to be made about the considerable seasonable variability of the POC delta 13C value, which depends on the ratio of terrigenic and planktonogenic components in the particulate organic matter.

Lead isotopes in lichen transplants around a Cu smelter in Russia determined by MC-ICP-MS reveal transient records of multiple sources.

PubMed

Spiro, B; Weiss, D J; Purvis, O W; Mikhailova, I; Williamson, B J; Coles, B J; Udachin, V

2004-12-15

Transplants of the lichen Hypogymnia physodes, which is relatively tolerant to SO2 and heavy metals, were deployed for 3 months over a 60 km long SW-NE transect centered on a highly polluting Cu smelter and its adjoining town of Karabash, southern Urals, Russia. The abundance of 206Pb, 207Pb, 208Pb, and 204Pb were determined by MC-ICP-MS. The measurement of 204Pb revealed critical features, which would otherwise remain concealed: (i) The precise isotope ratios referenced to 204Pb allowed several different sources to be resolved even within the small area covered: (a) the obvious pollutant source of the Karabash Cu smelter; (b) two dispersed sources, likely to include soil with lower and different contributions of thorogenic and uranogenic lead; and (c) one anthropogenic source with higher contribution of 235U derived Pb. (ii) In part of the transect, the Pb isotope composition changed while the Pb concentrations remained the same. This indicates that the Pb content of the transplantation material from the background site was largely replaced and that the transplants provide a transient record reflecting a continuous accumulation and loss of environmental Pb, probably mainly in the form of extracellular particles. Overall, the method of lichen transplantation coupled with Pb isotope ratio determinations proved effective in assessing the usefulness of lichens in biomonitoring and in resolving different sources of atmospheric deposition.

Thallium as a tracer of fluid-rock interaction in the shallow Mariana forearc

NASA Astrophysics Data System (ADS)

Nielsen, Sune G.; Klein, Frieder; Kading, Tristan; Blusztajn, Jerzy; Wickham, Katie

2015-11-01

Fluids driven off the subducting Pacific plate infiltrate the shallow Mariana forearc and lead to extensive serpentinization of mantle peridotite. However, the sources, pathways, and chemical modifications of ascending, slab-derived fluids remain poorly constrained and controversial. In this study, we use thallium (Tl) concentrations and isotopic ratios of serpentinized peridotite and rodingitized diabase from the South Chamorro and Conical Seamounts to discriminate between potential fluid sources with distinct Tl isotope compositions. Serpentinite samples from the Mariana forearc all display ε205 Tl > - 0.5 (where ε205 Tl = 10 , 000 × (205Tl /Tl203sample -205Tl /SRM 997 203Tl ) / (205Tl / SRM 997 203Tl )), which is significantly enriched in 205Tl compared to the normal mantle (ε205 Tl = - 2). Given that high temperature hydrothermal processes do not impart significant Tl isotope fractionation, the isotope compositions of the serpentinites must reflect that of the serpentinizing fluid. Pelagic sediments are the only known slab component that consistently displays ε205 Tl > - 0.5 and, therefore, we interpret the heavy Tl isotope signatures as signifying that the serpentinizing fluids were derived from subducting pelagic sediments. A rodingitized diabase from Conical Seamount was found to have an ε205 Tl of 0.8, suggesting that sediment-sourced serpentinization fluids could also affect diabase and other mafic lithologies in the shallow Mariana forearc. Forearc rodingitization of diabase led to a strong depletion in Tl content and a virtually complete loss of K, Na and Rb. The chemical composition of hybrid fluids resulting from serpentinization of harzburgite with concomitant rodingitization of diabase can be highly alkaline, depleted in Si, yet enriched in Ca, Na, K, and Rb, which is consistent with the composition of fluids emanating from mud volcanoes in the Mariana forearc. Our study suggests that fluid-rock interactions between sedimentary, mafic, and ultramafic lithologies are strongly interconnected even in the shallowest parts of subduction zones. We conclude that transfer of fluids and dissolved elements at temperatures and pressures below 400 °C and 1 GPa, respectively, must be taken into account when elemental budgets and mass transfer between the subducting plate, the forearc, the deep mantle and the ocean are evaluated.

Lead concentration distribution and source tracing of urban/suburban aquatic sediments in two typical famous tourist cities: Haikou and Sanya, China.

PubMed

Dong, Zhicheng; Bao, Zhengyu; Wu, Guoai; Fu, Yangrong; Yang, Yi

2010-11-01

The content and spatial distribution of lead in the aquatic systems in two Chinese tropical cities in Hainan province (Haikou and Sanyan) show an unequal distribution of lead between the urban and the suburban areas. The lead content is significantly higher (72.3 mg/kg) in the urban area than the suburbs (15.0 mg/kg) in Haikou, but quite equal in Sanya (41.6 and 43.9 mg/kg). The frequency distribution histograms suggest that the lead in Haikou and in Sanya derives from different natural and/or anthropogenic sources. The isotopic compositions indicate that urban sediment lead in Haikou originates mainly from anthropogenic sources (automobile exhaust, atmospheric deposition, etc.) which contribute much more than the natural sources, while natural lead (basalt and sea sands) is still dominant in the suburban areas in Haikou. In Sanya, the primary source is natural (soils and sea sands).

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.

The first investigation of Wilms' tumour atomic structure-nitrogen and carbon isotopic composition as a novel biomarker for the most individual approach in cancer disease

PubMed Central

Taran, Katarzyna; Frączek, Tomasz; Sikora-Szubert, Anita; Sitkiewicz, Anna; Młynarski, Wojciech; Kobos, Józef; Paneth, Piotr

2016-01-01

The paper describes a novel approach to investigating Wilms' tumour (nephroblastoma) biology at the atomic level. Isotope Ratio Mass Spectrometry (IRMS) was used to directly assess the isotope ratios of nitrogen and carbon in 84 Wilms' tumour tissue samples from 28 cases representing the histological spectrum of nephroblastoma. Marked differences in nitrogen and carbon isotope ratios were found between nephroblastoma histological types and along the course of cancer disease, with a breakout in isotope ratio of the examined elements in tumour tissue found between stages 2 and 3. Different isotopic compositions with regard to nitrogen and carbon content were observed in blastemal Wilms' tumour, with and without focal anaplasia, and in poorly- and well-differentiated epithelial nephroblastoma. This first assessment of nitrogen and carbon isotope ratio reveals the previously unknown part of Wilms' tumour biology and represents a potential novel biomarker, allowing for a highly individual approach to treating cancer. Furthermore, this method of estimating isotopic composition appears to be the most sensitive tool yet for cancer tissue evaluation, and a valuable complement to established cancer study methods with prospective clinical impact. PMID:27732932

Sulfur and Carbon Isotope Systematics in Middle-Upper Cambrian Port au Port Group From Western Newfoundland, Canada: Implications for Seawater Sulfate Concentrations

NASA Astrophysics Data System (ADS)

Hurtgen, M. T.; Pruss, S.; Knoll, A. H.

2006-12-01

The biogeochemical cycles of carbon and sulfur are intimately linked through a variety of feedbacks that operate on timescales of days to millions of years. For example, under anaerobic conditions, some bacteria respire organic matter by sulfate reduction, reducing sulfate to sulfide, which then reacts with iron to form iron sulfide (preserved as pyrite). On much longer timescales, increases in the fraction of total carbon buried as organic carbon can drive increases in atmospheric oxygen concentrations which then facilitate an increase in the extent to which sulfides on land are oxidatively weathered and ultimately delivered to the oceans as sulfate via rivers. Interestingly, these two processes impose very different isotope relationships between the C isotope composition of marine dissolved inorganic carbon (DIC) and the S isotope composition of seawater sulfate. The former leads to a positive correlation between δ13Ccarbonate and δ34Ssulfate whereas the latter prescribes a long-term negative correlation. Of course, the recognition of either a positive or negative correlation between δ13Ccarbonate and δ34Ssulfate depends strongly on the relative sizes of the DIC and seawater sulfate reservoirs-- neither of which is well constrained for the Cambrian Period. Here, we present a high-resolution δ34S (sulfate and pyrite) and δ13Ccarbonate record from the mixed carbonate-siliciclastic Middle-Upper Cambrian Port au Port Group in western Newfoundland, Canada. The δ34Ssulfate profile displays systematic shifts of >15‰ over relatively short stratigraphic distances (10 m, likely to represent < 1 Myr). C isotope values shift sympathetically throughout much of the composite section; however, important deviations from this relationship exist. First, in the Middle Cambrian March Point Formation, a 15‰- δ34Ssulfate decrease precedes a 3‰-δ13Ccarbonate fall suggesting that the sulfur cycle recorded the perturbation to the system before the carbon cycle did. Secondly, further up in the section, the Upper Cambrian Man O' War Member exhibits a ~6‰ positive C isotope excursion (SPICE Event) with almost no change in S isotope values. In combination, these data suggest that seawater sulfate concentrations were much lower than modern values, at least in this basin, resulting in a sulfate reservoir that was more susceptible to isotopic variation. Moreover, differences in the relationship between C and S isotopes indicate that the relative sizes of the marine DIC and sulfate reservoir changed through this interval and/or that the various perturbations recorded in the lower and upper parts of this succession affected the carbon and sulfur cycles in different ways.

The lead isotopic age of the Earth can be explained by core formation alone.

PubMed

Wood, Bernard J; Halliday, Alex N

2010-06-10

The meaning of the age of the Earth defined by lead isotopes has long been unclear. Recently it has been proposed that the age of the Earth deduced from lead isotopes reflects volatile loss to space at the time of the Moon-forming giant impact rather than partitioning into metallic liquids during protracted core formation. Here we show that lead partitioning into liquid iron depends strongly on carbon content and that, given a content of approximately 0.2% carbon, experimental and isotopic data both provide evidence of strong partitioning of lead into the core throughout the Earth's accretion. Earlier conclusions that lead is weakly partitioned into iron arose from the use of carbon-saturated (about 5% C) iron alloys. The lead isotopic age of the Earth is therefore consistent with partitioning into the core and with no significant late losses of moderately volatile elements to space during the giant impact.

New constraints on subduction inputs and volatile outputs along the Aleutian Arc

NASA Astrophysics Data System (ADS)

Lopez, T. M.; Fischer, T. P.; Plank, T. A.; Rizzo, A. L.; Rasmussen, D. J.; Cottrell, E.; Werner, C. A.; Kern, C.; Ilanko, T.; Buff, L.; Andrys, J.; Kelley, K. A.

2017-12-01

Volatile cycling drives volcanism in subduction zone settings. At arcs, volatiles can originate from the subducted slab, mantle wedge and/or crust. Each region has characteristic isotopic signatures, which can be used to fingerprint volatile provenance. We speculate that differences in subduction parameters, such as convergence angle, plate coupling and subducted sediment fluxes, may lead to differences in volatile provenance, which may in turn influence volcanic eruption style and frequency. Here we combine updated constraints on subduction inputs and volatile outputs to provide new insights into volatile cycling within the Aleutian Arc. The high proportion of organic carbon (80-100% to total carbon) in sediments subducting at the Aleutian trench stands out globally and predicts a light carbon isotopic composition of recycled volcanic fluids. We assess volatile outputs on volcanic timescales and along the arc by combining carbon (C), nitrogen (N) and helium (He) isotopic compositions of volcanic gases and new analyses of He and, where possible, C isotopes in olivine-hosted fluid inclusions. From our preliminary isotopic analyses of volcanic gases, we find a greater proportion of mantle-derived volatiles released from the Western segment of the Aleutian Arc (>40% mantle) compared with other volcanic arcs around the world (<30% mantle), where volatiles are sourced primarily from subducted or upper crustal carbonates. This trend may be due to the oblique convergence and low subducted sediment input in this region. The Aleutian Arc also exhibits among the lightest carbon isotope ratios of arcs worldwide (δ13C = -10 to -15‰), especially in the central part of the arc, where organic-bearing terrigneous sediment fills the trench and the convergence rate is high. New constraints on subduction inputs and outputs presented here will help discriminate between upper crustal and subducted carbon sources, and provide further insights into volatile cycling and subduction processes within the Aleutian Arc.

The Cd and Zn Isotope Compositions of PM10 in the Atmosphere of Paris: New Tools for Discrimination and Tracking of the Origin of Metallic Pollution

NASA Astrophysics Data System (ADS)

Petelet-Giraud, E.; Widory, D.; Innocent, C.; Quetel, C.; Le Bihan, O.; Fraboulet, I.; Forti, L.; Joos, E.; Goupil, G.; Canard, E.

2008-12-01

Due to their relatively high concentration in urban environments (from 10 to more than 50 μg.m-3), atmospheric particles (PM10) have potential damaging effects on the Public Health. Hence, the development of measures dealing with fine particulate matter is considered a priority by the EU Clean Air For Europe (CAFE) Program. Still, the origin of these airborne particles is subject to debate, as classical chemical methods showed their limitations. Recent studies have shown that stable isotopes of elements such as carbon, nitrogen or lead could be of great help in the search of new particle air pollution tracking tools. We will present here preliminary results on the pioneer use of stable isotope compositions of cadmium, zinc and mercury to help decipher the different possible origins of PM10 pollution in the atmosphere of Paris (France). Main potential sources were characterized: (1) waste incineration, (2) road traffic, (3) central heating and (4) coal-fired power plants. Results show that the use of cadmium (d114Cd) and zinc (d66Zn) isotopes, and the combination of both provides a reliable and precise tool for discriminating the different families of particle vectors. The isotope systematic of mercury (d200Hg) is more difficult to apprehend due to the low levels encountered (mercury is mainly present under gaseous form, but is still observed at low concentrations in particles), but does show significant variations between the different sources. Daily cumulative air samples were taken on three different locations, covering different scenarios in Paris city: 1) background pollution in Paris, 2) under the plume of a major pollution source and 3) Paris vicinity. Corresponding chemical and isotope analyses help identify the main vectors for the three elements (Cd, Zn and Hg) considered as well as assess their respective contributions to the levels of pollution observed.

Pb, Sr, and Nd isotopic compositions of a suite of Late Archean, igneous rocks, eastern Beartooth Mountains: implications for crust-mantle evolution

USGS Publications Warehouse

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

1988-01-01

A series of compositionally diverse, Late Archean rocks (2.74-2.79 Ga old) from the eastern Beartooth Mountains, Montana and Wyoming, U.S.A., have the same initial Pb, Sr, and Nd isotopic ratios. Lead and Sr initial ratios are higher and Nd initial ratios lower than would be expected for rocks derived from model mantle sources and strongly indicate the involvement of an older crustal reservoir in the genesis of these rocks. Crustal contamination during emplacement can be ruled out for a variety of reasons. Instead a model involving subduction of continental detritus and contamination of the overlying mantle as is often proposed for modern subduction environments is preferred. This contaminated mantle would have all the isotopic characteristics of mantle enriched by internal mantle metasomatism but would require no long-term growth or changes in parent to daughter element ratios. This contaminated mantle would make a good source for some of the Cenozoic mafic volcanics of the Columbia River, Snake River Plain, and Yellowstone volcanic fields that are proposed to come from ancient, enriched lithospheric mantle. The isotopic characteristics of the 2.70 Ga old Stillwater Complex are a perfect match for the proposed contaminated mantle which provides an alternative to crustal contamination during emplacement. The Pb isotopic characteristics of the Late Archean rocks of the eastern Beartooth Mountains are similar to those of other Late Archean rocks of the Wyoming Province and suggest that Early Archean, upper crustal rocks were common in this terrane. The isotopic signatures of Late Archean rocks in the Wyoming Province are distinctive from those of other Archean cratons in North America which are dominated by a MORB-like, Archean mantle source (Superior Province) and/or a long-term depleted crustal source (Greenland). ?? 1988.

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;

Using nitrate dual isotopic composition (δ15N and δ18O) as a tool for exploring sources and cycling of nitrate in an estuarine system: Elkhorn Slough, California

USGS Publications Warehouse

Wankel, Scott D.; Kendall, Carol; Paytan, Adina

2009-01-01

Nitrate (NO-3 concentrations and dual isotopic composition (??15N and ??18O) were measured during various seasons and tidal conditions in Elkhorn Slough to evaluate mixing of sources of NO-3 within this California estuary. We found the isotopic composition of NO-3 was influenced most heavily by mixing of two primary sources with unique isotopic signatures, a marine (Monterey Bay) and terrestrial agricultural runoff source (Old Salinas River). However, our attempt to use a simple two end-member mixing model to calculate the relative contribution of these two NO-3 sources to the Slough was complicated by periods of nonconservative behavior and/or the presence of additional sources, particularly during the dry season when NO-3 concentrations were low. Although multiple linear regression generally yielded good fits to the observed data, deviations from conservative mixing were still evident. After consideration of potential alternative sources, we concluded that deviations from two end-member mixing were most likely derived from interactions with marsh sediments in regions of the Slough where high rates of NO-3 uptake and nitrification result in NO-3 with low ?? 15N and high ??18O values. A simple steady state dual isotope model is used to illustrate the impact of cycling processes in an estuarine setting which may play a primary role in controlling NO -3 isotopic composition when and where cycling rates and water residence times are high. This work expands our understanding of nitrogen and oxygen isotopes as biogeochemical tools for investigating NO -3 sources and cycling in estuaries, emphasizing the role that cycling processes may play in altering isotopic composition. Copyright 2009 by the American Geophysical Union.