Measurement of stable isotopic enrichment and concentration of long-chain fatty acyl-carnitines in tissue by HPLC-MS.

PubMed

Sun, Dayong; Cree, Melanie G; Zhang, Xiao-Jun; Bøersheim, Elisabet; Wolfe, Robert R

2006-02-01

We have developed a new method for the simultaneous measurements of stable isotopic tracer enrichments and concentrations of individual long-chain fatty acyl-carnitines in muscle tissue using ion-pairing high-performance liquid chromatography-electrospray ionization quadrupole mass spectrometry in the selected ion monitoring (SIM) mode. Long-chain fatty acyl-carnitines were extracted from frozen muscle tissue samples by acetonitrile/methanol. Baseline separation was achieved by reverse-phase HPLC in the presence of the volatile ion-pairing reagent heptafluorobutyric acid. The SIM capability of a single quadrupole mass analyzer allows further separation of the ions of interest from the sample matrixes, providing very clean total and selected ion chromatograms that can be used to calculate the stable isotopic tracer enrichment and concentration of long-chain fatty acyl-carnitines in a single analysis. The combination of these two separation techniques greatly simplifies the sample preparation procedure and increases the detection sensitivity. Applying this protocol to biological muscle samples proves it to be a very sensitive, accurate, and precise analytical tool.

Defining a stable water isotope framework for isotope hydrology application in a large trans-boundary watershed (Russian Federation/Ukraine).

PubMed

Vystavna, Yuliya; Diadin, Dmytro; Huneau, Frédéric

2018-05-01

Stable isotopes of hydrogen ( 2 H) and oxygen ( 18 O) of the water molecule were used to assess the relationship between precipitation, surface water and groundwater in a large Russia/Ukraine trans-boundary river basin. Precipitation was sampled from November 2013 to February 2015, and surface water and groundwater were sampled during high and low flow in 2014. A local meteoric water line was defined for the Ukrainian part of the basin. The isotopic seasonality in precipitation was evident with depletion in heavy isotopes in November-March and an enrichment in April-October, indicating continental and temperature effects. Surface water was enriched in stable water isotopes from upstream to downstream sites due to progressive evaporation. Stable water isotopes in groundwater indicated that recharge occurs mainly during winter and spring. A one-year data set is probably not sufficient to report the seasonality of groundwater recharge, but this survey can be used to identify the stable water isotopes framework in a weakly gauged basin for further hydrological and geochemical studies.

Daily Variation of Heavy Carbon Dioxide in Mars Atmosphere

NASA Astrophysics Data System (ADS)

Livengood, T. A.; Kostiuk, Th; Kolasinski, J.; Hewagama, T.; Henning, W. G.; Sornig, M.; Stangier, T.; Krause, P.; Sonnabend, G.

2015-10-01

The atmosphere of Mars is significantly enriched in C and O heavy isotopes, detected by ground based high-resolution infrared spectroscopy as well as in situ measurements by the Phoenix lander and Mars Science Laboratory Curiosity rover. Heavy isotope enrichment is consistent with the preferential loss of light isotopes in eroding Mars' primordial atmosphere. Infrared spectroscopy of Mars collected in May 2012 as well as in March and May of 2014 from the NASA IRTF resolves rovibrational transitions of normal-isotope carbon dioxide as well as singly-substituted minor isotopologues, enabling remote measurements of carbon and oxygen isotope ratios as a function of latitude and local time of day. Earlier measurements obtained in October 2007 demonstrated that the relative abundance of O-18 increased linearly with increasing surface temperature over a relatively warm early-afternoon temperature range, but did not extend far enough to inspect the effect of late-afternoon cooling. These results imply that isotopically enriched gas is sequestered overnight when surface temperature is minimum and desorbs through the course of the day as temperature increases. Current spectroscopic constants indicate that the peak isotopic enrichment could be significantly greater than what has been measured in situ, apparently due to sampling the atmosphere at different time of day and surface temperature. The observing runs in 2012 and 2014 measured O-18 enrichment at several local times in both morning and afternoon sectors as well as at the subsolar, equatorial, and anti-subsolar latitudes. The two runs in 2014 have additionally observed O-17 and C-13 transitions in the morning sector, from local dawn to noon. These observations include a limited sampling of measurements over Gale Crater, which can be compared with contemporary in situ measurements by the Curiosity rover to investigate the degree of agreement between in situ and remote methods and potentially to calibrate the spectroscopic constants required to accurately evaluate isotope ratios all over Mars.

High-throughput simultaneous determination of plasma water deuterium and 18-oxygen enrichment using a high-temperature conversion elemental analyzer with isotope ratio mass spectrometry.

PubMed

Richelle, M; Darimont, C; Piguet-Welsch, C; Fay, L B

2004-01-01

This paper presents a high-throughput method for the simultaneous determination of deuterium and oxygen-18 (18O) enrichment of water samples isolated from blood. This analytical method enables rapid and simple determination of these enrichments of microgram quantities of water. Water is converted into hydrogen and carbon monoxide gases by the use of a high-temperature conversion elemental analyzer (TC-EA), that are then transferred on-line into the isotope ratio mass spectrometer. Accuracy determined with the standard light Antartic precipitation (SLAP) and Greenland ice sheet precipitation (GISP) is reliable for deuterium and 18O enrichments. The range of linearity is from 0 up to 0.09 atom percent excess (APE, i.e. -78 up to 5725 delta per mil (dpm)) for deuterium enrichment and from 0 up to 0.17 APE (-11 up to 890 dpm) for 18O enrichment. Memory effects do exist but can be avoided by analyzing the biological samples in quintuplet. This method allows the determination of 1440 samples per week, i.e. 288 biological samples per week. Copyright 2004 John Wiley & Sons, Ltd.

Isotope pattern deconvolution as rising tool for isotope tracer studies in environmental research

NASA Astrophysics Data System (ADS)

Irrgeher, Johanna; Zitek, Andreas; Prohaska, Thomas

2014-05-01

During the last decade stable isotope tracers have emerged as versatile tool in ecological research. Besides 'intrinsic' isotope tracers caused by the natural variation of isotopes, the intentional introduction of 'extrinsic' enriched stable isotope tracers into biological systems has gained significant interest. Hereby the induced change in the natural isotopic composition of an element allows amongst others for studying the fate and fluxes of metals, trace elements and species in organisms or provides an intrinsic marker or tag of particular biological samples. Due to the shoreless potential of this methodology, the number of publications dealing with applications of isotope (double) spikes as tracers to address research questions in 'real world systems' is constantly increasing. However, some isotope systems like the natural Sr isotopic system, although potentially very powerful for this type of application, are still rarely used, mainly because their adequate measurement/determination poses major analytical challenges; as e.g. Sr is available in significant amounts in natural samples. In addition, biological systems underlie complex processes such as metabolism, adsorption/desorption or oxidation/reduction. As a consequence, classic evaluation approaches such as the isotope dilution mass spectrometry equation are often not applicable because of the unknown amount of tracer finally present in the sample. Isotope pattern deconvolution (IPD), based on multiple linear regression, serves as simplified alternative data processing strategy to double spike isotope dilution calculations. The outstanding advantage of this mathematical tool lies in the possibility of deconvolving the isotope pattern in a spiked sample without knowing the quantities of enriched isotope tracer being incorporated into the natural sample matrix as well as the degree of impurities and species-interconversion (e.g. from sample preparation). Here, the potential of IPD for environmental tracer studies is critically discussed, where special emphasis is set on evaluating different data processing strategies on the example of enriched stable Sr isotopes.1 The analytical key parameters such as blank (Kr, Sr and Rb), variation of the natural Sr isotopic composition in the sample, mass bias, interferences (Rb) and total combined uncertainty are considered. A full metrological protocol for data processing using IPD is presented based on data gained during two transgenerational marking studies of fish, where the transfer of a Sr isotope double spike (84Sr and 86Sr) from female spawners of common carp (Cyprinus carpio L.) and brown trout (Salmo trutta f.f.)2 to the centre of the otoliths of their offspring was studied by (LA)-MC-ICP-MS. 1J. Irrgeher, A. Zitek, M. Cervicek and T. Prohaska, J. Anal. At. Spectrom., 2014, 29, 193-200. 2A. Zitek, J. Irrgeher, M. Kletzl, T. Weismann and T. Prohaska, Fish. Manage. Ecol., 2013, 20, 654-361.

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer.

PubMed

Spence, Michael J; Bottrell, Simon H; Thornton, Steven F; Richnow, Hans H; Spence, Keith H

2005-09-01

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.

Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C-valine isotopic ratios in complex biological samples.

PubMed

Godin, Jean-Philippe; Breuillé, Denis; Obled, Christiane; Papet, Isabelle; Schierbeek, Henk; Hopfgartner, Gérard; Fay, Laurent-Bernard

2008-10-01

On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure (13)C isotopic enrichment of underivatised amino acids (Asp, Thr-Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(delta(13)C) reported with this method was found to be below 1 per thousand . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (delta(13)C= -12.3 to 150.8 per thousand), the calculated root-mean-square (rms) of SD was 0.38 and 0.46 per thousand and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (delta(13)C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound (13)C-Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p>0.05). The results of this work indicate that the LC-IRMS was successful for high-precision (13)C isotopic measurements in tracer studies giving (13)C isotopic enrichment similar to the GC-C-IRMS but without the step of GC derivatisation. Therefore, for clinical studies requiring high-precision isotopic measurement, the LC-IRMS is the method of choice to measure the isotopic ratio.

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

NASA Astrophysics Data System (ADS)

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

2006-12-01

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

Tin isotope fractionation during magmatic processes and the isotope composition of the bulk silicate Earth

NASA Astrophysics Data System (ADS)

Wang, Xueying; Amet, Quentin; Fitoussi, Caroline; Bourdon, Bernard

2018-05-01

Tin is a moderately volatile element whose isotope composition can be used to investigate Earth and planet differentiation and the early history of the Solar System. Although the Sn stable isotope composition of several geological and archaeological samples has been reported, there is currently scarce information about the effect of igneous processes on Sn isotopes. In this study, high-precision Sn isotope measurements of peridotites and basalts were obtained by MC-ICP-MS with a double-spike technique. The basalt samples display small variations in δ124/116Sn ranging from -0.01 ± 0.11 to 0.27 ± 0.11‰ (2 s.d.) relative to NIST SRM 3161a standard solution, while peridotites have more dispersed and more negative δ124Sn values ranging from -1.04 ± 0.11 to -0.07 ± 0.11‰ (2 s.d.). Overall, basalts are enriched in heavy Sn isotopes relative to peridotites. In addition, δ124Sn in peridotites become more negative with increasing degrees of melt depletion. These results can be explained by different partitioning behavior of Sn4+ and Sn2+ during partial melting. Sn4+ is overall more incompatible than Sn2+ during partial melting, resulting in Sn4+-rich silicate melt and Sn2+-rich residue. As Sn4+ has been shown experimentally to be enriched in heavy isotopes relative to Sn2+, the effect of melting is to enrich residual peridotites in relatively more compatible Sn2+, which results in isotopically lighter peridotites and isotopically heavier mantle-derived melts. This picture can be disturbed partly by the effect of refertilization. Similarly, the presence of enriched components such as recycled oceanic crust or sediments could explain part of the variations in Sn isotopes in oceanic basalts. The most primitive peridotite analyzed in this study was used for estimating the Sn isotope composition of the BSE, with δ124Sn = -0.08 ± 0.11‰ (2 s.d.) relative to the Sn NIST SRM 3161a standard solution. Altogether, this suggests that Sn isotopes may be a powerful probe of redox processes in the mantle.

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

NASA Technical Reports Server (NTRS)

Chen, J. H.

1987-01-01

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

Isotope ratios of trace elements in samples from human nutrition studies determined by TIMS and ICP-MS: precision and accuracy compared.

PubMed

Turnlund, Judith R; Keyes, William R

2002-09-01

Stable isotopes are used with increasing frequency to trace the metabolic fate of minerals in human nutrition studies. The precision of the analytical methods used must be sufficient to permit reliable measurement of low enrichments and the accuracy should permit comparisons between studies. Two methods most frequently used today are thermal ionization mass spectrometry (TIMS) and inductively coupled plasma mass spectrometry (ICP-MS). This study was conducted to compare the two methods. Multiple natural samples of copper, zinc, molybdenum, and magnesium were analyzed by both methods to compare their internal and external precision. Samples with a range of isotopic enrichments that were collected from human studies or prepared from standards were analyzed to compare their accuracy. TIMS was more precise and accurate than ICP-MS. However, the cost, ease, and speed of analysis were better for ICP-MS. Therefore, for most purposes, ICP-MS is the method of choice, but when the highest degrees of precision and accuracy are required and when enrichments are very low, TIMS is the method of choice.

Isotopic Anomalies in Primitive Solar System Matter: Spin-State-Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

NASA Technical Reports Server (NTRS)

Wirstrom, Eva S.; Charnley, Steven B.; Cordiner, Martin A.; Milam, Stefanie N.

2012-01-01

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula, Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest N=15 enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system N-15 and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Human variation: delta/sup 13/C in adult bone collagen and the relation to diet in an isochronous C/sub 4/ (maize) archaeological population

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

Bumsted, M.P.

1984-10-01

Analysis of the stable isotopes of carbon (/sup 13/C and /sup 12/C in the standard ratio delta/sup 13/C) can distinguish the relative contributions of meat, cereals, and other plant foods to the diets of prehistoric people. This dissertation has examined an isochronous (non-cemetery) population of prehistoric Americans to ascertain the natural variation in isotopic composition amongst a group of maize-eaters. The seventeen adult females and fifteen adult males represent the largest human data set of prehistoric or contemporary samples for study of natural isotopic enrichment in which genetic, economic, disease, and temporal variables were controlled. Procedures for purifying remnant bonemore » protein from archaeological samples were developed or modified specifically to determine isotopic measurement. Cryogenic milling, cold acid demineralizing, gelatinizing, and an XAD-2 resin column were used to remove soil contaminants while preserving the chemical integrity of the bone protein. Measurements of total elemental carbon, hydrogen, and nitrogen of the unprocessed bone; amino acid analysis of selected gelatin samples; and stable carbon isotopic analysis were used to assess sample quality. Isotope values were lognormally distributed in this population (anti X = -1.15%) with the distribution and the means amongst males (anti X = -1.18%) significantly different from that of females (anti X = -1.13%). The isotopic diet model can be graphed with equilateral triangular coordinates to represent the relative contributions of meat, maize, and other plant foods. The graph can predict the maximum food contributions to the delta/sup 13/C of the prehistoric individuals measured. Isotopic variation in human bone protein is only partly due to the variable amount of enriched foods in the diet. Tissue enrichment which occurs at various metabolic levels must also be considered. 316 references, 20 figures, 10 tables.« less

Comparison of different mass spectrometry techniques in the measurement of L-[ring-13C6]phenylalanine incorporation into mixed muscle proteins

PubMed Central

Zabielski, Piotr; Ford, G. Charles; Persson, X. Mai; Jaleel, Abdul; Dewey, Jerry D.; Nair, K Sreekumaran

2013-01-01

Precise measurement of low enrichment of stable isotope labeled amino-acid tracers in tissue samples is a prerequisite in measuring tissue protein synthesis rates. The challenge of this analysis is augmented when small sample size is a critical factor. Muscle samples from human participants following an 8 hour intravenous infusion of L-[ring-13C6]phenylalanine and a bolus dose of L-[ring-13C6]phenylalanine in a mouse were utilized. Liquid Chromatography tandem mass spectrometry (LC/MS/MS), Gas Chromatography tandem mass spectrometry (GC/MS/MS) and Gas Chromatography/Mass spectrometry (GC/MS) were compared to the Gas Chromatography-Combustion-Isotope Ratio mass spectrometry (GC/C/IRMS), to measure mixed muscle protein enrichment of [ring13C6]phenylalanine enrichment. The sample isotope enrichment ranged from 0.0091 to 0.1312 Molar Percent excess (MPE). As compared with GC/C/IRMS, LC/MS/MS, GC/MS/MS and GC/MS showed coefficients of determination of R2 = 0.9962 and R2 = 0.9942, and 0.9217 respectively. However, the precision of measurements (coefficients of variation) for intra-assay are 13.0%, 1.7%, 6.3% and 13.5% and for inter-assay are 9.2%, 3.2%, 10.2% and 25% for GC/C/IRMS, LC/MS/MS, GC/MS/MS and GC/MS respectively. The muscle sample sizes required to obtain these results were 8μg, 0.8μg, 3μg and 3μg for GC/C/IRMS, LC/MS/MS, GC/MS/MS, and GC/MS respectively. We conclude that LC/MS/MS is optimally suited for precise measurements of L-[ring-13C6]phenylalanine tracer enrichment in low abundance and in small quantity samples. PMID:23378099

Comparison of pore water samplers and cryogenic distillation under laboratory and field conditions for soil water stable isotope analysis.

PubMed

Thoma, Michael; Frentress, Jay; Tagliavini, Massimo; Scandellari, Francesca

2018-02-15

We used pore water samplers (PWS) to sample for isotope analysis (1) only water, (2) soil under laboratory conditions, and (3) soil in the field comparing the results with cryogenic extraction (CE). In (1) and (2), no significant differences between source and water extracted with PWS were detected with a mean absolute difference (MAD) always lower than 2 ‰ for δ 2 H and 1 ‰ for δ 18 O. In (2), CE water was more enriched than PWS-extracted water, with a MAD respect to source water of roughly 8 ‰ for δ 2 H and 4 ‰ for δ 18 O. In (3), PWS water was enriched relative to CE water by 3 ‰ for δ 2 H and 0.9 ‰ for δ 18 O. The latter result may be due to the distinct water portions sampled by the two methods. Large pores, easily sampled by PWS, likely retain recent, and enriched, summer precipitation while small pores, only sampled by CE, possibly retain isotopically depleted water from previous winter precipitation or irrigation inputs. Accuracy and precision were greater for PWS relative to CE. PWS is therefore suggested as viable tool to extract soil water for stable isotope analysis, particularly for soils used in this study (sandy and silty loams).

The origin of volatile element depletion in early solar system material: Clues from Zn isotopes in chondrules

NASA Astrophysics Data System (ADS)

Pringle, Emily A.; Moynier, Frédéric; Beck, Pierre; Paniello, Randal; Hezel, Dominik C.

2017-06-01

Volatile lithophile elements are depleted in the different planetary materials to various degrees, but the origin of these depletions is still debated. Stable isotopes of moderately volatile elements such as Zn can be used to understand the origin of volatile element depletions. Samples with significant volatile element depletions, including the Moon and terrestrial tektites, display heavy Zn isotope compositions (i.e. enrichment of 66Zn vs. 64Zn), consistent with kinetic Zn isotope fractionation during evaporation. However, Luck et al. (2005) found a negative correlation between δ66Zn and 1/[Zn] between CI, CM, CO, and CV chondrites, opposite to what would be expected if evaporation caused the Zn abundance variations among chondrite groups. We have analyzed the Zn isotope composition of multiple samples of the major carbonaceous chondrite classes: CI (1), CM (4), CV (2), CO (4), CB (2), CH (2), CK (4), and CK/CR (1). The bulk chondrites define a negative correlation in a plot of δ66Zn vs 1/[Zn], confirming earlier results that Zn abundance variations among carbonaceous chondrites cannot be explained by evaporation. Exceptions are CB and CH chondrites, which display Zn systematics consistent with a collisional formation mechanism that created enrichment in heavy Zn isotopes relative to the trend defined by CI-CK. We further report Zn isotope analyses of chondrite components, including chondrules from Allende (CV3) and Mokoia (CV3), as well as an aliquot of Allende matrix. All chondrules are enriched in light Zn isotopes (∼500 ppm on 66Zn/64Zn) relative to the bulk, contrary to what would be expected if Zn were depleted during evaporation, on the other hand the matrix has a complementary heavy isotope composition. We report sequential leaching experiments in un-equilibrated ordinary chondrites, which show sulfides are isotopically heavy compared to silicates and the bulk meteorite by ca. +0.65 per mil on 66Zn/64Zn. We suggest isotopically heavy sulfides were removed from either chondrules or their precursors, thereby producing the light Zn isotope enrichments in chondrules.

On-line double isotope dilution laser ablation inductively coupled plasma mass spectrometry for the quantitative analysis of solid materials.

PubMed

Fernández, Beatriz; Rodríguez-González, Pablo; García Alonso, J Ignacio; Malherbe, Julien; García-Fonseca, Sergio; Pereiro, Rosario; Sanz-Medel, Alfredo

2014-12-03

We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6-21% for pressed pellets and 3-21% for fused solids were obtained from n=3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches. Copyright © 2014 Elsevier B.V. All rights reserved.

A novel membrane inlet mass spectrometer method to measure ¹⁵NH4₄⁺ for isotope-enrichment experiments in aquatic ecosystems.

PubMed

Yin, Guoyu; Hou, Lijun; Liu, Min; Liu, Zhanfei; Gardner, Wayne S

2014-08-19

Nitrogen (N) pollution in aquatic ecosystems has attracted much attention over the past decades, but the dynamics of this bioreactive element are difficult to measure in aquatic oxygen-transition environments. Nitrogen-transformation experiments often require measurement of (15)N-ammonium ((15)NH4(+)) ratios in small-volume (15)N-enriched samples. Published methods to determine N isotope ratios of dissolved ammonium require large samples and/or costly equipment and effort. We present a novel ("OX/MIMS") method to determine N isotope ratios for (15)NH4(+) in experimental waters previously enriched with (15)N compounds. Dissolved reduced (15)N (dominated by (15)NH4(+)) is oxidized with hypobromite iodine to nitrogen gas ((29)N2 and/or (30)N2) and analyzed by membrane inlet mass spectrometry (MIMS) to quantify (15)NH4(+) concentrations. The N isotope ratios, obtained by comparing the (15)NH4(+) to total ammonium (via autoanalyzer) concentrations, are compared to the ratios of prepared standards. The OX/MIMS method requires only small sample volumes of water (ca. 12 mL) or sediment slurries and is rapid, convenient, accurate, and precise (R(2) = 0.9994, p < 0.0001) over a range of salinities and (15)N/(14)N ratios. It can provide data needed to quantify rates of ammonium regeneration, potential ammonium uptake, and dissimilatory nitrate reduction to ammonium (DNRA). Isotope ratio results agreed closely (R = 0.998, P = 0.001) with those determined independently by isotope ratio mass spectrometry for DNRA measurements or by ammonium isotope retention time shift liquid chromatography for water-column N-cycling experiments. Application of OX/MIMS should simplify experimental approaches and improve understanding of N-cycling rates and fate in a variety of freshwater and marine environments.

Li Isotopes as Tracers of Fluid-Rock Interactions in Oceanic Hydrothermal Systems: Evidence From the Hess Deep Rift

NASA Astrophysics Data System (ADS)

Brant, C. O.; Coogan, L. A.; Gillis, K. M.

2004-12-01

Li isotopes have the potential to be powerful tracers of fluid-rock interactions at mid-ocean ridge hydrothermal systems due to the large isotopic difference between seawater (δ7Li = 31‰) and fresh MORB (δ7Li = 1.5 to 5.6 ‰). Sampling programs along tectonic escarpments at Hess Deep provide an ideal suite to examine the spatial variability of Li mobility and Li isotopic content within young (1 Ma) lavas and sheeted dikes formed at the fast-spreading East Pacific Rise towards the end of a segment. Previous work has shown that the lavas are relatively fresh, with minor alteration to clay minerals and Fe oxyhydroxides. Sheeted dikes are variably altered to amphibole-dominated assemblages, with localized zones where chlorite dominates. Sr and O isotope data correlate with these regional patterns. Preliminary data, collected by Thermo X-series quadrupole ICP-MS, show that the lavas have similar Li concentrations to fresh MORB (5 to 6 ppm) and are slightly enriched in δ7Li (4.1 to 7.7 ‰). There is a positive correlation between Li content and δ7Li within the lavas, however, the trend is not a simple mixing line between seawater and fresh MORB, being offset to lower δ7Li in the altered component. Similar to previous studies, these relationships support the prediction that 6Li is preferentially retained in low temperature clay minerals. Sheeted dykes are depleted in Li (0.8-4.63 ppm) and most samples are enriched in δ7Li (6.7-15.4 ‰) relative to fresh MORB. These samples show an inverse relationship between decreasing concentration and increasing isotopic enrichment. This implies that 6Li is not simply preferentially retained in the replacement mineral assemblages. The degree of isotopic enrichment appears to increase with increasing clinopyroxene alteration, and is greatest for amphibolite dominated assemblages. A broad positive correlation between Li concentration and δ18O is observed in the dikes. Thus Li isotopes are sensitive indicators of the nature and extent of hydrothermal interactions for both high and low temperature processes.

Li Isotopes as Tracers of Fluid-Rock Interactions in Oceanic Hydrothermal Systems: Evidence From the Hess Deep Rift

NASA Astrophysics Data System (ADS)

Brant, C. O.; Coogan, L. A.; Gillis, K. M.

2007-12-01

Li isotopes have the potential to be powerful tracers of fluid-rock interactions at mid-ocean ridge hydrothermal systems due to the large isotopic difference between seawater (δ7Li = 31‰) and fresh MORB (δ7Li = 1.5 to 5.6 ‰). Sampling programs along tectonic escarpments at Hess Deep provide an ideal suite to examine the spatial variability of Li mobility and Li isotopic content within young (1 Ma) lavas and sheeted dikes formed at the fast-spreading East Pacific Rise towards the end of a segment. Previous work has shown that the lavas are relatively fresh, with minor alteration to clay minerals and Fe oxyhydroxides. Sheeted dikes are variably altered to amphibole-dominated assemblages, with localized zones where chlorite dominates. Sr and O isotope data correlate with these regional patterns. Preliminary data, collected by Thermo X-series quadrupole ICP-MS, show that the lavas have similar Li concentrations to fresh MORB (5 to 6 ppm) and are slightly enriched in δ7Li (4.1 to 7.7 ‰). There is a positive correlation between Li content and δ7Li within the lavas, however, the trend is not a simple mixing line between seawater and fresh MORB, being offset to lower δ7Li in the altered component. Similar to previous studies, these relationships support the prediction that 6Li is preferentially retained in low temperature clay minerals. Sheeted dykes are depleted in Li (0.8-4.63 ppm) and most samples are enriched in δ7Li (6.7-15.4 ‰) relative to fresh MORB. These samples show an inverse relationship between decreasing concentration and increasing isotopic enrichment. This implies that 6Li is not simply preferentially retained in the replacement mineral assemblages. The degree of isotopic enrichment appears to increase with increasing clinopyroxene alteration, and is greatest for amphibolite dominated assemblages. A broad positive correlation between Li concentration and δ18O is observed in the dikes. Thus Li isotopes are sensitive indicators of the nature and extent of hydrothermal interactions for both high and low temperature processes.

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.

Improved sample preparation of glyphosate and methylphosphonic acid by EPA method 6800A and time-of-flight mass spectrometry using novel solid-phase extraction.

PubMed

Wagner, Rebecca; Wetzel, Stephanie J; Kern, John; Kingston, H M Skip

2012-02-01

The employment of chemical weapons by rogue states and/or terrorist organizations is an ongoing concern in the United States. The quantitative analysis of nerve agents must be rapid and reliable for use in the private and public sectors. Current methods describe a tedious and time-consuming derivatization for gas chromatography-mass spectrometry and liquid chromatography in tandem with mass spectrometry. Two solid-phase extraction (SPE) techniques for the analysis of glyphosate and methylphosphonic acid are described with the utilization of isotopically enriched analytes for quantitation via atmospheric pressure chemical ionization-quadrupole time-of-flight mass spectrometry (APCI-Q-TOF-MS) that does not require derivatization. Solid-phase extraction-isotope dilution mass spectrometry (SPE-IDMS) involves pre-equilibration of a naturally occurring sample with an isotopically enriched standard. The second extraction method, i-Spike, involves loading an isotopically enriched standard onto the SPE column before the naturally occurring sample. The sample and the spike are then co-eluted from the column enabling precise and accurate quantitation via IDMS. The SPE methods in conjunction with IDMS eliminate concerns of incomplete elution, matrix and sorbent effects, and MS drift. For accurate quantitation with IDMS, the isotopic contribution of all atoms in the target molecule must be statistically taken into account. This paper describes two newly developed sample preparation techniques for the analysis of nerve agent surrogates in drinking water as well as statistical probability analysis for proper molecular IDMS. The methods described in this paper demonstrate accurate molecular IDMS using APCI-Q-TOF-MS with limits of quantitation as low as 0.400 mg/kg for glyphosate and 0.031 mg/kg for methylphosphonic acid. Copyright © 2012 John Wiley & Sons, Ltd.

Isotopic Anomalies in Primitive Solar System Matter: Spin-State Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

NASA Technical Reports Server (NTRS)

Wirstrom, Eva S.; Charnley, Steven B.; Cordiner, Martin A.; Milan, Stefanie N.

2012-01-01

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15, This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar core. Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotop c enrichments measured in carbonaceous meteorites, However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores, We also show that while the nitriles, HCN and HNC, contain the greatest N-15 enrichment, this is not expected to correlate with extreme D emichment. These calculations therefore support the view that Solar System N-15 and D isotopic anomalies have an interstellar heritage, We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Quantification of Stable Isotope Traces Close to Natural Enrichment in Human Plasma Metabolites Using Gas Chromatography-Mass Spectrometry.

PubMed

Krämer, Lisa; Jäger, Christian; Trezzi, Jean-Pierre; Jacobs, Doris M; Hiller, Karsten

2018-02-14

Currently, changes in metabolic fluxes following consumption of stable isotope-enriched foods are usually limited to the analysis of postprandial kinetics of glucose. Kinetic information on a larger diversity of metabolites is often lacking, mainly due to the marginal percentage of fully isotopically enriched plant material in the administered food product, and hence, an even weaker 13 C enrichment in downstream plasma metabolites. Therefore, we developed an analytical workflow to determine weak 13 C enrichments of diverse plasma metabolites with conventional gas chromatography-mass spectrometry (GC-MS). The limit of quantification was increased by optimizing (1) the metabolite extraction from plasma, (2) the GC-MS measurement, and (3) most importantly, the computational data processing. We applied our workflow to study the catabolic dynamics of 13 C-enriched wheat bread in three human subjects. For that purpose, we collected time-resolved human plasma samples at 16 timepoints after the consumption of 13 C-labeled bread and quantified 13 C enrichment of 12 metabolites (glucose, lactate, alanine, glycine, serine, citrate, glutamate, glutamine, valine, isoleucine, tyrosine, and threonine). Based on isotopomer specific analysis, we were able to distinguish catabolic profiles of starch and protein hydrolysis. More generally, our study highlights that conventional GC-MS equipment is sufficient to detect isotope traces below 1% if an appropriate data processing is integrated.

Quantification of Stable Isotope Traces Close to Natural Enrichment in Human Plasma Metabolites Using Gas Chromatography-Mass Spectrometry

PubMed Central

Krämer, Lisa; Jäger, Christian; Jacobs, Doris M.; Hiller, Karsten

2018-01-01

Currently, changes in metabolic fluxes following consumption of stable isotope-enriched foods are usually limited to the analysis of postprandial kinetics of glucose. Kinetic information on a larger diversity of metabolites is often lacking, mainly due to the marginal percentage of fully isotopically enriched plant material in the administered food product, and hence, an even weaker 13C enrichment in downstream plasma metabolites. Therefore, we developed an analytical workflow to determine weak 13C enrichments of diverse plasma metabolites with conventional gas chromatography-mass spectrometry (GC-MS). The limit of quantification was increased by optimizing (1) the metabolite extraction from plasma, (2) the GC-MS measurement, and (3) most importantly, the computational data processing. We applied our workflow to study the catabolic dynamics of 13C-enriched wheat bread in three human subjects. For that purpose, we collected time-resolved human plasma samples at 16 timepoints after the consumption of 13C-labeled bread and quantified 13C enrichment of 12 metabolites (glucose, lactate, alanine, glycine, serine, citrate, glutamate, glutamine, valine, isoleucine, tyrosine, and threonine). Based on isotopomer specific analysis, we were able to distinguish catabolic profiles of starch and protein hydrolysis. More generally, our study highlights that conventional GC-MS equipment is sufficient to detect isotope traces below 1% if an appropriate data processing is integrated. PMID:29443915

Fast-Neutron Activation of Long-Lived Isotopes in Enriched Ge

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

Elliott, Steven R.; Guiseppe, Vincente; LaRoque, B. H.

2010-11-16

We measured the production of 57Co, 54Mn, 68Ge, 65Zn, and 60Co in an sample of Ge enriched in isotope 76 due to high-energy neutron interactions. These isotopes are critical in understanding background in Ge detectors used for double-beta decay experiments. These isotopes are produced by cosmogenic-neutron interactions in the detectors while they reside on the Earth's surface. We compared the measured production to that predicted by cross-section calculations based on CEM03.02. The cross section calculations over-predict our measurements by approximately a factor of 2-3 depending on isotope. We then use the measured cosmic-ray neutron ux and our results to predictmore » the cosmogenic production rate with an accuracy near 15%.« less

Preliminary study on copper isotopes of the Zijinshan ore field, Fujian Province, SE China

NASA Astrophysics Data System (ADS)

Zhao, Hai-Xiang

2017-04-01

Zijinshan Cu-Au polymetallic ore field is located in Southeast China, tectonically belonging to the Interior Cathaysia Block. It is a complete porphyry-epithermal mineralization system, including Luoboling porphyry Cu-Mo deposit, Zijinshan high sulfidation Cu-Au deposit, Yueyang low sulfidation Ag-Au deposit, Wuziqilong and Longjiangting transitional style Cu deposits, etc. Main ore minerals from Zijinshan and Wuziqilong deposits are covellite and digenite. Copper isotopic compositions of these two minerals were analyzed. Copper isotope ratios are reported in the standard delta notation: δ65 Cu‰¯[ (65Cu/63Cu)Sample/(65Cu/63Cu) ERM-AE633-1] ×1000. The overall δ65Cu values for the analysed samples vary from -2.76 to 1.33‰Ṫhe Zijinshan Cu-Au deposit show large Cu isotopic variability (-2.76 to 1.33), among which covellite samples range from -2.76‰ to 0.38‰ with -0.79‰ in average and digenite samples range from -1.8‰ to 1.33‰ with -0.11‰ in average. During the leaching process of hypogene sulphides, 65Cu was leached more easily and then trapped in the supergene enrichment zone. Therefore, enrichment minerals should be enriched in 65Cu and the leached cap enriched in 63Cu. Thus the relationship of δ65Cu values for different Cu reservoirs should be leached cap minerals < hypogene sulphides < enrichment minerals. Nonexistence of enriched δ65Cu values indicate that the major copper minerals (mainly covellite and digenite) in the Zijinshan Cu-Au deposit and Wuziqilong Cu deposit are of hypogene origin rather than secondary origin. At the Wuziqilong Cu deposit, Cu isotopes has narrow range from 0.16‰ to 0.43‰ with 0.31‰ in average, which is typically of hypogene origin. Two coexisting covellite -digenite fractionations (δ65Cu =δ65Cucovellite - δ65Cudigenite) are 0.27‰ and 0.18‰ relatively. For minerals of the Cu-S system, from chalcocite (Cu2S) to covellite (CuS), proportions of Cu(II) become higher and higher. The classical definition of the crystallographic structure of covellite indicated that one third of the Cu is Cu(II) and digenite (Cu1.8S) has one ninth of Cu(II). Therefore, covellite is more oxidized species and has higher δ65Cu compared with coexisting digenite.

The sources and time-integrated evolution of diamond-forming fluids - Trace elements and isotopic evidence

NASA Astrophysics Data System (ADS)

Klein-BenDavid, Ofra; Pearson, D. Graham; Nowell, Geoff M.; Ottley, Chris; McNeill, John C. R.; Logvinova, Alla; Sobolev, Nikolay V.

2014-01-01

Sub-micrometer inclusions in fibrous diamond growth zones carry high-density fluids (HDF) from which the host diamonds have precipitated. The chemistry of these fluids is our best opportunity of characterizing the diamond-forming environment. The major and trace element patterns of diamond-forming fluids vary widely. Such elemental signatures can be easily modified by a variety of mantle processes whereas radiogenic isotopes give a clear fingerprint of the time-integrated evolution of the fluid source region. Thus, the combination of elemental and isotope data is a powerful tool in constraining the origin of fluids from which diamonds precipitate. Here we present combined trace element composition (34 diamonds) and Sr isotopic data (23 diamonds) for fluid-rich diamonds from six worldwide locations. The Nd and Pb isotopic composition of two of the diamonds were also obtained. Several of the samples were analyzed in at least 2 locations to investigate variations in the fluid during diamond growth. The data was acquired using an off-line laser sampling technique followed by solution ICPMS and TIMS analysis. The Sr isotopic compositions of diamond fluids from the different suites range between convecting mantle values for Udachnaya (87Sr/86Sr363 = 0.70300 ± 16 to 0.70361 ± 4), to highly enriched values, up to 87Sr/86Sr = 0.72330 ± 3, for a diamond from Congo. No isochronous relationships were observed in any of the suites. The lowest Nd isotopic composition recorded so far in a diamond is from Congo (εNd71 = -40.4), which also contains the most radiogenic Sr isotopic composition. In contrast, a less enriched but still rather unradiogenic Nd isotope composition (εNd540 = -11) was obtained for a diamond from Snap Lake, which has moderately radiogenic Sr isotopic enrichment (87Sr/86Sr540 = 0.70821 ± 1). The Pb isotopic system measured in one diamond indicates a complex evolution for the fluid source, with extreme 207Pb/204Pb ratio (15.810 ± 3) and moderate, kimberlite-like 206Pb/204Pb and 208Pb/204Pb ratios. A multi-stage evolution of the diamond-forming fluids source can be constrained from our new isotopic data, indicating an Achaean enrichment event resulting in elevated U/Pb, Rb/Sr ratios and enrichment in LREEs. This source underwent a more recent fractionation, in the last 500 Myr that may have been related to the diamond-forming event. There is a strong correspondence between fluids with relatively unradiogenic Sr isotopes and relatively low (La, Nd, Sm)/(Nb, Zr) and (Ba, Th)/(Nb) ratios. Sr isotopic enrichment is accompanied by an increase in these ratios. The least trace element enriched and most isotopically depleted fluids are from the high-Mg carbonatitic suite. Thus, HDFs could be derived from asthenospheric mantle as low degree melts that interact to varying degrees with an ancient, metasomatized, rutile- and phlogopite bearing, sub continental lithosphere mantle. The internal heterogeneity in the Sr isotopic ratios within a single diamond suite and even within single diamonds may indicate fluid-mixing processes. Such mixing may occur during migration through preferred mantle veins and may be affected by the small-scale geochemical variability within them.

Effects of glacial meltwater inflows and moat freezing on mixing in an ice-covered antarctic lake as interpreted from stable isotope and tritium distributions

USGS Publications Warehouse

Miller, L.G.; Aiken, G.R.

1996-01-01

Perennially ice-covered lakes in the McMurdo Dry Valleys have risen several meters over the past two decades due to climatic warming and increased glacial meltwater inflow. To elucidate the hydrologic responses to changing climate and the effects on lake mixing processes we measured the stable isotope (??18O and ??D) and tritium concentrations of water and ice samples collected in the Lake Fryxell watershed from 1987 through 1990. Stable isotope enrichment resulted from evaporation in stream and moat samples and from sublimation in surface lake-ice samples. Tritium enrichment resulted from exchange with the postnuclear atmosphere in stream and moat samples. Rapid injection of tritiated water into the upper water column of the make and incorporation of this water into the ice cover resulted in uniformly elevated tritium contents (> 3.0 TU) in these reservoirs. Tritium was also present in deep water, suggesting that a component of bottom water was recently at the surface. During summer, melted lake ice and stream water forms the moat. Water excluded from ice formation during fall moat freezing (enriched in solutes and tritium, and depleted in 18O and 2H relative to water below 15-m depth) may sink as density currents to the bottom of the lake. Seasonal lake circulation, in response to climate-driven surface inflow, is therefore responsible for the distribution of both water isotopes and dissolved solutes in Lake Fryxell.

Minor isotope safeguards techniques (MIST): Analysis and visualization of gas centrifuge enrichment plant process data using the MSTAR model

NASA Astrophysics Data System (ADS)

Shephard, Adam M.; Thomas, Benjamin R.; Coble, Jamie B.; Wood, Houston G.

2018-05-01

This paper presents a development related to the use of minor isotope safeguards techniques (MIST) and the MSTAR cascade model as it relates to the application of international nuclear safeguards at gas centrifuge enrichment plants (GCEPs). The product of this paper is a derivation of the universal and dimensionless MSTAR cascade model. The new model can be used to calculate the minor uranium isotope concentrations in GCEP product and tails streams or to analyze, visualize, and interpret GCEP process data as part of MIST. Applications of the new model include the detection of undeclared feed and withdrawal streams at GCEPs when used in conjunction with UF6 sampling and/or other isotopic measurement techniques.

Stable Carbon Isotope Characterization of CO2 Loss in Acid Mine Drainage Impacted Stream Water: Observations from a Laboratory Experiment

NASA Astrophysics Data System (ADS)

Ali, H. N.; Atekwana, E. A.

2007-05-01

Water from an acid mine drainage spring, ground water from a mine tailings pile, stream water and tap water were acidified to simulate acid mine drainage (AMD) contamination. The objective was to determine how acidification of stream water by AMD affected DIC loss and carbon isotope fraction. Two 20 L HDP containers (reactors) containing samples from each source were left un-acidified and allowed to evolve under ambient conditions for several weeks in the laboratory and two others were acidified. Acidification was carried out progressively with sulfuric acid to pH <3. For acidified samples, one reactor was acidified open to the atmosphere and the other closed from contact with atmosphere and CO2(g) was collected under vacuum. The un-acidified samples did not show significant alkalinity and DIC loss, and the 13C of DIC was enriched with time. The acidified samples showed decrease in alkalinity and DIC and increase in the 13C of DIC and CO2(g) with progressive acidification. The enrichment of 13C of DIC for un-acidified samples was due to exchange with atmospheric CO2. On the other hand, the 13C enrichment in the acidified samples was due to fractionation during dehydration of HCO3- and diffusive loss of CO2(g) from the aqueous phase. The actual values measured depended on the amount of CO2 lost from the aqueous phase during acidification. Samples with greater CO2 loss (closed acidification) had greater 13C enrichment. Beyond the HCO3- titration end point, the δ13C of DIC and CO2(g) was similar and nearly constant. The result of this study suggests that AMD effects on DIC can be modeled as a first order kinetic reaction and the isotope enrichment modeled using Rayleigh distillation.

Investigation of isotope effects of ozone as a function of temperature

NASA Astrophysics Data System (ADS)

McMahon, Daniel J.

Ozone is an important oxidizer in the atmosphere and plays a crucial role as a cleanser, removing various compounds such NOx and SOx. It also is intriguing to those that study stable isotopes as it has a unique signature found in no other oxygen containing molecule. Ozone is observed to fractionate mass independently, which means it does not follow the typical delta 17O /delta18O = 0.52 ratio expected for molecules enriched with 17O and 18O. The magnitude of ozone's mass independent enrichment has been studied in laboratory experiments and atmospheric observations but its explanation is still incomplete. Symmetry of the isotopically substituted ozone is postulated to be the source of mass independent enrichment and this thesis will build on that explanation to examine the magnitude of isotopic enrichment as a function of temperature. Understanding of the kinetics of ozone formation has come a long way from early predictions of enrichments >200‰ However, while our ability to accurately model ozone's bulk isotopic enrichment has improved to include separate rates for the formation of asymmetric and symmetric ozone, rate experiments are sparse for 17O and of low precision. To improve our understanding of ozone's enrichment, this study presents a temperature dependent enrichment experiment and series of models to predict asymmetric mass independent fractionation. This also served to examine ozone's enrichment in the troposphere by using an open flow experimental setup which is in contrast to previous works examining ozone enrichment in a closed system. Our experimental observations show that under tropospheric conditions, ozone should have delta17O ≈ 75‰, delta18O ≈ 80‰, and delta 17O ≈ 33‰. The models were able to match experimental values, often within 1‰, and with minimal assumptions, predict asymmetric ozone to have delta17O=47.5‰. This value is important as ozone transfers its terminal atom to species it oxidizes and will be the starting point to using ozone as a tracer in atmospheric reactions. Modeling improves our understanding of ozone's enrichments but these predictions must be validated by atmospheric observations. Previous tropospheric ozone sampling studies produced data of low precision but still showed relatively good agreement with our laboratory observations. In order to obtain better isotopic data a proxy method for sampling ozone's terminal atom is needed. Reaction with nitrite in solution is promising as the reaction is rapid and efficient. However we were unable to obtain tropospheric ozone observations as nitrite processing methods could not be perfected to remove nitrate blank concentrations. We do present the merits of using nitrite to react with atmospheric ozone and the suggest purification steps that may allow this method to be successful in the future.

Silylated Derivatives Retain Carbon and Alter Expected 13C-Tracer Enrichments Using Continuous Flow-Combustion-Isotope Ratio Mass Spectrometry

PubMed Central

Shinebarger, Steven R.; Haisch, Michael; Matthews, Dwight E.

2008-01-01

Continuous-flow inlets from oxidation reactors are commonly used systems for biological sample introduction into isotope ratio mass spectrometers (IRMS) to measure 13C enrichment above natural abundance. Because the samples must be volatile enough to pass through a gas chromatograph, silylated derivatization reactions are commonly used to modify biological molecules to add the necessary volatility. Addition of a t-butyldimethylsilyl (TBDMS) group is a common derivatization approach. However, we have found that samples do not produce the expected increment in measured 13C abundance as the TBDMS derivatives. We have made measurements of 13C enrichment of leucine and glutamate standards of known 13C enrichment using derivatives without silicon (N-acetyl n-propyl ester), with silicon (TBDMS), and an intermediate case. The measurements of 13C in amino acids derivatized without silicon were as expected. The 13C enrichment measurements using the TBDMS derivative were higher than expected, but could be corrected to produce the expected 13C enrichment measurement by IRMS if one carbon was removed per silicon. We postulate that the silicon in the derivative forms silicon carbide compounds in the heated cupric oxide reactor, rather than forming silicon dioxide. Doing so reduces the amount of CO2 formed from the carbon in the sample. Silylated derivatives retain carbon with the silicon and must be used carefully and with correction factors to measure 13C enrichments by continuous-flow IRMS. PMID:12510745

Carbon and hydrogen isotopic reversals in deep basin gas: Evidence for limits to the stability of hydrocarbons

USGS Publications Warehouse

Burruss, R.C.; Laughrey, C.D.

2010-01-01

During studies of unconventional natural gas reservoirs of Silurian and Ordovician age in the northern Appalachian basin we observed complete reversal of the normal trend of carbon isotopic composition, such that ??13C methane (C1) >??13C ethane (C2) >??13C propane (C3). In addition, we have observed isotopic reversals in the ??2H in the deepest samples. Isotopic reversals cannot be explained by current models of hydrocarbon gas generation. Previous observations of partial isotopic reversals have been explained by mixing between gases from different sources and thermal maturities. We have constructed a model which, in addition to mixing, requires Rayleigh fractionation of C2 and C3 to cause enrichment in 13C and create reversals. In the deepest samples, the normal trend of increasing enrichment of 13C and 2H in methane with increasing depth reverses and 2H becomes depleted as 13C becomes enriched. We propose that the reactions that drive Rayleigh fractionation of C2 and C3 involve redox reactions with transition metals and water at late stages of catagenesis at temperatures on the order of 250-300??C. Published ab initio calculated fractionation factors for C-C bond breaking in ethane at these temperatures are consistent with our observations. The reversed trend in ??2H in methane appears to be caused by isotopic exchange with formation water at the same temperatures. Our interpretation that Rayleigh fractionation during redox reactions is causing isotopic reversals has important implications for natural gas resources in deeply buried sedimentary basins. ?? 2010.

An assessment of the isotopic (2H/18O) integrity of water samples collected and stored by unattended precipitation totalizers

NASA Astrophysics Data System (ADS)

Terzer, Stefan; Wassenaar, Leonard I.; Douence, Cedric; Araguas-Araguas, Luis

2016-04-01

The IAEA-WMO Global Network of Isotopes in Precipitation (GNIP) provides worldwide δ18O and δ2H data for numerous hydrological and climatological studies. The traditional GNIP sample collection method relies on weather station operators to accumulate precipitation obtained from manual rain gauges. Over the past decades, widespread weather station automatization resulted in the increased use of unattended precipitation totalizers that accumulate and store the rainwater in the field for up to one month. Several low-tech measures were adopted to prevent in situ secondary evaporative isotopic enrichment (SEE) of totalized water samples (i.e. disequilibrium isotopic fractionation after precipitation is stored in the collection device). These include: (a) adding a 0.5-1 cm floating layer of paraffin oil to the totalizer bottle, (b) using an intake tube leading from the collection funnel and submerged to the bottom of the totalizer bottle, or (c) placing a table tennis ball in the funnel aiming to reduce evaporation of the collected water from the receiving bottle to the atmosphere. We assessed the isotopic integrity of stored rainwater samples for three totalizers under controlled settings: each aforementioned totalizer was filled with a 100 or 500 mL of isotopically known water and installed in the field with the intake funnels sheltered to prevent rainwater collection. Potential evapotranspiration (PET) was obtained from on-site meteorological recordings. Stored evaporative loss from each totalizer was evaluated on a monthly basis; gravimetrically and by analysing δ18O and δ2H of the stored water, for a period of 6 months and a cumulative PET of ˜500 mm. The gravimetric and isotope results revealed that for smaller water volumes (100 ml, corresponding to ca. 5 mm of monthly precipitation), negligible isotope enrichment (δ18O) was observed in the paraffin-oil based totalizer, whereas unacceptable evaporative isotope effects were observed for the ball-in-funnel collector. For the submerged-tube sampler, the evaporative effect depended on the amount of stored water: 100 ml showed unacceptable isotopic enrichment, whereas the SEE of 500 ml stored water was acceptable. These data allowed us to estimate the impact of secondary evaporative enrichment on a device-specific basis as a function of PET. Based on global PET grids (e.g. CGIAR data), and benchmarking the expected SEE against the reasonable uncertainty of isotope spectrometry (< ±0.1‰ for δ18O), these findings reveal the most suitable totalizer device for any given climatic condition. Under extreme conditions (e.g. high aridity, little precipitation vs. high PET), a paraffin-oil based rain totalizer is most appropriate for monthly collections. Submerged-tube samplers may be considered if either a higher frequency of collection were possible, or monthly under pluvial/temperate climate conditions. The use of ball-in-funnel type totalizers are not recommended at all, unless samples could be collected on a daily basis.

Daily Variation of Isotope Ratios in Mars Atmospheric Carbon Dioxide

NASA Astrophysics Data System (ADS)

Livengood, Timothy A.; Kostiuk, Theodor; Kolasinski, John R.; Hewagama, Tilak; Henning, Wade G.; Sornig, Manuela; Stangier, Tobias; Krause, Pia; Sonnabend, Guido; Mahaffy, Paul R.

2014-11-01

The atmosphere of Mars has been shown by ground based high-resolution infrared spectroscopy and in situ measurements with the Phoenix lander and Mars Science Laboratory Curiosity rover to be enriched in C and O heavy isotopes, consistent with preferential loss of light isotopes in eroding Mars’ primordial atmosphere. The relative abundance of heavy isotopes, combined with contemporary measurements of loss rates to be obtained with MAVEN, will enable estimating the primordial atmospheric inventory on Mars. IR spectroscopy of Mars collected in May 2012 as well as in March and May of 2014 from the NASA IRTF has resolved transitions of all three singly-substituted minor isotopologues of carbon dioxide in addition to the normal isotope, enabling remote measurements of all the carbon and oxygen isotope ratios as a function of latitude, longitude, and time of day. Earlier measurements obtained in October 2007 demonstrated that the relative abundance of O-18 increased linearly with increasing surface temperature over a relatively warm early-afternoon temperature range, but did not extend far enough to inspect the effect of late-afternoon cooling. These results imply that isotopically enriched gas is sequestered overnight when surface temperature is minimum and desorbs through the course of the day as temperature increases. Current spectroscopic constants indicate that the peak isotopic enrichment could be significantly greater than what has been measured in situ, apparently due to sampling the atmosphere at different time of day and surface temperature. The observing runs in 2012 and 2014 measured O-18 enrichment at several local times in both morning and afternoon sectors as well as at the subsolar, equatorial, and anti-subsolar latitudes. The two runs in 2014 have additionally observed O-17 and C-13 transitions in the morning sector, from local dawn to noon. These observations include a limited sampling of measurements over Gale Crater, which can be compared with contemporary in situ measurements by the Curiosity rover to investigate the degree of agreement between in situ and remote methods and potentially to calibrate the spectroscopic constants required to accurately evaluate isotope ratios all over Mars.

Status of stable isotope enrichment, products, and services at the Oak Ridge National Laboratory

NASA Astrophysics Data System (ADS)

Scott Aaron, W.; Tracy, Joe G.; Collins, Emory D.

1997-02-01

The Oak Ridge National Laboratory (ORNL) has been supplying enriched stable and radioactive isotopes to the research, medical, and industrial communities for over 50 y. Very significant changes have occurred in this effort over the past several years, and, while many of these changes have had a negative impact on the availability of enriched isotopes, more recent developments are actually improving the situation for both the users and the producers of enriched isotopes. ORNL is still a major producer and distributor of radioisotopes, but future isotope enrichment operations to be conducted at the Isotope Enrichment Facility (IEF) will be limited to stable isotopes. Among the positive changes in the enriched stable isotope area are a well-functioning, long-term contract program, which offers stability and pricing advantages; the resumption of calutron operations; the adoption of prorated conversion charges, which greatly improves the pricing of isotopes to small users; ISO 9002 registration of the IEF's quality management system; and a much more customer-oriented business philosophy. Efforts are also being made to restore and improve upon the extensive chemical and physical form processing capablities that once existed in the enriched stable isotope program. Innovative ideas are being pursued in both technical and administrative areas to encourage the beneficial use of enriched stable isotopes and the development of related technologies.

Determination of urea kinetics by isotope dilution with [13C]urea and gas chromatography-isotope ratio mass spectrometry (GC-IRMS) analysis.

PubMed

Kloppenburg, W D; Wolthers, B G; Stellaard, F; Elzinga, H; Tepper, T; de Jong, P E; Huisman, R M

1997-07-01

1. Stable urea isotopes can be used to study urea kinetics in humans. The use of stable urea isotopes for studying urea kinetic parameters in humans on a large scale is hampered by the high costs of the labelled material. We devised a urea dilution for measurement of the distribution volume, production rate and clearance of urea in healthy subjects and renal failure patients using the inexpensive single labelled [13C]urea isotope with subsequent analysis by headspace chromatography-isotope ratio MS (GC-IRMS) of the [13C]urea enrichment. 2. The method involves measurement of the molar percentage excess of [13C]urea in plasma samples taken over a 4 h period after an intravenous bolus injection of [13C]urea. During the sample processing procedure, the plasma samples together with calibration samples containing a known molar percentage excess of [13C]urea are acidified with phosphoric acid to remove endogenous CO2, and are subsequently incubated with urease to convert the urea present in the plasma samples into CO2. The 13C enrichment of the generated CO2 is analysed by means of GC-IRMS. This method allows measurement of the molar percentage excess of [13C]urea to an accuracy of 0.02%. 3. Reproducibility studies showed that the sample processing procedure [within-run coefficient of variation (CV) < 2.8% and between-run CV < 8.8%] and the GC-IRMS analysis (within-day CV < 1.3% and between-day CV < 1.3%) could be repeated with good reproducibility. 4. In clinical urea kinetic studies in a healthy subject and in a renal failure patient without residual renal function, reproducible values of the distribution volume, production rate and clearance of urea were determined using minimal amounts of [13C]urea (25-50 mg). 5. Because only low [13C]urea enrichments are needed in this urea dilution method using GC-IRMS analysis, the costs of urea kinetic studies are reduced considerably, especially in patients with renal failure.

Microscale Variations in the 13C Content of the Murchison Meteorite

NASA Astrophysics Data System (ADS)

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

1993-07-01

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

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.

Method for enriching a middle isotope using vibration-vibration pumping

DOEpatents

Rich, Joseph W.; Homicz, Gregory F.; Bergman, Richard C.

1989-01-01

Method for producing isotopically enriched material by vibration-vibration excitation of gaseous molecules wherein a middle mass isotope of an isotopic mixture including lighter and heavier mass isotopes preferentially populates a higher vibrational mode and chemically reacts to provide a product in which it is enriched. The method can be used for vibration-vibration enrichment of .sup.17 O in a CO reactant mixture.

Trace Element and Cu Isotopic Tracers of Subsurface Flow and Transport in Wastewater Irrigated Soils

NASA Astrophysics Data System (ADS)

Carte, J.; Fantle, M. S.

2017-12-01

An understanding of subsurface flow paths is critical for quantifying the fate of contaminants in wastewater irrigation systems. This study investigates the subsurface flow of wastewater by quantifying the distribution of trace contaminants in wastewater irrigated soils. Soil samples were collected from the upper 1m of two wetlands at Penn State University's wastewater irrigation site, at which all effluent from the University's wastewater treatment plant has been sprayed since 1983. Major and trace element and Cu isotopic composition were determined for these samples, in addition to wastewater effluent and bedrock samples. The upper 20 cm of each wetland shows an enrichment of Bi, Cd, Cr, Cu, Mo, Ni, Pb, and Zn concentrations relative to deep (>1m) soils at the site by a factor of 1.7-3.5. Each wetland also has a subsurface clay rich horizon with Bi, Cu, Li, Ni, Pb, and Zn concentrations enriched by a factor of 1.4 to 5 relative to deep soils. These subsurface horizons directly underlie intervals that could facilitate preferential effluent flow: a gravel layer in one wetland, and a silty loam with visible mottling, an indication of dynamic water saturation, in the other. Trace metal concentrations in other horizons from both wetlands fall in the range of the deep soils. Significant variability in Cu isotopic composition is present in soils from both wetlands, with δ65Cu values ranging from 0.74‰ to 5.09‰. Soil δ65Cu correlates well with Cu concentrations, with lighter δ65Cu associated with higher concentrations. The Cu isotopic composition of the zones of metal enrichment are comparable to the ostensible average wastewater effluent δ65Cu value (0.61‰), while other horizons have considerably heavier δ65Cu values. We hypothesize that wastewater is the source of the metal enrichments, as each of the enriched elements are present as contaminants in wastewater, and the enrichments are located in clay-rich horizons conducive to trace metal immobilization due to adsorption. This hypothesis will be further tested by modeling with the reactive transport code CrunchTope. This study provides evidence that trace element and isotopic composition of soils can be useful tracers of subsurface hydrologic pathways and elemental fate and transport.

Are leaf physiological traits related to leaf water isotopic enrichment in restinga woody species?

PubMed

Rosado, Bruno H P; De Mattos, Eduardo A; Sternberg, Leonel Da S L

2013-09-01

During plant-transpiration, water molecules having the lighter stable isotopes of oxygen and hydrogen evaporate and diffuse at a faster rate through the stomata than molecules having the heavier isotopes, which cause isotopic enrichment of leaf water. Although previous models have assumed that leaf water is well-mixed and isotopically uniform, non-uniform stomatal closure, promoting different enrichments between cells, and different pools of water within leaves, due to morpho-physiological traits, might lead to inaccuracies in isotopic models predicting leaf water enrichment. We evaluate the role of leaf morpho-physiological traits on leaf water isotopic enrichment in woody species occurring in a coastal vegetation of Brazil known as restinga. Hydrogen and oxygen stable isotope values of soil, plant stem and leaf water and leaf traits were measured in six species from restinga vegetation during a drought and a wet period. Leaf water isotopic enrichment relative to stem water was more homogeneous among species during the drought in contrast to the wet period suggesting convergent responses to deal to temporal heterogeneity in water availability. Average leaf water isotopic enrichment relative to stem water during the drought period was highly correlated with relative apoplastic water content. We discuss this observation in the context of current models of leaf water isotopic enrichment as a function of the Péclet effect. We suggest that future studies should include relative apoplastic water content in isotopic models.

Bioaccumulation and enantiomeric profiling of organochlorine pesticides and persistent organic pollutants in the killer whale (Orcinus orca) from British and Irish waters.

PubMed

McHugh, Brendan; Law, Robin J; Allchin, Colin R; Rogan, Emer; Murphy, Sinead; Foley, M Barry; Glynn, Denise; McGovern, Evin

2007-11-01

Concentrations and enantiomeric profiles for a range of organochlorine compounds are reported in blubber samples from a number of individual killer whales (Orcinus orca) from British and Irish waters. Elevated contaminant levels and enriched isotopic ratios were determined in one individual whale sampled in the Scottish Western Isles compared to the others suggesting marine mammal based dietary influences. The potential application of isotopic ratios to model contaminant uptake, enantioselective enrichment and accumulation is demonstrated. Data are presented which provide information on enantioselective enrichment factors (EFs) for o,p'-DDT, alpha-HCH and toxaphene congeners CHB26 and CHB 50. This dataset further improves the current database on reported levels of a number of contaminants and provides additional background information on potential metabolic processes in killer whales from British and Irish waters.

Isotopic composition of hydrogen in insoluble organic matter from cherts

NASA Technical Reports Server (NTRS)

Krishnamurthy, R. V.; Epstein, S.

1991-01-01

Robert (1989) reported the presence of unusually enriched hydrogen in the insoluble HF-HCl residue extracted from two chert samples of Eocene and Pliocene ages. Since the presence of heavy hydrogen might be due to the incorporation of extraterrestrial materials, we desired to reexamine the same samples to isolate the D-rich components. Our experiments did not reveal any D-rich components, but the hydrogen isotope composition of the insoluble residue of the two chert samples was well within the range expected for terrestrial organic matter. We also describe a protocol that needs to be followed in the hydrogen isotope analysis of any insoluble organic matter.

Effect of sample preparation techniques for carbon and nitrogen stable isotope analysis of hydroxyapatite structures in the form of elasmobranch vertebral centra.

PubMed

Christiansen, Heather M; Hussey, Nigel E; Wintner, Sabine P; Cliff, Geremy; Dudley, Sheldon F J; Fisk, Aaron T

2014-03-15

Bulk stable isotope analysis (SIA) provides an important tool for the study of animal ecology. Elasmobranch vertebral centra can be serially sampled to obtain an isotopic history of an individual over ontogeny. The measured total δ(13)C value, however, may be misinterpreted due to the inclusion of the (13)C-rich inorganic portion. Hydrochloric acid (HCl) is commonly used to remove the inorganic portion of hydroxyapatite structures before undertaking SIA, but more recently ethylenediaminetetraacetic acid (EDTA) has been recommended for elasmobranch vertebrae. These acid treatments may introduce uncertainty on measured δ(13)C and δ(15)N values above instrument precision and the effect of small sample size remains untested for elasmobranch vertebrae. Using a non-dilution program on an isotope ratio mass spectrometer the minimum sample weight of vertebrae required to obtain accurate isotopic values was determined for three shark species: white (Carcharodon carcharias), tiger (Galeocerdo cuvier), and sand tiger (Carcharias taurus). To examine if acid treatment completely removes the inorganic component of the vertebrae or whether the technique introduces its own uncertainty on measured δ(13)C and δ(15)N values, vertebrae samples were analyzed untreated and following EDTA treatment. The minimum sample weight required for accurate stable isotope values and the percentage sample yield following EDTA treatment varied within and among species. After EDTA treatment, white shark vertebrae were all enriched in (13)C and depleted in (15) N, tiger shark vertebrae showed both enrichment and depletion of (13)C and (15)N, and sand tiger shark vertebrae were all depleted in (13)C and (15)N. EDTA treatment of elasmobranch vertebrae produces unpredictable effects (i.e. non-linear and non-correctable) among species in both the percentage sample yield and the measured δ(13)C and δ(15)N values. Prior to initiating a large-scale study, we strongly recommend investigating (i) the minimum weight of vertebral material required to obtain consistent isotopic values and (ii) the effects of EDTA treatment, specific to the study species and the isotope ratio mass spectrometer employed. Copyright © 2014 John Wiley & Sons, Ltd.

Titanium Isotopes Link the High 3He/4He Reservoir to Continent Formation

NASA Astrophysics Data System (ADS)

Millet, M. A.; Jackson, M. G.; Dauphas, N.; Burton, K. W.; Williams, H. M.; Kurz, M. D.; Doucelance, R.; Smithies, H.; Champion, D. C.; Nowell, G. M.

2016-12-01

Elevated 3He/4He ratios found in ocean island basalts (OIB) argue for the survival of an early-formed reservoir (>4.5 Ga) in the Earth's mantle [1]. However, its nature remains debated. A characteristic of high 3He/4He OIBs is their anomalous enrichment in Ti abundance relative to elements of similar incompatibility (Sm and Tb). Here we use a new geochemical tool, the stable isotopes of Titanium, to investigate the origin of Ti enrichment of high 3He/4He OIBs. Recent work [2] has shown that Ti isotopes are a powerful tracer of oxide-melt equilibrium in magmatic systems. Results show that primitive OIB samples from localities associated with low 3He/4He ratios (≤15 R/Ra) have δ49Ti values within error of the mantle (δ49Ti=0.005±0.005 [2]) and chondrite values (+0.004±0.010 [3]) regardless of their Ti anomaly (0.93He/4He ratios (>25R/Ra) display δ49Ti values ranging from mantle-like to enriched in light isotopes (up to -0.065‰±0.005) that are negatively correlated with their Ti/Ti* and uncorrelated to indices of magma differentiation. This indicates that i) elevated Ti/Ti* in high 3He/4He OIBs is a mantle source signature and ii) that the high 3He/4He reservoir is enriched in light isotopes of Ti relative to the BSE. This enrichment in light isotopes is balanced by the heavy δ49Ti values and negative Ti/Ti* of Archean Tonalite-Throndhjemite-Granodiorite samples (TTG) from the Pilbara and Yilgarn Craton (+0.20<δ49Ti<+0.40), a proxy for early-formed, juvenile continental crust. Given the chondritic composition of the Earth's mantle and the inability of the typical mantle lithologies to fractionate Ti isotopes, this implies that the Ti enrichment of the high 3He/4He mantle reservoir is linked to the recycling of residues of partial melting events in the presence of rutile (TiO2), a process that drove continent formation in the Archean and possibly earlier. In addition, since these residues cannot display elevated 3He/4He ratios, it requires the Ti-He signature of the high 3He/4He reservoir is due to recycling of entire slab packages. [1] Rizo et al., Science, 2016 [2] Millet et al., EPSL, 2016 [3] Greber et al., LPSC, 2016

Isotopic composition of reduced and oxidized sulfur in the Canary Islands: implications for the mantle S cycle

NASA Astrophysics Data System (ADS)

Beaudry, P.; Longpre, M. A.; Wing, B. A.; Bui, T. H.; Stix, J.

2017-12-01

The Earth's mantle contains distinct sulfur reservoirs, which can be probed by sulfur isotope analyses of volcanic rocks and gases. We analyzed the isotopic composition of reduced and oxidized sulfur in a diverse range of volcanically derived materials spanning historical volcanism in the Canary Islands. Our sample set consists of subaerial volcanic tephras from three different islands, mantle and sedimentary xenoliths, as well as lava balloon samples from the 2011-2012 submarine El Hierro eruption and associated crystal separates. This large sample set allows us to differentiate between the various processes responsible for sulfur isotope heterogeneity in the Canary archipelago. Our results define an array in triple S isotope space between the compositions of the MORB and seawater sulfate reservoirs. Specifically, the sulfide values are remarkably homogeneous around d34S = -1 ‰ and D33S = -0.01 ‰, while sulfate values peak at d34S = +4 ‰ and D33S = +0.01 ‰. Lava balloons from the El Hierro eruption have highly enriched sulfate d34S values up to +19.3 ‰, reflecting direct interaction between seawater sulfate and the erupting magma. Several sulfate data points from the island of Lanzarote also trend towards more positive d34S up to +13.8 ‰, suggesting interaction with seawater sulfate-enriched lithologies or infiltration of seawater within the magmatic system. On the other hand, the modal values and relative abundances of S2- and S6+ in crystal separates suggest that the Canary Island mantle source has a d34S around +3 ‰, similar to the S-isotopic composition of a peridotite xenolith from Lanzarote. We infer that the S2- and S6+ modes reflect isotopic equilibrium between those species in the magmatic source, which requires 80 % of the sulfide to become oxidized after melting, consistent with measured S speciation. This 34S enrichment of the source could be due to the recycling of hydrothermally-altered oceanic crust, which has been previously suggested for the Canary Island hotspot on the basis of radiogenic isotope characteristics.

Method for isotope enrichment by photoinduced chemiionization

DOEpatents

Dubrin, James W.

1985-01-01

Isotope enrichment, particularly .sup.235 U enrichment, is achieved by irradiating an isotopically mixed vapor feed with radiant energy at a wavelength or wavelengths chosen to selectively excite the species containing a desired isotope to a predetermined energy level. The vapor feed if simultaneously reacted with an atomic or molecular reactant species capable of preferentially transforming the excited species into an ionic product by a chemiionization reaction. The ionic product, enriched in the desired isotope, is electrostatically or electromagnetically extracted from the reaction system.

D and 18O enrichment measurements in biological fluids in a continuous-flow elemental analyser with an isotope-ratio mass spectrometer using two configurations.

PubMed

Ripoche, N; Ferchaud-Roucher, V; Krempf, M; Ritz, P

2006-09-01

In doubly labelled water studies, biological sample enrichments are mainly measured using off-line techniques (equilibration followed by dual-inlet introduction) or high-temperature elemental analysis (HT-EA), coupled with an isotope-ratio mass spectrometer (IRMS). Here another continuous-flow method, (CF-EA/IRMS), initially dedicated to water, is tested for plasma and urine analyses. The elemental analyser configuration is adapted for each stable isotope: chromium tube for deuterium reduction and glassy carbon reactor for 18O pyrolysis. Before on-line conversion of water into gas, each matrix is submitted to a short and easy treatment, which is the same for the analysis of the two isotopes. Plasma is passed through centrifugal filters. Urine is cleaned with black carbon and filtered (0.45 microm diameter). Tested between 150 and 300 ppm in these fluids, the D/H ratio response is linear with good repeatability (SD<0.2 ppm) and reproducibility (SD<0.5 ppm). For 18O/16O ratios (from 2000 to 2200 ppm), the same repeatability is obtained with a between-day precision lower than 1.4 ppm. The accuracy on biological samples is validated by comparison to classical dual-inlet methods: 18O analyses give more accurate results. The data show that enriched physiological fluids can be successfully analysed in CF-EA/IRMS. Copyright (c) 2006 John Wiley & Sons, Ltd.

Application of non-lethal stable isotope analysis to assess feeding patterns of juvenile pallid sturgeon Scaphirhynchus albus: a comparison of tissue types and sample preservation methods

USGS Publications Warehouse

Andvik, R.T.; VanDeHey, J.A.; Fincel, M.J.; French, William E.; Bertrand, K.N.; Chipps, Steven R.; Klumb, Robert A.; Graeb, B.D.S.

2010-01-01

Traditional techniques for stable isotope analysis (SIA) generally require sacrificing animals to collect tissue samples; this can be problematic when studying diets of endangered species such as the pallid sturgeon Scaphirhynchus albus. Our objectives were to (i) determine if pectoral fin tissue (non-lethal) could be a substitute for muscle tissue (lethal) in SIA of juvenile pallid sturgeon, and (ii) evaluate the influence of preservation techniques on stable isotope values. In the laboratory, individual juvenile pallid sturgeon were held for up to 186 day and fed chironomids, fish, or a commercially available pellet diet. Significant, positive relationships (r² ≥ 0.8) were observed between fin and muscle tissues for both δ15N and δ13C; in all samples isotopes were enriched in fins compared to muscle tissue. Chironomid and fish based diets of juvenile pallid sturgeon were distinguishable for fast growing fish (0.3 mm day−1) using stable δ15N and δ13C isotopes. Frozen and preserved fin tissue δ15N isotopes were strongly related (r2 = 0.89) but δ13C isotopes were weakly related (r2 = 0.16). Therefore, freezing is recommended for preservation of fin clips to avoid the confounding effect of enrichment by ethanol. This study demonstrates the utility of a non-lethal technique to assess time integrated food habits of juvenile pallid sturgeon and should be applicable to other threatened or endangered species.

Volatile Content of the Mid-ocean Ridge Mantle Inferred from Off-axis Seamounts and Intra-transform Lavas

NASA Astrophysics Data System (ADS)

Shimizu, K.; Saal, A. E.; Hauri, E. H.; Nagle, A.; Forsyth, D. W.; Niu, Y.

2011-12-01

Off-axis seamounts and intra-transform lavas provide more direct geochemical information of the mantle than axial lavas. These smaller volumes of melts undergo lower extent of crystal fractionation and mixing compared to basalts erupting within the ridge axis due to a lack of long-lived magma chambers or along axis melt migration. Therefore, their study provide not only a more reliable approach to determine the volatile content of the intrinsic components forming the Earth's upper mantle, but also help constrain mantle convection, heterogeneity, and crustal recycling. Samples from the Quebrada-Discovery-Gofar (QDG) transform fault system (EPR 3°-5°S) and from northern EPR seamounts (5°-15° N) were collected during KN182-13 (R/V Knorr) and RAIT 02 (R/V Thomas Washington) expeditions, respectively. 159 submarine glasses were analyzed for major elements, trace elements, and volatile elements by triplicate analyses, as well as for Sr and Nd isotopes in a subset of samples. The QDG and northern EPR seamounts have similar trace element and isotopic composition that is consistent with melting of two-component mantle common to both regions. The degree of trace element enrichment (e.g. Th/La), isotopic composition, and depth of melt segregation (e.g. Sm/Yb) have a positive correlation and range from ultra depleted to relatively enriched compositions. In order to investigate the primary volatile content of submarine glasses we first considered shallow level processes, such as volatile degassing, sulfide saturation and interaction of melt with hydrothermally altered material. The vapor-melt equilibrium pressure (Dixon et al., 1995) indicates that the majority of the samples were super-saturated in CO2-H2O vapor at the pressure of eruption, which implies rapid magma ascent rate that prevented complete CO2 degassing. Samples that were sulfide saturated (Liu et al., 2007) and contaminated by seawater or seawater derived material (high Cl/K) were filtered out. F/Nd, Cl/K, and H2O/Ce ratios in our samples positively correlate with Th/La, Sm/Yb, and isotope ratios suggesting that the enriched mantle component is also enriched in volatile contents. S/Dy ratios are the exception, with relatively constant values in both enriched, and depleted basalts. Although it has been argued that correlation between Sr, Nd and Pb isotope ratios and fractionation corrected major element in seamount samples indicate different mantle lithologies under the mid-ocean ridges, we will show that such correlation might be an artifact of ignoring the effect of water during the correction for fractional crystallization. [1] Dixon et al. (1995) J. Pet., 36, 1607-1631. [2] Liu et al. (2007) Geochim Cosmochim Ac., 71, 1783-1799.

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;

Silicon Isotope Geochemistry of Ocean Island Basalts: Mantle Heterogeneities and Contribution of Recycled Oceanic Crust and Lithosphere

NASA Astrophysics Data System (ADS)

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

2015-12-01

The study of Silicon (Si) isotopes in Ocean Island Basalts (OIB) has the potential to elucidate between possible heterogeneities in the mantle. Relatively large (~several per mil per atomic mass unit) Si isotope fractionation occurs in low-temperature environments during biochemical and geochemical precipitation of dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes [1]. In contrast, only a limited range (~tenths of a per mil) of Si isotope fractionation has been observed in high-temperature igneous processes [2]. Therefore, Si isotopes may be useful as tracers for the presence of crustal material (derived from low-temperature surface processes) in OIB source regions in a manner similar to more conventional stable isotope systems, such as O. Here we present the first comprehensive set of high-precision Si isotope data obtained by MC-ICP-MS for a diverse suite of OIBs, including new data for the Canary Islands. Samples represent the Pacific, Atlantic, and Indian Ocean basins and include representative end-members for the EM-1, EM-2, and HIMU mantle components. Average δ30Si values for OIBs representing the EM-1 (-0.32 ± 0.06‰, 2 sd), EM-2 (-0.30 ± 0.01‰, 2 sd), and HIMU (-0.34 ± 0.09‰, 2 sd) mantle components are all in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth [3]. However, small systematic variations are present; HIMU (Mangaia, Cape Verde, La Palma) and Iceland OIBs are enriched in the lighter isotopes of Si (δ30Si values lower than MORB). Further, the difference in Si isotope composition between La Palma and El Heirro (Canary Islands) has previously been observed for O isotopes [4], suggesting a relationship between the Si and O isotope mantle systematics. The Si isotope variations among OIBs may be explained by the sampling of a primitive mantle reservoir enriched in the light isotopes of Si, as suggested by [5], but most likely reflects the incorporation of recycled altered oceanic crust and lithosphere in the plume source. References: [1] Ziegler et al., GCA 2005 [2] Savage et al., GCA 2011 [3] Savage et al., EPSL 2010 [4] Day et al., Geology 2009 [5] Huang et al., GCA 2014

Shifts in rotifer life history in response to stable isotope enrichment: testing theories of isotope effects on organismal growth

PubMed Central

2017-01-01

In ecology, stable isotope labelling is commonly used for tracing material transfer in trophic interactions, nutrient budgets and biogeochemical processes. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism growth and metabolism. This assumption is, however, challenged by theoretical considerations and experimental studies on kinetic isotope effects in vivo. Here, I demonstrate profound changes in life histories of the rotifer Brachionus plicatilis fed 15N-enriched algae (0.4–5.0 at%); i.e. at the enrichment levels commonly used in ecological studies. These findings support theoretically predicted effects of heavy isotope enrichment on growth, metabolism and ageing in biological systems and underline the importance of accounting for such effects when using stable isotope labelling in experimental studies. PMID:28405367

The potential of isotopically enriched magnesium to study bone implant degradation in vivo.

PubMed

Draxler, Johannes; Martinelli, Elisabeth; Weinberg, Annelie M; Zitek, Andreas; Irrgeher, Johanna; Meischel, Martin; Stanzl-Tschegg, Stefanie E; Mingler, Bernhard; Prohaska, Thomas

2017-03-15

This pilot study highlights the substantial potential of using isotopically enriched (non-radioactive) metals to study the fate of biodegradable metal implants. It was possible to show that magnesium (Mg) release can be observed by combining isotopic mass spectrometry and isotopic pattern deconvolution for data reduction, even at low amounts of Mg released a from slowly degrading 26 Mg enriched (>99%) Mg metal. Following implantation into rats, structural in vivo changes were monitored by μCT. Results showed that the applied Mg had an average degradation rate of 16±5μmyear -1 , which corresponds with the degradation rate of pure Mg. Bone and tissue extraction was performed 4, 24, and 52weeks after implantation. Bone cross sections were analyzed by laser ablation inductively coupled plasma mass spectrometry (ICP-MS) to determine the lateral 26 Mg distribution. The 26 Mg/ 24 Mg ratios in digested tissue and excretion samples were analyzed by multi collector ICP-MS. Isotope pattern deconvolution in combination with ICP-MS enabled detection of Mg pin material in amounts as low as 200ppm in bone tissues and 20ppm in tissues up to two fold increased Mg levels with a contribution of pin-derived Mg of up to 75% (4weeks) and 30% (24weeks) were found adjacent to the implant. After complete degradation, no visual bone disturbance or residual pin-Mg could be detected in cortical bone. In organs, increased Δ 26 Mg/ 24 Mg values up to 16‰ were determined compared to control samples. Increased Δ 26 Mg/ 24 Mg values were detected in serum samples at a constant total Mg level. In contrast to urine, feces did not show a shift in the 26 Mg/ 24 Mg ratios. This investigation showed that the organism is capable of handling excess Mg well and that bones fully recover after degradation. Magnesium alloys as bone implants have faced increasing attention over the past years. In vivo degradation and metabolism studies of these implant materials have shown the promising application in orthopaedic trauma surgery. With advance in Mg research it has become increasingly important to monitor the fate of the implant material in the organism. For the first time, the indispensible potential of isotopically enriched materials is documented by applying 26 Mg enriched Mg implants in an animal model. Therefore, the spatial distribution of pin-Mg in bone and the pin-Mg migration and excretion in the organism could be monitored to better understand metal degradation as well as Mg turn over and excretion. Copyright © 2017. Published by Elsevier Ltd.

Mass dependence of calcium isotope fractionations in crown-ether resin chromatography.

PubMed

Fujii, Yasuhiko; Nomura, Masao; Kaneshiki, Tositaka; Sakuma, Yoichi; Suzuki, Tatsuya; Umehara, Saori; Kishimoto, Tadahumi

2010-06-01

Benzo 18-crown-6-ether resin was synthesised by the phenol condensation polymerisation process in porous silica beads, of which particle diameter was ca 60micro Calcium adsorption chromatography was performed with the synthesised resin packed in a glass column. The effluent was sampled in fractions, and the isotopic abundance ratios of (42)Ca, (43)Ca, (44)Ca, and (48)Ca against (40)Ca were measured by a thermo-ionisation mass spectrometer. The enrichment of heavier calcium isotopes was observed at the front boundary of calcium adsorption chromatogram. The mass dependence of mutual separation of calcium isotopes was analysed by using the three-isotope-plots method. The slopes of three-isotope-plots indicate the relative values of mutual separation coefficients for concerned isotopic pairs. The results have shown the normal mass dependence; isotope fractionation is proportional to the reduced mass difference, (M - M')/MM', where M and M' are masses of heavy and light isotope, respectively. The mass dependence clarifies that the isotope fractionations are originated from molecular vibration. The observed separation coefficient epsilon is 3.1x10(-3) for the pair of (40)Ca and (48)Ca. Productivity of enriched (48)Ca by crown-ether-resin was discussed as the function of the separation coefficient and the height equivalent to the theoretical plate.

Recycling Seamounts: Implications for Mantle Source Heterogeneities

NASA Astrophysics Data System (ADS)

Madrigal, P.; Gazel, E.

2016-12-01

Isolated seamounts formed away from plate boundaries and/or known hotspot tracks are widely distributed in the Earth's oceanic plates. Despite their pervasiveness, the origin and composition of the magmatic sources that create these seamounts are still unknown. Moreover, as the seamount provinces travel along with the oceanic plate towards subduction trenches these volcanic edifices become subducted materials that are later recycled into the mantle. Using radiogenic isotopes (Sr-Nd-Pb) from present-day non-plume ocean island basalts (OIB) sampled by drilling and dredging as well as by normal processes of accretion to subduction margins, we modeled the isotopic evolution of these enriched reservoirs to assess their role as discrete components contributing to upper mantle heterogeneity. Our evidence suggests that a highly enriched mantle reservoir can originate from OIB-type subducted material that gets incorporated and stirred throughout the upper mantle in a shorter time period ( 200 Ma-500 Ma) than other highly enriched components like ancient subducted oceanic crust (>1 Ga), thought to be the forming agent of the HIMU mantle reservoir endmember. Enriched signatures from intraplate volcanism can be described by mixing of a depleted component like DMM and an enriched reservoir like non-plume related seamounts. Our data suggests that the isotopic evolution in time of a seamount-province type of reservoir can acquire sufficiently enriched compositions to resemble some of the most enriched magmas on Earth. This "fast-forming" (between 200 and 500 Ma) enriched reservoir could also explain some of the enriched signatures commonly present in intraplate and EMORB magmas unrelated to deep mantle plume upwellings.

Sulphur tracer experiments in laboratory animals using 34S-labelled yeast.

PubMed

Martínez-Sierra, J Giner; Moreno Sanz, F; Herrero Espílez, P; Marchante Gayón, J M; Rodríguez Fernández, J; García Alonso, J I

2013-03-01

We have evaluated the use of (34)S-labelled yeast to perform sulphur metabolic tracer experiments in laboratory animals. The proof of principle work included the selection of the culture conditions for the preparation of sulphur labelled yeast, the study of the suitability of this labelled yeast as sulphur source for tracer studies using in vitro gastrointestinal digestion and the administration of the (34)S-labelled yeast to laboratory animals to follow the fate and distribution of (34)S in the organism. For in vitro gastrointestinal digestion, the combination of sodium dodecyl sulphate-polyacrylamide gel electrophoresis and high-performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICP-MS) showed that labelled methionine, cysteine and other low molecular weight sulphur-containing biomolecules were the major components in the digested extracts of the labelled yeast. Next, in vivo kinetic experiments were performed in healthy Wistar rats after the oral administration of (34)S-labelled yeast. The isotopic composition of total sulphur in tissues, urine and faeces was measured by double-focusing inductively coupled plasma mass spectrometry after microwave digestion. It was observed that measurable isotopic enrichments were detected in all samples. Finally, initial investigations on sulphur isotopic composition of serum and urine samples by HPLC-ICP-MS have been carried out. For serum samples, no conclusive data were obtained. Interestingly, chromatographic analysis of urine samples showed differential isotope enrichment for several sulphur-containing biomolecules.

Strong Water Isotopic Anomalies in the Martian Atmosphere: Probing Current and Ancient Reservoirs

NASA Technical Reports Server (NTRS)

Villanueva, G. L.; Mumma, M. J.; Novak, R. E.; Käufl, H. U.; Hartogh, P.; Encrenaz, T.; Tokunaga, A.; Khayat, A.; Smith, M. D.

2015-01-01

We measured maps of atmospheric water (H2O) and its deuterated form (HDO) across the martian globe, showing strong isotopic anomalies and a significant high deuterium/hydrogen (D/H) enrichment indicative of great water loss. The maps sample the evolution of sublimation from the north polar cap, revealing that the released water has a representative D/H value enriched by a factor of about 7 relative to Earth's ocean [Vienna standard mean ocean water (VSMOW)]. Certain basins and orographic depressions show even higher enrichment, whereas high-altitude regions show much lower values (1 to 3 VSMOW). Our atmospheric maps indicate that water ice in the polar reservoirs is enriched in deuterium to at least 8 VSMOW, which would mean that early Mars (4.5 billion years ago) had a global equivalent water layer at least 137 meters deep.

Strong water isotopic anomalies in the martian atmosphere: probing current and ancient reservoirs.

PubMed

Villanueva, G L; Mumma, M J; Novak, R E; Käufl, H U; Hartogh, P; Encrenaz, T; Tokunaga, A; Khayat, A; Smith, M D

2015-04-10

We measured maps of atmospheric water (H2O) and its deuterated form (HDO) across the martian globe, showing strong isotopic anomalies and a significant high deuterium/hydrogen (D/H) enrichment indicative of great water loss. The maps sample the evolution of sublimation from the north polar cap, revealing that the released water has a representative D/H value enriched by a factor of about 7 relative to Earth's ocean [Vienna standard mean ocean water (VSMOW)]. Certain basins and orographic depressions show even higher enrichment, whereas high-altitude regions show much lower values (1 to 3 VSMOW). Our atmospheric maps indicate that water ice in the polar reservoirs is enriched in deuterium to at least 8 VSMOW, which would mean that early Mars (4.5 billion years ago) had a global equivalent water layer at least 137 meters deep. Copyright © 2015, American Association for the Advancement of Science.

Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates.

PubMed

Moerdijk-Poortvliet, Tanja C W; Schierbeek, Henk; Houtekamer, Marco; van Engeland, Tom; Derrien, Delphine; Stal, Lucas J; Boschker, Henricus T S

2015-07-15

We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of δ(13)C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence, although LC/IRMS is expected to be more accurate and precise, no direct comparison has been reported. GC/IRMS with the aldonitrile penta-acetate (ANPA) derivatisation method was compared with LC/IRMS without derivatisation. A large number of glucose standards and a variety of natural samples were analysed for five neutral carbohydrates at natural abundance as well as at (13)C-enriched levels. Gas chromatography/chemical ionisation mass spectrometry (GC/CIMS) was applied to check for incomplete derivatisation of the carbohydrate, which would impair the accuracy of the GC/IRMS method. The LC/IRMS technique provided excellent precision (±0.08‰ and ±3.1‰ at natural abundance and enrichment levels, respectively) for the glucose standards and this technique proved to be superior to GC/IRMS (±0.62‰ and ±19.8‰ at natural abundance and enrichment levels, respectively). For GC/IRMS measurements the derivatisation correction and the conversion of carbohydrates into CO2 had a considerable effect on the measured δ(13)C values. However, we did not find any significant differences in the accuracy of the two techniques over the full range of natural δ(13)C abundances and (13)C-labelled glucose. The difference in the performance of GC/IRMS and LC/IRMS diminished when the δ(13)C values were measured in natural samples, because the chromatographic performance and background correction became critical factors, particularly for LC/IRMS. The derivatisation of carbohydrates for the GC/IRMS method was complete. Although both LC/IRMS and GC/IRMS are reliable techniques for compound-specific stable carbon isotope analysis of carbohydrates (provided that derivatisation is complete and the calibration requirements are met), LC/IRMS is the technique of choice. The reasons for this are the improved precision, simpler sample preparation, and straightforward isotopic calibration. Copyright © 2015 John Wiley & Sons, Ltd.

Early diagenesis and organic matter preservation--A molecular stable isotope perspective

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

Macko, S.A.; Engel, M.H.; Qian, Y.

1992-01-01

Through new developments in stable isotope capability, gas chromatography coupled to a stable isotope ratio mass spectrometer (GC/IRMS), the molecular pathways of the diagenetic reactions can be observed on the components themselves. The authors report the results of laboratory-controlled degradation experiments of fresh organic substrates. Isotopically resolvable materials were used. Seagrass showed slight enrichments in [delta]N-15 with little change in [delta]C-13 following four weeks of decomposition. During that period the identifiable amino acid content decreased by approx. 50% for each amino acid. Mixtures of marine sediment with the same seagrass showed enrichments in nitrogen with associated depletions in carbon isotopicmore » compositions over the same time span. Control experiments on the sediments without added fresh seagrass showed no change in isotopic content. These changes are attributed to hydrolysis, deamination and decarboxylation reactions. Isotopic fractionations of similar size and direction have been observed in laboratory studies on peptide hydrolysis and natural samples of particulate organic materials. At the molecular level, using GC/IRMS, certain amino acids are seen to decrease in C-13 content while others become increasingly enriched in C-13. Similar reactions are seen in carbohydrates. The molecular isotope approach indicates that the process of diagenesis and preservation is significantly more complex than simple breakdown and loss. A large portion of the organic matter eventually preserved in organic-rich deposits can be attributed to new production in the deposit.« less

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

NASA Astrophysics Data System (ADS)

Ewing, Tanya A.; Müntener, Othmar

2018-05-01

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

Hydrogen and carbon isotope systematics in hydrogenotrophic methanogenesis under H2-limited and H2-enriched conditions: implications for the origin of methane and its isotopic diagnosis

NASA Astrophysics Data System (ADS)

Okumura, Tomoyo; Kawagucci, Shinsuke; Saito, Yayoi; Matsui, Yohei; Takai, Ken; Imachi, Hiroyuki

2016-12-01

Hydrogen and carbon isotope systematics of H2O-H2-CO2-CH4 in hydrogenotrophic methanogenesis and their relation to H2 availability were investigated. Two H2-syntrophic cocultures of fermentatively hydrogenogenic bacteria and hydrogenotrophic methanogens under conditions of <102 Pa-H2 and two pure cultures of hydrogenotrophic methanogens under conditions of 105 Pa-H2 were tested. Carbon isotope fractionation between CH4 and CO2 during hydrogenotrophic methanogenesis was correlated with pH2, as indicated in previous studies. The hydrogen isotope ratio of CH4 produced during rapid growth of the thermophilic methanogen Methanothermococcus okinawensis under high pH2 conditions ( 105 Pa) was affected by the isotopic composition of H2, as concluded in a previous study of Methanothermobacter thermautotrophicus. This " {δ D}_{{H}_2} effect" is a possible cause of the diversity of previously reported values for hydrogen isotope fractionation between CH4 and H2O examined in H2-enriched culture experiments. Hydrogen isotope fractionation between CH4 and H2O, defined by (1000 + {δ D}_{{CH}_4} )/(1000 + {δ D}_{{H}_2O} ), during hydrogenotrophic methanogenesis of the H2-syntrophic cocultures was in the range 0.67-0.69. The hydrogen isotope fractionation of our H2-syntrophic dataset overlaps with those obtained not only from low- pH2 experiments reported so far but also from natural samples of "young" methane reservoirs (0.66-0.74). Conversely, such hydrogen isotope fractionation is not consistent with that of "aged" methane in geological samples (≥0.79), which has been regarded as methane produced via hydrogenotrophic methanogenesis from the carbon isotope fractionation. As a possible process inducing the inconsistency in hydrogen isotope signatures between experiments and geological samples, we hypothesize that the hydrogen isotope signature of CH4 imprinted at the time of methanogenesis, as in the experiments and natural young methane, may be altered by diagenetic hydrogen isotope exchange between extracellular CH4 and H2O through reversible reactions of the microbial methanogenic pathway in methanogenic region and/or geological methane reservoirs.

An experimental study of the isotopic enrichment in Ar, Kr, and Xe when trapped in water ice

NASA Technical Reports Server (NTRS)

Notesco, G.; Laufer, D.; Bar-Nun, A.; Owen, T.

1999-01-01

The isotopic enrichment of argon, krypton, and xenon, when trapped in water ice, was studied experimentally. The isotopes were found to be enriched according to their (m1/m2)1/2 ratio. These enrichment factors could be useful for comparison among the uncertain cosmic or solar isotopic ratios, the hopeful in situ cometary ratio, and those in Earth's atmosphere, in the context of cometary delivery of volatiles to Earth.

Isotopic signals from precipitation and denitrification in nitrate in a northern hardwood forest

NASA Astrophysics Data System (ADS)

Goodale, C. L.; Wexller, S.

2012-12-01

Denitrification can represent an important term in the nitrogen budget of small catchments; however, this process varies greatly over space and time and is notoriously difficult to quantify. Measurements of the natural abundance of stable isotopes of nitrogen and oxygen in dissolved nitrate in stream- and river water can sometimes provide evidence of denitrification, particularly in large river basins or agriculturally impacted catchments. To date, however, this approach has provided little to no evidence of denitrification in catchments in temperate forests. Here, we examined d15N and d18O of nitrate in water samples collected during summer 2011 not only from streams and precipitation, but also from groundwater from the hydrologic reference watershed (W3) drained by Paradise Brook, at the Hubbard Brook Experimental Forest, in the White Mountains, New Hampshire. Despite low nitrate concentrations (< 0.5 to 8.8 uM nitrate) dual-isotopic signals of nitrate sources and nitrogen cycle processes were clearly distinguishable, including sources from atmospheric deposition, and from nitrification of atmospheric ammonium and from or soil organic nitrogen, as well as nitrate affected by soil denitrification. An atmospheric signal from nitrate in precipitation (enriched with 18O) was observed immediately following a precipitation event in mid-July contributing roughly 22% of stream nitrate export on this date. Stream samples the day following this and other storms showed this export of event nitrate to be short-lived. Hillslope piezometers showed low nitrate concentrations and high d15N- and d18O-nitrate values (averaging 12 and 18 per mil, repectively) indicating denitrification, which preferentially removes isotopically light N and O in N gases and leaves isotopically heavy nitrate behind. These samples showed a positive relationship between nitrogen and oxygen isotopic composition with a regression line slope of 0.76 (R2 = 0.68), and an isotope enrichment factor -12.7 per mil for denitrification removal of nitrate in these hillslope soils. The isotopic composition of a time series of samples from three riparian piezometers crossing Paradise Brook shows strong connections between the riparian soil water and the stream, as well as a different dominant source of nitrate in each piezometer. Repeated surveys of stream nitrate show modest positive enrichment in N and O isotopes with a slope between 18O and 15N of 0.96, indicating either in- or near-stream denitrification or mixing between stream and hillslope water bearing a stronger denitrification signal. The dual isotope approach provides detailed information on nitrogen cycling dynamics during the summer in a northern hardwood forested catchment. Together, these observations provide strong isotopic evidence for rapid rates of denitrification during summer in the soils of this small forested catchment.

A practical method for the determination of total selenium in environmental samples using isotope dilution-hydride generation-inductively coupled plasma-mass spectrometry

USGS Publications Warehouse

Kleckner, Amy E.; Kakouros, Evangelos; Stewart, A. Robin

2017-01-01

A safe, practical, and accurate method for the determination of selenium (Se) in range of environmental samples was developed. Small sample masses, 5–20 mg, were amended with 82Se enriched isotope for the isotope dilution (ID), preceding a multi-step wet digestion with nitric acid (HNO3) and hydrogen peroxide (H2O2). Samples were incubated in an autoclave for 3 h at 20 psi and 126°C. Digestates were subsequently reduced with concentrated hydrochloric acid to Se(IV) the most favorable valence for hydride generation (HG). The solutions were then analyzed on an ICP-MS equipped with Flow Injection system (FIAS-400). Polyatomic, isobaric, and background interferences were removed through the use of HG and ID with an 82Se enriched isotope spike. Recoveries for certified reference materials were determined and averaged 96% for biological tissues (NRCC DOLT3, DOLT4, DORM2, TORT2, and TORT3, and NIST 2976) and 108% for estuarine sediment (NRCC PACS2) with an average coefficient of variation for replicate measurements of ∼ 3.5%. Limit of detection was 0.13 ng Se g−1 dry weight or 0.19 ng Se L−1. This method can be broadly applied to biological tissues, sediments, suspended particulates, and water samples with minimal modifications making this method highly useful for assessing the ecotoxicology of total Se in aquatic ecosystems.

Calcium kinetics with microgram stable isotope doses and saliva sampling

NASA Technical Reports Server (NTRS)

Smith, S. M.; Wastney, M. E.; Nyquist, L. E.; Shih, C. Y.; Wiesmann, H.; Nillen, J. L.; Lane, H. W.

1996-01-01

Studies of calcium kinetics require administration of tracer doses of calcium and subsequent repeated sampling of biological fluids. This study was designed to develop techniques that would allow estimation of calcium kinetics by using small (micrograms) doses of isotopes instead of the more common large (mg) doses to minimize tracer perturbation of the system and reduce cost, and to explore the use of saliva sampling as an alternative to blood sampling. Subjects received an oral dose (133 micrograms) of 43Ca and an i.v. dose (7.7 micrograms) of 46Ca. Isotopic enrichment in blood, urine, saliva and feces was well above thermal ionization mass spectrometry measurement precision up to 170 h after dosing. Fractional calcium absorptions determined from isotopic ratios in blood, urine and saliva were similar. Compartmental modeling revealed that kinetic parameters determined from serum or saliva data were similar, decreasing the necessity for blood samples. It is concluded from these results that calcium kinetics can be assessed with micrograms doses of stable isotopes, thereby reducing tracer costs and with saliva samples, thereby reducing the amount of blood needed.

Non-lethal sampling of walleye for stable isotope analysis: a comparison of three tissues

USGS Publications Warehouse

Chipps, Steven R.; VanDeHey, J.A.; Fincel, M.J.

2012-01-01

Stable isotope analysis of fishes is often performed using muscle or organ tissues that require sacrificing animals. Non-lethal sampling provides an alternative for evaluating isotopic composition for species of concern or individuals of exceptional value. Stable isotope values of white muscle (lethal) were compared with those from fins and scales (non-lethal) in walleye, Sander vitreus (Mitchill), from multiple systems, size classes and across a range of isotopic values. Isotopic variability was also compared among populations to determine the potential of non-lethal tissues for diet-variability analyses. Muscle-derived isotope values were enriched compared with fins and depleted relative to scales. A split-sample validation technique and linear regression found that isotopic composition of walleye fins and scales was significantly related to that in muscle tissue for both δ13C and δ15N (r2 = 0.79–0.93). However, isotopic variability was significantly different between tissue types in two of six populations for δ15N and three of six populations for δ13C. Although species and population specific, these findings indicate that isotopic measures obtained from non-lethal tissues are indicative of those obtained from muscle.

Hybrid Interferometric/Dispersive Atomic Spectroscopy For Nuclear Materials Analysis

NASA Astrophysics Data System (ADS)

Morgan, Phyllis K.

Laser-induced breakdown spectroscopy (LIBS) is an optical emission spectroscopy technique that holds promise for detection and rapid analysis of elements relevant for nuclear safeguards and nonproliferation, including the measurement of isotope ratios. One important application of LIBS is the measurement of uranium enrichment (235U/238U), which requires high spectral resolution (e.g., 25 pm for the 424.437 nm U II line). Measuring uranium enrichment is important in nuclear nonproliferation and safeguards because the uranium highly enriched in the 235U isotope can be used to construct nuclear weapons. High-resolution dispersive spectrometers necessary for such measurements are typically bulky and expensive. A hybrid interferometric/dispersive spectrometer prototype, which consists of an inexpensive, compact Fabry-Perot etalon integrated with a low to moderate resolution Czerny-Turner spectrometer, was assembled for making high-resolution measurements of nuclear materials in a laboratory setting. To more fully take advantage of this low-cost, compact hybrid spectrometer, a mathematical reconstruction technique was developed to accurately reconstruct relative line strengths from complex spectral patterns with high resolution. Measurement of the mercury 313.1555/313.1844 nm doublet from a mercury-argon lamp yielded a spectral line intensity ratio of 0.682, which agrees well with an independent measurement by an echelle spectrometer and previously reported values. The hybrid instrument was used in LIBS measurements and achieved the resolution needed for isotopic selectivity of LIBS of uranium in ambient air. The samples used were a natural uranium foil (0.7% of 235U) and a uranium foil highly enriched in 235U to 93%. Both samples were provided by the Penn State University's Breazeale Nuclear Reactor. The enrichment of the uranium foils was verified using a high-purity germanium detector and dedicated software for multi-group spectral analysis. Uranium spectral line widths of ˜10 pm were measured at a center wavelength 424.437 nm, clearly discriminating the natural from the highly enriched uranium at that wavelength. The 424.167 nm isotope shift (˜6 pm), limited by spectral broadening, was only partially resolved but still discernible. This instrument and reconstruction method could enable the design of significantly smaller, portable high-resolution instruments with isotopic specificity, benefiting nuclear safeguards, treaty verification, nuclear forensics, and a variety of other spectroscopic applications.

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

USGS Publications Warehouse

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

2007-01-01

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

The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography-IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations.

PubMed

Bezemer, Karlijn D B; Koeberg, Mattijs; van der Heijden, Antoine E D M; van Driel, Chris A; Blaga, Cornelia; Bruinsma, Jildert; van Asten, Arian C

2016-09-01

Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)-IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone-TATP combinations. The extent of negative (δ(13) C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (δ(2) H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (δ(18) O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC-IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound-specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations. © 2016 American Academy of Forensic Sciences.

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.

Discrimination of carbon and nitrogen isotopes from milk to serum and vibrissae in Alaska Steller sea lions (Eumetopias jubatus)

USGS Publications Warehouse

Stegall, V.K.; Farley, Sean D.; Rea, Lorrie D.; Pitcher, K.W.; Rye, R.O.; Kester, C.L.; Stricker, C.A.; Bern, C.R.

2008-01-01

Knowledge of diet-tissue stable isotope discrimination is required to properly interpret stable isotope values and to identify possible diet shifts, such as might be expected from nursing through weaning. This study compared ??13C and ??15N of paired serum and vibrissal roots with those of ingested milk (n = 52) from free-ranging Steller sea lion (Eumetopias jubatus (Schreber, 1776)) pups (1-11 months) and juveniles (14-27 months) to estimate diet-tissue discrimination. Mean 15N enrichment from ingested milk to serum was 2.1??? ?? 0.6%??? and ??15N at the root of the vibrissae (representing current growth) were not significantly different from serum values. Milk was enriched for mean 13C by 5.0??? ?? 1.0%??? and 7.3??? ?? 1.2??? relative to serum and vibrissal roots, respectively, which was due to the presence of 13C-depleted lipids in milk. This was confirmed by lipid extraction from a subset of milk and serum samples, resulting in a 5.8??? ?? 1.0??? change only in milk. This study established that vibrissal roots and serum are reflective of a milk diet with approximately 2.0??? 15N enrichment, and vibrissal roots reflect serum and lipid-extracted milk values with approximately 2.0??? 13C enrichment. These discrimination factors are important to establish for stable isotope studies assessing diet shifts. ?? 2008 NRC.

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

Campbell, Keri; Judge, Elizabeth J.; Dirmyer, Matthew R.

Surrogate nuclear explosive debris was synthesized and characterized for major, minor, and trace elemental composition as well as uranium isotopics. The samples consisted of an urban glass matrix, equal masses soda lime and cement, doped with 500 ppm uranium with varying enrichments. The surface and cross section morphology were measured with SEM, and the major elemental composition was determined by XPS. LA-ICP-MS was used to measure the uranium isotopic abundance comparing different sampling techniques. Furthermore, the results provide an example of the utility of LA-ICP-MS for forensics applications.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Mass Spectrometric Investigation of Silicon Extremely Enriched in (28)Si: From (28)SiF4 (Gas Phase IRMS) to (28)Si Crystals (MC-ICP-MS).

PubMed

Pramann, Axel; Rienitz, Olaf

2016-06-07

A new generation of silicon crystals even further enriched in (28)Si (x((28)Si) > 0.999 98 mol/mol), recently produced by companies and institutes in Russia within the framework of a project initiated by PTB, were investigated with respect to their isotopic composition and molar mass M(Si). A modified isotope dilution mass spectrometric (IDMS) method treating the silicon as the matrix containing a so-called virtual element (VE) existing of the isotopes (29)Si and (30)Si solely and high resolution multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) were applied in combination. This method succeeds also when examining the new materials holding merely trace amounts of (29)Si (x((29)Si) ≈ 5 × 10(-6) mol/mol) and (30)Si (x((30)Si) ≈ 7 × 10(-7) mol/mol) extremely difficult to detect with lowest uncertainty. However, there is a need for validating the enrichment in (28)Si already in the precursor material of the final crystals, silicon tetrafluoride (SiF4) gas prior to crystal production. For that purpose, the isotopic composition of selected SiF4 samples was determined using a multicollector magnetic sector field gas-phase isotope ratio mass spectrometer. Contaminations of SiF4 by natural silicon due to storing and during the isotope ratio mass spectrometry (IRMS) measurements were observed and quantified. The respective MC-ICP-MS measurements of the corresponding crystal samples show-in contrast-several advantages compared to gas phase IRMS. M(Si) of the new crystals were determined to some extent with uncertainties urel(M) < 1 × 10(-9). This study presents a clear dependence of the uncertainty urel(M(Si)) on the degree of enrichment in (28)Si. This leads to a reduction of urel(M(Si)) during the past decade by almost 3 orders of magnitude and thus further reduces the uncertainty of the Avogadro constant NA which is one of the preconditions for the redefinition of the SI unit kilogram.

Additional Sr Isotopic Heterogeneity in Zagami Olivine-Rich Lithology

NASA Technical Reports Server (NTRS)

Misawa, K.; Niihara, T.; Shih, C.-Y; Reese, Y. D.; Nyquist, L. E.; Yoneda, S.; Yamashita, H.

2012-01-01

Prior isotopic analyses of Zagami have established differing initial Sr-87/Sr-86 (ISr) ratios of among Zagami lithologies, fine-grained (FG), coarse-grained (CG), and dark mottled lithologies (DML)]. The Zagami sample (KPM-NLH000057) newly allocated from the Kanagawa Prefectural Museum of Natural History contained DML and the Ol-rich lithology which included more ferroan olivines (Ol-rich: Fa(sub 97- 99) vs late-stage melt pockets: Fa(sub 90-97)]). We have combined mineralogy-petrology and Rb-Sr isotopic studies on the Kanagawa Zagami sample, which will provide additional clues to the genesis of enriched shergottites and to the evolution of Martian crust and mantle

Negative Oxygen Isotope Effect in Manganites with an Ordered Cation Arrangement in a High Magnetic Field

NASA Astrophysics Data System (ADS)

Taldenkov, A. N.; Snegirev, V. V.; Babushkina, N. A.; Kalitka, V. S.; Kaul', A. R.

2018-03-01

The oxygen isotope effect in PrBaMn2 16-18 O5.97 manganite with an ordered cation arrangement is studied. The field dependences of magnetic susceptibility and magnetization are measured in the temperature range 100-270 K and magnetic fields up to 32 T. A significant increase in the temperature of the spin-reorientation antiferromagnet-ferromagnet phase transition is detected in samples enriched in heavy oxygen 18O (negative isotope effect). The transition temperature and the isotope effect depend strongly on the magnetic field. An H-T phase diagram is plotted for samples with various isotope compositions. An analysis of the experimental results demonstrates that the detected negative isotope effect and the giant positive isotope effect revealed earlier in doped manganites have the same nature. The mechanisms of appearance of isotope effects are discussed in terms of the double exchange model under a polaron narrowing of the free carrier band.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

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

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

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

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole L.

We demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security applications.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

DOE PAGES

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole; ...

2017-06-19

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Reaction paths and host phases of uranium isotopes (235U; 238U), Saanich Inlet

NASA Astrophysics Data System (ADS)

Amini, M.; Holmden, C. E.; Francois, R. H.

2009-12-01

In recent times, Uranium has become increasingly the focus of stable isotope fractionation studies. Variations in 238U/235U have been reported as a result of redox reactions [1,2] from the nuclear field shift effect [3], and a mass-dependent, microbially-mediated, kinetic isotope effect [4]. The 238U/235U variability caused by changes in environmental redox conditions leads to an increase in the 238U/235U ratios of the reduced U species sequestered into marine sediments. This points to U isotope variability as a new tool to study ancient ocean redox changes. However, the process by which reduced sediments become enriched in the heavy isotopes of U is not yet known, and hence the utility of 238U/235U as a redox tracer remains to be demonstrated. In order to further constrain sedimentary U enrichment and related isotope effect, we are investigating U isotopic compositions of water samples and fresh surface sediment grab samples over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. U was sequentially extracted from sediments in order to characterize specific fractions for their isotopic composition. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10‰ (2sd). Fifteeen analyses of seawater yielded δ238U of -0.42±0.08‰ (2sd). The results for the water samples indicate a homogenous δ238U value throughout the Saanich Inlet water column that matches the global seawater signature. All of the water samples from above and below average -0.42±0.05‰ (2sd). In contrast, a plankton net sample yielded a distinctly different, (about 0.5‰ lighter) isotope value. Bacterial reduction experiments [4] have also shown isotope enrichment factors of about -0.3‰. In addition, metal isotope fractionation occurs during adsorption with the light isotope being preferentially adsorbed [5]. Whether plankton mediated chemical reduction or scavenging causes this fractionation will be further investigated by leaching experiments on sediment trap samples. By contrast, weak acidic leachates (at pH 6) of suboxic bottom sediments, tend towards higher δ238U values. For oxic sediments, U contents of this fraction were below detection limit. Stronger leaching at pH 3 removed most of the uranium from suboxic and oxic sediments. For oxic sediments, this fraction yields the seawater δ238U signature, while the U released from the suboxic sample is about 0.2‰ heavier. This matches the value for previously reported bulk analyses of suboxic sediments [1] implying that the reduced sedimentary U is released by this treatment,. Major and trace element analyses and XRD patterns will help relating this fraction to a specific mineral or reactive phase. [1] Weyer et al. (2007) GCA 72, 345-399. [2] Stirling et al. (2007) EPSL 264, 208-225. [3] Schauble (2007) GCA 71, 2170-2189. [4] Rademacher et al. (2006) Environ. Sci. Technol. 40,6943-6948. [5] Wasylenki (2009) GCA A1419.

Hf-Nd isotope constraints on the origin of the Cretaceous Caribbean plateau and its relationship to the Galápagos plume

NASA Astrophysics Data System (ADS)

Thompson, P. M. E.; Kempton, P. D.; White, R. V.; Kerr, A. C.; Tarney, J.; Saunders, A. D.; Fitton, J. G.; McBirney, A.

2004-01-01

Formation of the Cretaceous Caribbean plateau, including the komatiites of Gorgona, has been linked to the currently active Galápagos hotspot. We use Hf-Nd isotopes and trace element data to characterise both the Caribbean plateau and the Galápagos hotspot, and to investigate the relationship between them. Four geochemical components are identified in the Galápagos mantle plume: two 'enriched' components with ɛHf and ɛNd similar to enriched components observed in other mantle plumes, one moderately enriched component with high Nb/Y, and a fourth component which most likely represents depleted MORB source mantle. The Caribbean plateau basalt data form a linear array in Hf-Nd isotope space, consistent with mixing between two mantle components. Combined Hf-Nd-Pb-Sr-He isotope and trace element data from this study and the literature suggest that the more enriched Caribbean end member corresponds to one or both of the enriched components identified on Galápagos. Likewise, the depleted end member of the array is geochemically indistinguishable from MORB and corresponds to the depleted component of the Galápagos system. Enriched basalts from Gorgona partially overlap with the Caribbean plateau array in ɛHf vs. ɛNd, whereas depleted basalts, picrites and komatiites from Gorgona have a high ɛHf for a given ɛNd, defining a high- ɛHf depleted end member that is not observed elsewhere within the Caribbean plateau sequences. This component is similar, however, in terms of Hf-Nd-Pb-He isotopes and trace elements to the depleted plume component recognised in basalts from Iceland and along the Reykjanes Ridge. We suggest that the Caribbean plateau represents the initial outpourings of the ancestral Galápagos plume. Absence of a moderately enriched, high Nb/Y component in the older Caribbean plateau (but found today on the island of Floreana) is either due to changing source compositions of the plume over its 90 Ma history, or is an artifact of limited sampling. The high- ɛHf depleted component sampled by the Gorgona komatiites and depleted basalts is unique to Gorgona and is not found in the Caribbean plateau. This may be an indication of the scale of heterogeneity of the Caribbean plateau system; alternatively Gorgona may represent a separate oceanic plateau derived from a completely different Pacific plume, such as the Sala y Gomez.

The Origin and Evolution of Nucleosynthetic Sr Isotope Variability in Calcium and Aluminum-rich Refractory Inclusions

NASA Astrophysics Data System (ADS)

Myojo, Kunihiro; Yokoyama, Tetsuya; Okabayashi, Satoki; Wakaki, Shigeyuki; Sugiura, Naoji; Iwamori, Hikaru

2018-01-01

Nucleosynthetic isotope anomalies in meteorites are useful for investigating the origin of materials in the protoplanetary disk and dynamical processes of planetary formation. In particular, calcium and aluminum-rich inclusions (CAIs) found in chondrites are key minerals for decoding the initial conditions of the solar system before the accretion of small planetary bodies. In this study, we report isotopic analyses for three Allende CAIs, fluffy type A (FTA), type B, and fine-grained spinel rich (FS) inclusions, with a specific emphasis on the measurements of 84Sr/86Sr ratios. It was found that the average μ 84Sr values (106 relative deviations from a standard material) were 175, 129, and 56 ppm for the samples of FTA, type B, and FS inclusions, respectively. Additionally, the FTA samples exhibited heterogeneous μ 84Sr values, while those for the type B and FS inclusions were homogeneous within individual inclusions. The elevated μ 84Sr values were most likely explained by the relative enrichment of r-process nuclides in the CAI formation region. The variation of μ 84Sr values between the FTA and type B inclusions, as well as within the FTA inclusion, suggests the presence of multiple CAI source reservoirs with distinct isotopic compositions, which is either inherited from isotopic heterogeneity in the molecular cloud or caused by the selective destruction of r-process-enriched supernova grains via nebular thermal processing. On the other hand, the reaction between a refractory precursor of the FS inclusion and a gaseous reservoir enriched in Mg, Si, and 16O resulted in the lowest μ 84Sr values for the FS inclusion.

Use of Nitrogen-15-Enriched Escherichia coli as a Bacterial Tracer in Karst Aquifers.

PubMed

Ward, James W; Warden, John G; Bandy, Ashley M; Fryar, Alan E; Brion, Gail M; Macko, Stephen A; Romanek, Christopher S; Coyne, Mark S

2016-11-01

Karst aquifers are susceptible to contamination by microorganisms, but relatively few studies have used bacteria as tracers. We demonstrate the utility of Escherichia coli enriched in the stable isotope nitrogen-15 ( 15 N) as a novel bacterial tracer. Nonpathogenic E. coli from two springs in central Kentucky were grown on 15 N-enriched media. Survival of E. coli and persistence of the isotopic signal were assessed in two sets of laboratory experiments conducted with sterilized spring water in dark microcosms at 14 °C. First, isotopically labeled bacteria survived for 130 d at concentrations within one log unit of the average initial value, and there was no significant difference in δ 15 N values from Day 1 to Day 130. Second, water samples with E. coli were inoculated with either of two different species of protozoa (Tetrahymena pyriformis or Colpoda steinii). During 7 d, δ 15 N values increased in T. pyriformis while bacterial populations decreased. In a field test, following a 2.1-cm rainfall, 15 N-labeled E. coli, solutes (rhodamine WT dye and bromide), and latex microspheres were injected into a sinkhole approximately 530 m upgradient of a spring. Breakthrough of all tracers coincided, but microspheres were remobilized by subsequent storms, unlike other tracers. Enriched E. coli exhibited more tailing than solute tracers during the initial storm-flow recession. These results indicate that 15 N-enriched E. coli is a viable tracer of bacterial transport in karst aquifers, although predation may attenuate the isotopic signal in systems that are not rapidly flushed. © 2016, National Ground Water Association.

Spatially-Resolved Analyses of Aerodynamic Fallout from a Uranium-Fueled Nuclear Test

DOE PAGES

Lewis, L. A.; Knight, K. B.; Matzel, J. E.; ...

2015-07-28

The fiive silicate fallout glass spherules produced in a uranium-fueled, near-surface nuclear test were characterized by secondary ion mass spectrometry, electron probe microanalysis, autoradiography, scanning electron microscopy, and energy-dispersive x-ray spectroscopy. Several samples display compositional heterogeneity suggestive of incomplete mixing between major elements and natural U ( 238U/ 235U = 0.00725) and enriched U. Samples exhibit extreme spatial heterogeneity in U isotopic composition with 0.02 < 235U/ 238U < 11.84 among all five spherules and 0.02 < 235U/ 238U < 7.41 within a single spherule. Moreover, in two spherules, the 235U/ 238U ratio is correlated with changes in major elementmore » composition, suggesting the agglomeration of chemically and isotopically distinct molten precursors. Two samples are nearly homogenous with respect to major element and uranium isotopic composition, suggesting extensive mixing possibly due to experiencing higher temperatures or residing longer in the fireball. Linear correlations between 234U/ 238U, 235U/ 238U, and 236U/ 238U ratios are consistent with a two-component mixing model, which is used to illustrate the extent of mixing between natural and enriched U end members.« less

Isotopic separation of snowmelt runoff during an artificial rain-on-snow event

NASA Astrophysics Data System (ADS)

Juras, Roman; Pavlasek, Jirka; Šanda, Martin; Jankovec, Jakub; Linda, Miloslav

2013-04-01

Rain-on-snow events are common phenomenon in the climate conditions of central Europe, mainly during the spring snowmelt period. These events can cause serious floods in areas with seasonal snow. The snowpack hit by rain is able to store a fraction of rain water, but runoff caused by additional snowmelt also increases. Assessment of the rainwater ratio contributing to the outflow from the snowpack is therefore critical for discharge modelling. A rainfall simulator and water enriched by deuterium were used for the study of rainwater behaviour during an artificial rain-on-snow event. An area of 1 m2 of the snow sample, which was 1.2 m deep, consisting of ripped coarse-grained snow, was sprayed during the experiment with deuterium enriched water. The outflow from the snowpack was measured and samples of outflow water were collected. The isotopic content of deuterium was further analyzed from these samples by means of laser spectroscopy for the purpose of hydrograph separation. The concentration of deuterium in snow before and after the experiment was also investigated. The deuterium enriched water above the natural concentration of deuterium in snowpack was detected in the outflow in 7th minute from start of spraying, but the significant increase of deuterium concentration in outflow was observed in 19th minute. The isotopic hydrograph separation estimated, that deuterium enriched rainwater became the major part (> 50% volumetric) of the outflow in 28th minute. The culmination of the outflow (1.23 l min-1) as well as deuterium enriched rainwater fraction (63.5%) in it occurred in 63th minute, i.e. right after the end of spraying. In total, 72.7 l of deuterium enriched water was sprayed on the snowpack in 62 minutes. Total volume of outflow (after 12.3 hours) water was 97.4 l, which contained 48.3 l of deuterium enriched water (i.e. 49.6 %) and 49.1 l (50.4 %) of the melted snowpack. The volume of 24.4 l of deuterium enriched spray-water was stored in the snowpack. The increased total output v. input of the water volume was caused by the warmer spray-water induced snowmelt also connecting separated liquid layers in the snowpack within the process of infiltration and drainage. Key words: deuterium tracer, rainfall simulator, snowmelt

A 1.5 Ma record of plume-ridge interaction at the Western Galápagos Spreading Center (91°40‧-92°00‧W)

NASA Astrophysics Data System (ADS)

Herbrich, Antje; Hauff, Folkmar; Hoernle, Kaj; Werner, Reinhard; Garbe-Schönberg, Dieter; White, Scott

2016-07-01

Shallow (elevated) portions of mid-ocean ridges with enriched geochemical compositions near hotspots document the interaction of hot, geochemically-enriched plume mantle with shallow depleted upper mantle. Whereas the spatial variations in geochemical composition of ocean crust along the ridge axis in areas where plume-ridge interaction is taking place have been studied globally, only restricted information exists concerning temporal variations in geochemistry of ocean crust formed through plume-ridge interaction. Here we present a detailed geochemical study of 0-1.5 Ma ocean crust sampled from the Western Galápagos Spreading Center (WGSC) axis to 50 km north of the axis, an area that is presently experiencing a high influx of mantle material from the Galápagos hotspot. The tholeiitic to basaltic andesitic fresh glass and few bulk rock samples have incompatible element abundances and Sr-Nd-Pb isotopic compositions intermediate between depleted normal mid-ocean-ridge basalt (N-MORB) from >95.5°W along the WGSC and enriched lavas from the Galápagos Archipelago, displaying enriched (E-)MORB type compositions. Only limited and no systematic geochemical variations are observed with distance from the ridge axis for <1.0 Ma old WGSC crust, whereas 1.0-1.5 Ma old crust trends to more enriched isotopic compositions in 87Sr/86Sr, 143Nd/144Nd, 207Pb/204Pb and 208Pb/204Pb isotope ratios. On isotope correlation diagrams, the data set displays correlations between depleted MORB and two enriched components. Neither the geographically referenced geochemical domains of the Galápagos Archipelago nor the end members used for principal component analysis can successfully describe the observed mixing relations. Notably an off-axis volcanic cone at site DR63 has the appropriate composition to serve as the enriched component for the younger WGSC and could represent a portion of the northern part of the Galápagos plume not sampled south of the WGSC. Similar compositions to samples from volcanic cone DR63 have been found in the northern part of the 11-14 Ma Galápagos hotspot track offshore Costa Rica, indicating that this composition is derived from the northern portion of the Galápagos plume. The older WGSC requires involvement of an enriched mantle two (EMII) type source, not recognized thus far in the Galápagos system, and is interpreted to reflect entrained material either from small-scale heterogeneities within the upper mantle or from the mantle transition zone. Overall the source material for the 0-1.5 Ma WGSC ocean crust appears to represent mixing of depleted upper mantle with Northern Galápagos Plume material of relatively uniform composition in relatively constant proportions.

The Origin of EM1 Signatures in Basalts From Tristan da Cunha and Gough

NASA Astrophysics Data System (ADS)

Stracke, A.; Willbold, M.; Hemond, C.

2004-12-01

A long-standing hypothesis is that enriched mantle 1 (EM-1)-type ocean island basalt (OIB) sources contain pelagic sediments. Pelagic sediments range in composition from clays to calcareous or siliceous oozes and encompass a wide range of chemical compositions [1]. For geochemical purposes the use of the term pelagic sediments is often restricted to a special group of pelagic sediments with distinctive enrichment of Rare Earth Elements (REE). The geochemical composition of such REE-enriched pelagic sediments, however, is by no means representative of the geochemical composition of pelagic sediments in general. The extremely high REE/non-REE element ratios in REE-enriched pelagic sediments (e.g. high Lu/Hf, Sm/Hf, La/Nb, La/Th, Eu/Ti, and Gd/Ti ratios) translate into high 176Hf/177Hf ratios for given 143Nd/144Nd ratios with time. OIB sources containing this special variety of REE-enriched pelagic sediment should therefore plot above the oceanic basalt array and mixing arrays with these sources are expected to have a shallow slope in a Hf-Nd isotope diagram. Here we present new Hf-Nd isotope and trace element data for EM-1-type OIB from Tristan da Cunha and Gough in the South Atlantic Ocean. The samples from Tristan have a small range in Hf-Nd isotopic composition and plot within the oceanic basalt array in a Hf-Nd isotope diagram. Samples from Gough form a trend with a slope slightly steeper than that of the ocean basalt array in a Hf-Nd isotope diagram. OIB in general have a very restricted range in Gd/Ti and Sm/Hf ratios, and high La/Nb are associated with low Lu/Hf ratios. In detail, samples from Tristan and Gough have the lowest Lu/Hf and highest La/Nb ratios. Thus from the combined Hf-Nd isotope and trace element composition of basalts from Tristan and Gough involvement of this special variety of (REE-enriched) pelagic sediments can be excluded. Similar observations are made, and thus similar arguments hold, for other EM-1-type localities (Walvis ridge [2] and Pitcairn island [3]). Due to the considerable spread in geochemical composition of pelagic or any other group of sediments (e.g. marine sediments with a higher proportion of terrigenous components), it is difficult to attribute characteristic elemental or isotopic signatures to certain groups of sediment. Moreover, subducting sediments are complex mixtures of different types of sediment [1]. Thus it is difficult to find unique evidence either in favor of or against the involvement of sediments in general at Tristan and Gough, or any other individual OIB locality. Also, it appears highly unlikely that sub-arc processing has an equalizing effect on the composition of different subducting sediments [4]. Associating the similar isotopic characteristics of certain OIB groups and/or mantle-end-members (e.g. EM-1) to recycled sediments is therefore also problematic. [1] Plank, T. and C. H. Langmuir, Chem. Geol., 145, 325-394, 1998. [2] Salters, V. J. M. and X. Li, Geochim. Cosmochim. Acta, 68, A554, 2004. [3] Eisele, J., M. Sharma, J. G. Galer, J. Blichert-Toft, C. W. Devey and A. W. Hofmann, Earth Plan. Sci. Lett., 196, 197-212, 2002. [4] Johnson, M. C. and T. Plank, Geochem., Geophys., Geosys., 1, pp. 29, 1999.

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.

Method for production of an isotopically enriched compound

DOEpatents

Watrous, Matthew G.

2012-12-11

A method is presented for producing and isolating an isotopically enriched compound of a desired isotope from a parent radionuclide. The method includes forming, or placing, a precipitate containing a parent radionuclide of the desired daughter isotope in a first reaction zone and allowing sufficient time for the parent to decay into the desired gaseous daughter radioisotope. The method further contemplates collecting the desired daughter isotope as a solid in a second reaction zone through the application of temperatures below the freezing point of the desired isotope to a second reaction zone that is connected to the first reaction zone. Specifically, a method is presented for producing isotopically enriched compounds of xenon, including the radioactive isotope Xe-131m and the stable isotope Xe-131.

Zircon Hf-O isotopic constraints on the origin of Late Mesozoic felsic volcanic rocks from the Great Xing'an Range, NE China

NASA Astrophysics Data System (ADS)

Gong, Mingyue; Tian, Wei; Fu, Bin; Wang, Shuangyue; Dong, Jinlong

2018-05-01

The voluminous Late Mesozoic magmatism was related to extensive re-melting of juvenile materials that were added to the Central East Asia continent in Phanerozoic time. The most favoured magma generation mechanism of Late Mesozoic magmas is partial melting of underplated lower crust that had radiogenic Hf-Nd isotopic characteristics, but this mechanism faces difficulties when interpreting other isotopic data. The tectonic environment controlling the generation of the Late Mesozoic felsic magmas is also in dispute. In this study, we obtained new U-Pb ages, and geochemical and isotopic data of representative Jurassic (154.4 ± 1.5 Ma) and Cretaceous (140.2 ± 1.5 Ma) felsic volcanic samples. The Jurassic sample has inherited zircon cores of Permian age, with depleted mantle-like εHf(t) of +7.4 - +8.5, which is in contrast with those of the magmatic zircons (εHf(t) = +2.4 ± 0.7). Whereas the inherited cores and the magmatic zircons have identical mantle-like δ18O composition ranges (4.25-5.29‰ and 4.69-5.54‰, respectively). These Hf-O isotopic characteristics suggest a mixed source of enriched mantle materials rather than ancient crustal components and a depleted mantle source represented by the inherited Permian zircon core. This mechanism is manifested by the eruption of Jurassic alkaline basalts originated from an enriched mantle source. The Cretaceous sample has high εHf(t) of +7.0 - +10.5, suggesting re-melting of a mafic magma derived from a depleted mantle-source. However, the sub-mantle zircon δ18O values (3.70-4.58‰) suggest the depleted mantle-derived mafic source rocks had experienced high temperature hydrothermal alteration at upper crustal level. Therefore, the Cretaceous felsic magma, if not all, could be generated by re-melting of down-dropped supracrustal volcanic rocks that experienced high temperature oxygen isotope alteration. The two processes, enriched mantle-contribution and supracrustal juvenile material re-melting, are new generation mechanisms of the Late Mesozoic magmas from Central East Asia. Rift settings may have controlled these processes throughout crustal and mantle levels.

Airsheds, Isotopes and Ecosystem Metabolism in Mountainous Terrain

NASA Astrophysics Data System (ADS)

Sulzman, E.; Barnard, H.; Bond, B. J.; Czarnomski, N. M.; Hauck, M.; Kayler, Z.; Mix, A. C.; Pypker, T.; Rugh, W.; Unsworth, M.

2005-12-01

At least 20% of the terrestrial surface of the earth is covered by mountains, which contain many of the world's most productive ecosystems. Interactions between vegetation and the physical environment are often very different in mountains than on flat land. However, few studies have addressed these unique interactions, and many of the tools used to measure and monitor ecosystem metabolism are difficult or impossible to use in complex, mountainous terrain. In a project we call the "Andrews Airshed study" located in western Oregon Cascades, we aim to identify and explore sources of variation in the isotopic composition of ecosystem respiration (δ13CR-eco) and airflow patterns in cold-air drainage, with the eventual aim of "inverting" this understanding so that we can use δ13CR-eco to monitor intra- and inter-annual variations in ecosystem metabolism on a basin scale. We are measuring patterns of airflow, quantifying the CO2 concentration in the flow, and measuring the carbon isotope composition of ecosystem-respired CO2 as well as soil-respired CO2 (δ13CR-soil), which accounts for more than half of δ13CR-eco. We have designed an automated air sampling device that we programmed to sample air at 10 ppm intervals from 30 m above the stream in our 100 ha, deeply-incised watershed. Samples are collected via Valco valves into stainless steel tubing that can be connected directly to an isotope ratio mass spectrometer. We also designed and installed soil gas sampling probes, which are located in five 10 m2 sampling plots from ridge top to valley floor to the opposite ridge top. Weekly samples (May-Sept, 2005) of air from soil and the nocturnal air flow show seasonal variation in δ13CR-eco over a 2 per mil range, with more enriched values corresponding to lower soil moisture. Soil-respired CO2 also reveal seasonality and are isotopically enriched compared with above-ground air. δ13CR-soil values from north- and south-facing slopes of the watershed differ by 1 per mil, with south-facing values consistently enriched relative to those of the north-facing slope. We are concurrently conducting studies to determine the appropriate footprint of respired CO2 in the nocturnal airstream, which will allow us to overlay the data properly.

A new method for stable carbon isotope analysis of chlorofluorocarbons in contaminated groundwater

NASA Astrophysics Data System (ADS)

Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

2015-04-01

Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been widely used as refrigerants, propellants, solvents, foaming agents and are important intermediates in the production of anesthetics and other fluorinated compounds. Due to their ozone depletion potential, production was banned for most uses under the Montreal Protocol (1987) and its amendments and atmospheric mixing ratios have started to decrease. In addition to the atmosphere, CFCs and HCFCs have been detected in groundwater, and emissions from various sources such as landfill sites are still ongoing. Previous studies have shown that both abiotic and biotic transformation of CFCs may occur under certain conditions. To investigate degradation that may take place in soils and groundwaters, a purge and trap method (P&T) has been developed to measure the stable carbon isotopic composition of CFCs and HCFCs extracted from waters. A set of pure phase working standards (HCFC-22, CFC-11, CFC-113) has been prepared offline and characterized by sealed tube combustion dual inlet mass spectrometry. Comparison between isotopic standards and CFCs extracted by our method demonstrates the sample P&T extraction steps do not induce significant δ13C fractionation (lt;0.5 per mill). Standards characterized by continuous flow CSIA (compound specific isotope analysis) after extraction agree with offline characterized values. Evaporation experiments were carried out to investigate any isotope effects due to volatile loss that might occur either due to sampling methods or sample handling in the lab. Monitoring δ13C values during progressive evaporation showed small isotopic fractionation associated with evaporation. Enrichment factors, obtained from Rayleigh plots, showed inverse isotope fractionation i.e depletion in 13C in the remaining compound. Notably, this effect is in the opposite direction to the fractionation (13C enrichment) that is likely to be associated with abiotic or biotic transformation effects. This bodes well for the use of CSIA to identify and monitor transformation in the field as any isotopic effects due to volatile loss would only result in a conservative estimate of transformation but not confuse the degradation signal. As a result, enrichment factors in field samples might be underestimated and lead to a more conservative estimate of degradation at contaminated sites. CFCs from several suppliers were characterized to investigate δ13C variation between sources and between different CFC compounds. Significant differences were observed between all measured compounds. However for each compound, δ13C values determined in this study were similar to ranges reported previously for other pure phase CFCs - suggesting a consistent range of source signatures may exist for each compound. As a last step of method evaluation, water samples from a contaminated industrial site were measured. This first preliminary field data will be discussed in comparison to pure phase compounds and with respect to potential degradation.

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.

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

NASA Astrophysics Data System (ADS)

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

2009-05-01

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

The influence of microclimates and fog on stable isotope signatures used in interpretation of regional hydrology: East Maui, Hawaii

USGS Publications Warehouse

Scholl, M.A.; Gingerich, S.B.; Tribble, G.W.

2002-01-01

Stable isotopes of precipitation, ground water and surface water measured on the windward side of East Maui from 0 to 3055 m altitude were used to determine recharge sources for stream flow and ground water. Correct interpretation of the hydrology using rainfall ??18O gradients with altitude required consideration of the influence of fog, as fog samples had isotopic signatures enriched by as much as 3??? in ??18O and 21??? in ??D compared to volume-weighted average precipitation at the same altitude. The isotopic analyses suggested that fog drip was a major component of stream flow and shallow ground water at higher altitudes in the watershed. 18O/altitude gradients in rainfall were comparable for similar microclimates on Maui (this study) and Hawaii Island (1990-1995 study), however, East Maui ??18O values for rain in trade-wind and high-altitude microclimates were enriched compared to those from Hawaii Island. Isotopes were used to interpret regional hydrology in this volcanic island aquifer system. In part of the study area, stable isotopes indicate discharge of ground water recharged at least 1000 m above the sample site. This deep-flowpath ground water was found in springs from sea level up to 240 m altitude, indicating saturation to altitudes much higher than a typical freshwater lens. These findings help in predicting the effects of ground water development on stream flow in the area. Published by Elsevier Science B.V.

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.

Method for enriching a gaseous isotopic mixture with at least one isotope

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

de Mevergnies, M.N.; Fettweis, P.

1982-02-02

There is described a method for enriching a gas-like isotopic mixture with at least one isotope, in which a mixture of Cf2Cl2 and O2 is irradiated by means of a pulsed and focalized laser beam having an optical frequency corresponding to a wave number lying in the band from 920 to 945 cm-1 to enrich the residual Cf2Cl2 with 37Cl, in the band from 1050 to 1075 cm-1 to produce CoF2 enriched with 13C and/or in the band from 1080 to 1095 cm-1 to enrich the residual Cf2Cl2 with 35Cl and 13C.

Production of beta-gamma coincidence spectra of individual radioxenon isotopes for improved analysis of nuclear explosion monitoring data

NASA Astrophysics Data System (ADS)

Haas, Derek Anderson

Radioactive xenon gas is a fission product released in the detonation of nuclear devices that can be detected in atmospheric samples far from the detonation site. In order to improve the capabilities of radioxenon detection systems, this work produces beta-gamma coincidence spectra of individual isotopes of radioxenon. Previous methods of radioxenon production consisted of the removal of mixed isotope samples of radioxenon gas released from fission of contained fissile materials such as 235U. In order to produce individual samples of the gas, isotopically enriched stable xenon gas is irradiated with neutrons. The detection of the individual isotopes is also modeled using Monte Carlo simulations to produce spectra. The experiment shows that samples of 131mXe, 133 Xe, and 135Xe with a purity greater than 99% can be produced, and that a sample of 133mXe can be produced with a relatively low amount of 133Xe background. These spectra are compared to models and used as essential library data for the Spectral Deconvolution Analysis Tool (SDAT) to analyze atmospheric samples of radioxenon for evidence of nuclear events.

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

USGS Publications Warehouse

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

1999-01-01

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

Deproteinization assessment using isotopically enriched compounds to trace the coprecipitation of low-molecular-weight selenium species with proteins.

PubMed

Godin, Simon; Bouzas-Ramos, Diego; Fontagné-Dicharry, Stéphanie; Bouyssière, Brice; Bueno, Maïté

2017-08-01

Studies have shown that information related to the presence of low-molecular-weight metabolites is frequently lost after deproteinization of complex matrices, such as blood and plasma, during sample preparation. Therefore, the effect of several deproteinization reagents on low-molecular-weight selenium species has been compared by species-specific isotope labeling. Two isotopically enriched selenium tracers were used to mimic models of small inorganic anionic ( 77 Se-selenite) and organic zwitterionic ( 76 Se-selenomethionine) species. The results presented here show that the use of a methanol-acetonitrile-acetone (1:1:1 v/v/v) mixture provided approximately two times less tracer loss from plasma samples in comparison with the classic procedure using acetonitrile, which may not be optimal as it leads to important losses of low-molecular-weight selenium species. In addition, the possible interactions between selenium tracers and proteins were investigated, revealing that both coprecipitation phenomena and association with proteins were potentially responsible for selenite tracer losses during protein precipitation in blood samples. However, coprecipitation phenomena were found to be fully responsible for losses of both tracers observed in plasma samples and of the selenomethionine tracer in blood samples. This successfully applied strategy is anticipated to be useful for more extensive future studies in selenometabolomics. Copyright © 2017 Elsevier Inc. All rights reserved.

New Insights from Zinc and Copper Isotopic Compositions into the Sources of Atmospheric Particulate Matter from Two Major European Cities.

PubMed

Gonzalez, R Ochoa; Strekopytov, S; Amato, F; Querol, X; Reche, C; Weiss, D

2016-09-20

This study reports spatial and temporal variability of Zn and Cu isotopes in atmospheric particulate matter (PM) collected in two major European cities with contrasting atmospheric pollution, Barcelona and London. We demonstrate that nontraditional stable isotopes identify source contributions of Zn and Cu and can play a major role in future air quality studies. In Barcelona, samples of fine PM were collected at street level at sites with variable traffic density. The isotopic signatures ranged between -0.13 ± 0.09 and -0.51 ± 0.05‰ for δ(66)ZnIRMM and between +0.04 ± 0.20 and +0.33 ± 0.15‰ for δ(65)CuAE633. Copper isotope signatures similar to those of Cu sulfides and Cu/Sb ratios within the range typically found in brake wear suggest that nonexhaust emissions from vehicles are dominant. Negative Zn isotopic signatures characteristic for gaseous emissions from smelting and combustion and large enrichments of Zn and Cd suggest contribution from metallurgical industries. In London, samples of coarse PM collected on the top of a building over 18 months display isotope signatures ranging between +0.03 ± 0.04 and +0.49 ± 0.02‰ for δ(66)ZnIRMM and between +0.37 ± 0.17 and +0.97 ± 0.21‰ for δ(65)CuAE633. Heavy Cu isotope signatures (up to +0.97 ± 0.21‰) and higher enrichments and Cu/Sb ratios during winter time indicate important contribution from fossil fuel combustion. The positive δ(66)ZnIRMM signatures are in good agreement with signatures characteristic for ore concentrates used for the production of tires and galvanized materials, suggesting nonexhaust emissions from vehicles as the main source of Zn pollution.

Synthesis and characterization of surrogate nuclear explosion debris: urban glass matrix

DOE PAGES

Campbell, Keri; Judge, Elizabeth J.; Dirmyer, Matthew R.; ...

2017-07-26

Surrogate nuclear explosive debris was synthesized and characterized for major, minor, and trace elemental composition as well as uranium isotopics. The samples consisted of an urban glass matrix, equal masses soda lime and cement, doped with 500 ppm uranium with varying enrichments. The surface and cross section morphology were measured with SEM, and the major elemental composition was determined by XPS. LA-ICP-MS was used to measure the uranium isotopic abundance comparing different sampling techniques. Furthermore, the results provide an example of the utility of LA-ICP-MS for forensics applications.

The plasma separation process as a pre-cursor for large scale radioisotope production

NASA Astrophysics Data System (ADS)

Stevenson, Nigel R.

2001-07-01

Radioisotope production generally employs either accelerators or reactors to convert stable (usually enriched) isotopes into the desired product species. Radioisotopes have applications in industry, environmental sciences, and most significantly in medicine. The production of many potentially useful radioisotopes is significantly hindered by the lack of availability or by the high cost of key enriched stable isotopes. To try and meet this demand, certain niche enrichment processes have been developed and commercialized. Calutrons, centrifuges, and laser separation processes are some of the devices and techniques being employed to produce large quantities of selective enriched stable isotopes. Nevertheless, the list of enriched stable isotopes in sufficient quantities remains rather limited and this continues to restrict the availability of many radioisotopes that otherwise could have a significant impact on society. The Plasma Separation Process is a newly available commercial technique for producing large quantities of a wide range of enriched isotopes and thereby holds promise of being able to open the door to producing new and exciting applications of radioisotopes in the future.

Estimating pothole wetland connectivity to Pipestem Creek ...

EPA Pesticide Factsheets

Understanding hydrologic connectivity between wetlands and perennial streams is critical to understanding how reliant stream flow is on wetlands within their watershed. We used the isotopic evaporation signal in water to examine wetland-stream hydrologic connectivity within the Pipestem Creek watershed, North Dakota, a watershed dominated by prairie-pothole wetlands. During a wetter-than-normal decade, Pipestem Creek exhibited an evaporated-water signal that had approximately half the isotopic-enrichment signal found in most evaporatively enriched pothole wetlands. If evaporation was mainly occurring within the stream, we expected the evaporation signal to increase from upstream towards downstream. However, the signal either remained similar or decreased downstream over the two years of sampling. Groundwater measured at the water table adjacent to Pipestem Creek had isotopic values that indicated recharge from winter precipitation and had no significant evaporative enrichment. Using isotopic theory and discharge data, we estimated the surface area of open water necessary to generate the evaporation signal found within Pipestem Creek over time. The range of evaporating surface-area estimates was highly dynamic, spanning from 35 to 2380 ha of open water contributing to streamflow over time, and varied primarily with the amount of discharge. The median value (417 ha) was well above the surface area of the Pipestem Creek network (245 ha), and only two periods

Intra- and Inter-Annual Variability in Surface Hydrology in Northern Arizona from δ18O of Tree-Ring Cellulose

NASA Astrophysics Data System (ADS)

Whittaker, T. E.; Galewsky, J.; Scuderi, L. A.; Sharp, Z. D.

2010-12-01

The primary goal of our research is to better understand how the surface hydrology of semi-arid sites in the Southwestern U.S. is affected by the annual cycles of precipitation and evaporation. Both are tied to relative strength of the North American Monsoon, El Niño-Southern Oscillation and, on shorter timescales, the occasional passage of tropical cyclone remnants. To achieve this we aim to develop high-resolution stable oxygen isotope ratio (δ18O) profiles of tree-ring cellulose for much of the last 20 years that can be ground-truthed to direct meteorological observations. It is well documented that δ18O of alpha-cellulose extracted from wood reflects hydrological conditions of a trees’ environment at the time the tree grew. Primary controls on isotopic variability are changes in source waters and relative humidity during the growing season. We sampled rings from ≥ 10 Pinus ponderosa (Douglas) at six stands along an east-west transect across northern Arizona. Annual precipitation at these sites has a bimodal distribution with almost all annual rainfall occurring during the summer monsoon (Jul, Aug) and winter storms. At Flagstaff, in the center of our study area, monthly mean precipitation δ18O values are enriched ~6‰ during the monsoon relative to winter storms. P. ponderosa (Dougl.) rings display distinct early- and latewood bands. Earlywood typically forms using winter storm precipitation that has resided within the soil until the tree began growing and ought to reflect the isotopic composition of this water. Latewood δ18O reportedly reflect summer rainfall isotopic values. We investigate the eleven year period 1994-2004. This range encompasses the transition into the present ‘drought’, the intense 1997/98 El Niño, and the passage of the remnants of Hurricanes Nora (1997) and Javier (2004). Individual rings are sliced into subsamples of mass ~1.5 mg (yielding 3-13 samples/ring). Early isotopic data from these samples display three significant trends. First, isotopic variability in a given annual ring is closely matched at intra- and inter-tree scales in a single stand (inter-site comparisons unavailable at time of writing). Second, isotopic values demonstrate that trees growing within meters of each other do not begin/cease growing simultaneously, which has implications for low-resolution isotope cross-dating studies. Third, and most significantly, earlywood samples are consistently enriched in 18O relative to latewood samples by on average ~6‰. This result is unexpected based on the isotopic composition of local precipitation and suggests that rates of evaporative enrichment of 18O in soil and leaf moisture during the growing season vary and with significant effect. Further investigation of this phenomenon will incorporate IsoGSM model output of growing season precipitation and water vapor δ18O for the period of study.

Method for laser induced isotope enrichment

DOEpatents

Pronko, Peter P.; Vanrompay, Paul A.; Zhang, Zhiyu

2004-09-07

Methods for separating isotopes or chemical species of an element and causing enrichment of a desired isotope or chemical species of an element utilizing laser ablation plasmas to modify or fabricate a material containing such isotopes or chemical species are provided. This invention may be used for a wide variety of materials which contain elements having different isotopes or chemical species.

Soil water stable isotopes reveal evaporation dynamics at the soil-plant-atmosphere interface of the critical zone

NASA Astrophysics Data System (ADS)

Sprenger, Matthias; Tetzlaff, Doerthe; Soulsby, Chris

2017-07-01

Understanding the influence of vegetation on water storage and flux in the upper soil is crucial in assessing the consequences of climate and land use change. We sampled the upper 20 cm of podzolic soils at 5 cm intervals in four sites differing in their vegetation (Scots Pine (Pinus sylvestris) and heather (Calluna sp. and Erica Sp)) and aspect. The sites were located within the Bruntland Burn long-term experimental catchment in the Scottish Highlands, a low energy, wet environment. Sampling took place on 11 occasions between September 2015 and September 2016 to capture seasonal variability in isotope dynamics. The pore waters of soil samples were analyzed for their isotopic composition (δ2H and δ18O) with the direct-equilibration method. Our results show that the soil waters in the top soil are, despite the low potential evaporation rates in such northern latitudes, kinetically fractionated compared to the precipitation input throughout the year. This fractionation signal decreases within the upper 15 cm resulting in the top 5 cm being isotopically differentiated to the soil at 15-20 cm soil depth. There are significant differences in the fractionation signal between soils beneath heather and soils beneath Scots pine, with the latter being more pronounced. But again, this difference diminishes within the upper 15 cm of soil. The enrichment in heavy isotopes in the topsoil follows a seasonal hysteresis pattern, indicating a lag time between the fractionation signal in the soil and the increase/decrease of soil evaporation in spring/autumn. Based on the kinetic enrichment of the soil water isotopes, we estimated the soil evaporation losses to be about 5 and 10 % of the infiltrating water for soils beneath heather and Scots pine, respectively. The high sampling frequency in time (monthly) and depth (5 cm intervals) revealed high temporal and spatial variability of the isotopic composition of soil waters, which can be critical, when using stable isotopes as tracers to assess plant water uptake patterns within the critical zone or applying them to calibrate tracer-aided hydrological models either at the plot to the catchment scale.

The oxygen isotope enrichment of leaf-exported assimilates--does it always reflect lamina leaf water enrichment?

PubMed

Gessler, Arthur; Brandes, Elke; Keitel, Claudia; Boda, Sonja; Kayler, Zachary E; Granier, André; Barbour, Margaret; Farquhar, Graham D; Treydte, Kerstin

2013-10-01

The oxygen stable isotope composition of plant organic matter (OM) (particularly of wood and cellulose in the tree ring archive) is valuable in studies of plant-climate interaction, but there is a lack of information on the transfer of the isotope signal from the leaf to heterotrophic tissues. We studied the oxygen isotopic composition and its enrichment above source water of leaf water over diel courses in five tree species covering a broad range of life forms. We tracked the transfer of the isotopic signal to leaf water-soluble OM and further to phloem-transported OM. Observed leaf water evaporative enrichment was consistent with values predicted from mechanistic models taking into account nonsteady-state conditions. While leaf water-soluble OM showed the expected (18)O enrichment in all species, phloem sugars were less enriched than expected from leaf water enrichment in Scots pine (Pinus sylvestris), European larch (Larix decidua) and Alpine ash (Eucalyptus delegatensis). Oxygen atom exchange with nonenriched water during phloem loading and transport, as well as a significant contribution of assimilates from bark photosynthesis, can explain these phloem (18)O enrichment patterns. Our results indicate species-specific uncoupling between the leaf water and the OM oxygen isotope signal, which is important for the interpretation of tree ring data. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

Neutron capture cross sections of Kr

NASA Astrophysics Data System (ADS)

Fiebiger, Stefan; Baramsai, Bayarbadrakh; Couture, Aaron; Krtička, Milan; Mosby, Shea; Reifarth, René; O'Donnell, John; Rusev, Gencho; Ullmann, John; Weigand, Mario; Wolf, Clemens

2018-01-01

Neutron capture and β- -decay are competing branches of the s-process nucleosynthesis path at 85Kr [1], which makes it an important branching point. The knowledge of its neutron capture cross section is therefore essential to constrain stellar models of nucleosynthesis. Despite its importance for different fields, no direct measurement of the cross section of 85Kr in the keV-regime has been performed. The currently reported uncertainties are still in the order of 50% [2, 3]. Neutron capture cross section measurements on a 4% enriched 85Kr gas enclosed in a stainless steel cylinder were performed at Los Alamos National Laboratory (LANL) using the Detector for Advanced Neutron Capture Experiments (DANCE). 85Kr is radioactive isotope with a half life of 10.8 years. As this was a low-enrichment sample, the main contaminants, the stable krypton isotopes 83Kr and 86Kr, were also investigated. The material was highly enriched and contained in pressurized stainless steel spheres.

Isotope enrichment by frequency-tripled temperature tuned neodymium laser photolysis of formaldehyde

DOEpatents

Marling, John B.

1977-01-01

Enrichment of carbon, hydrogen and/or oxygen isotopes by means of isotopically selective photo-predissociation of formaldehyde is achieved by irradiation provided by a frequency-tripled, temperature tuned neodymium laser.

Spatial and Temporal Mapping of Distributed Surface and Groundwater Stable Isotopes Enables New insights into Hydrologic Processes Operating at the Catchment Scale

NASA Astrophysics Data System (ADS)

Cole, A.; Boutt, D. F.

2017-12-01

Isotopic analyses of d18O and d2H of water transiting the hydrologic cycle have allowed hydrologists to better understand the portioning of water between the different components of the water cycle. Isoscapes on a large spatial scale have been created to show isotopic variation in waters as a function of elevation, temperature, distance to coast and precipitation. This has not been done on a 10,000 sq mi area, sub-regional scale or for that matter exhaustively sampled the important components of the terrestrial hydrologic cycle (groundwater, surface water and soil waters). We present the spatial and temporal isotopic results of an ongoing study across Massachusetts, USA, to establish an isotopic baseline for the region. Our current database consists of water samples from 50 precipitation sites, 333 ground water sites and 421 surface water sites. The isotopic signature of d18O and d2H of the samples are measured by a wavelength scanned cavity ring-down spectrometry on un-acidified water samples by a Picarro Cavity Ring Down Spectrometer (L2120-I) analyzer. Our results show that groundwater ranges from -11 to -1 ‰ δ18O across Massachusetts. Wells show a correlation with elevation; at higher elevations groundwater is more depleted in the heavy isotopes than compared with wells located at a lower elevation. Surface, groundwater and precipitation depict a seasonal evaporative enrichment, with waters being lighter during the months and heavier during the summer months. Based on Massachusetts location relative to the coast, there is a large variability in the mean d18O of precipitation with rain being heavy near the coast and lighter with increasing distance from the coast. HYSPLIT trajectory models will be used to determine how source affects isotopic composition. Within Massachusetts the isotopic composition of groundwater in till, glacial fluvial and bedrock aquifers are distinct which indicates the potential for surface and groundwater interaction. Our data also indicates groundwater enrichment in the heavy isotopes. In order to further determine the interrelationship between surface and groundwater we will measure chloride on both surface and groundwater and relate the results. This dataset will become an important tool for water management and water resources.

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.

Re-Os Isotope Systematics in Lunar Soils and Breccias

NASA Technical Reports Server (NTRS)

Chen, J. H.; Papanastassiou, D. A; Wasserburg, G. J.

2002-01-01

Lunar soil and breccia samples show a narrow range in 187Os/188Os, in the range for H-chondrites and unfractionated irons. All samples show enrichments in 187Re/188Os, possibly reflecting loss of Os, associated with the terminal lunar cataclysm. Additional information is contained in the original extended abstract.

Ion laser isotope enrichment by photo-predissociation of formaldehyde

DOEpatents

Marling, John B.

1977-06-17

Enrichment of carbon, hydrogen and/or oxygen isotopes by means of isotopically selective photo-predissociation of formaldehyde is achieved by irradiation with a fixed frequency ion laser, specifically, a neon, cadmium, or xenon ion laser.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

NASA Astrophysics Data System (ADS)

Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

2014-01-01

Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e. equivalent to ~ 8 ng of amino sugar carbon. Our results obtained from δ13C analysis of amino sugars in selected marine sediment samples showed that muramic acid had isotopic imprints from indigenous bacterial activities, whereas glucosamine and galactosamine were mainly derived from organic detritus. The analysis of stable carbon isotopic compositions of amino sugars opens a promising window for the investigation of microbial metabolisms in marine sediments and the deep marine biosphere.

Extreme isotopic variations in the upper mantle: evidence from Ronda

NASA Astrophysics Data System (ADS)

Reisberg, Laurie; Zindler, Alan

1986-12-01

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

Pb-isotopic Features of Primitive Rocks from Hess Deep: Distinguishing between EPR and Cocos-Nazca Mantle Source(s)

NASA Astrophysics Data System (ADS)

Jean, M. M.; Falloon, T.; Gillis, K. M.

2014-12-01

We have acquired high-precision Pb-isotopic signatures of primitive lithologies (basalts/gabbros) recovered from IODP Expedition 345.The Hess Deep Rift, located in the vicinity of the Galapagos triple junction (Cocos, Nazca, and Pacific), is viewed as one the best-studied tectonic windows into fast-spreading crust because a relatively young (<1.5 Ma) cross section of oceanic crust. This allows for (1) characterization of the mantle source(s) at Hess Deep, (2) insight into the extent of isotopic homogeneity or heterogeneity in the area, and (3) constrain the relative contributions from the intruding Cocos-Nazca spreading center. The observed Pb-isotopic variation at Hess Deep covers almost the entire range of EPR MORB (10°N to -5°S). Hess Deep samples range from 208Pb (37.3-38.25), 207Pb (15.47-15.58), 206Pb (17.69-18.91). These compositions suggest that this part of Hess Deep mantle is no more isotopically homogeneous than EPR mantle. Two distinct arrays are also observed: 208Pb-enriched (r2=0.985; n=30) and 208Pb-depleted (r2=0.988; n=6). The 208Pb/204Pb isotopes indicates that the Pb-source for some of the samples at Hess Deep had very low Th/U ratios, whereas other areas around the Galapagos microplate seem to have more "normal" ratios. These trends are less apparent when viewed with 207Pb-isotopes. Instead, the majority of basalts and gabbros follow the NHRL, however, at the depleted-end of this array a negative excursion to more enriched compositions is observed. This negative but linear trend could signify an alteration trend or mixing with an EMI-type mantle source, yet this mixing is not observed with 208Pb. This trend is also observed at Pito Deep, which has similar origins to Hess Deep (Barker et al., 2008; Pollack et al., 2009). The Galapagos region has been considered a testing ground for mixing of HIMU, Enriched Mantle, and Depleted Mantle reservoirs (e.g., Schilling et al., 2002). According to our data, however, an EPR-component must also be considered. We model Hess Deep Pb-isotopes as a 4-component system. EPR-DM-EM comprise a 'local' reservoir, but the majority of samples contain a mixture of modified-HIMU-EM-EPR, a product of incoming plume material entrained within the Galapagos Spreading Center.

Fractionation of Nitrogen and Oxygen Isotopes and Roles of Bacteria during Denitrification

NASA Astrophysics Data System (ADS)

Kang, J.; Buyanjargal, A.; Jeen, S. W.

2017-12-01

Nitrate in groundwater can cause health and environmental problems when not properly treated. The purpose of this study was to develop a treatment method for nitrate in groundwater using organic carbon-based reactive mixtures (i.e., wood chips and gravel) through column experiments and to evaluate reaction mechanisms responsible for the treatment. The column experiments were operated for a total of 19 months. The results from the geochemical analyses for the experiments suggest that cultures of denitrifying bacteria used organic carbon while utilizing nitrate as their electron acceptor via denitrification process. Proteobacteria was the most abundant phylum in all samples, accounting for 45.7% of the bacterial reads, followed by Firmicutes (22.6%) and Chlorobi (10.6%). Bacilli, Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, and Actinobacteria_c consisted of 32, 30, 23, 11, and 2% of denitrifying bacteria class. The denitrification process caused fractionation of nitrogen and oxygen isotopes of nitrate while nitrate concentration decreased. When fitted to the Rayleigh's fractionation model, enrichment factors (ɛ) were 11.5‰ and 5.6‰ for 15N and 18O isotopes, respectively. Previous studies suggested that nitrogen isotope enrichment factors of denitrification are within the range of 4.7 to 40‰ and oxygen isotopic enrichment factors are between 8 and 18.3‰. This study shows that nitrate in groundwater can be effectively treated using passive treatment systems, such as permeable reactive barriers (PRBs), and denitrificaton is the dominant process reponsible for the removal of nitrate.

Comparison between PGAA and ID-AMS analysis for determining chlorine content in whole rock basalt

NASA Astrophysics Data System (ADS)

di Nicola, L.; Schnabel, C.; Wilcken, K. M.; Gméling, K.

2009-04-01

Accurate determination of chlorine concentrations in terrestrial rocks is of importance for the interpretation of terrestrial in-situ cosmogenic 36Cl. Neutron capture by 35Cl, together with production from Ca and K, is one of the three major production pathways of 36Cl in rocks. Here, we present an inter-comparison of chlorine determinations by two procedures. The first approach is an independent Cl determination by prompt gamma (neutron) activation analysis (PGAA). The second method is isotope dilution based on isotopically-enriched stable chlorine carrier added during chemical sample preparation for accelerator mass spectrometry (ID-AMS). Twenty six (26) whole rock samples have been processed for PGAA and ID-AMS analyses. Elemental analysis by PGAA provides concentrations of major, minor and trace elements including the target elements for 36Cl production (K, Ca, Ti, and Fe), as well as of neutron absorbers and neutron moderators (H, B, Cl, Sm and Gd). The Cl concentrations determined during this study constitute the first inter-comparison for concentrations below 100 μCl/g. Our results show no significant difference in Cl concentrations between methods, and comparable uncertainties. This agreement guarantees that during the procedure we employ for whole rock sample no significant loss of stable chlorine from either the spike or the sample occurs before isotopic equilibration, prior to AgCl precipitation. Furthermore, we show that the elemental analysis by PGAA offers anadvance for the interpretation of 36Cl measurements. It allows simultaneous measurement of major and most trace element concentrations with a precision necessary for calculating the relative contributions to 36Cl production rates of the different mechanisms. Finally, the Cl concentration can be used to optimize the amount of isotopically-enriched spike for AMS-ID sample preparation for 36Cl.

HIMU-type Mid-Ocean Ridge Basalts Incorporate a Primitive Component

NASA Astrophysics Data System (ADS)

Tucker, J.; Mukhopadhyay, S.; Schilling, J. E.

2011-12-01

Samples from 5°N to 7°S along the MAR axis span a range of compositions from depleted MORB (La/SmN ~0.5, 206Pb/204Pb ~18) to very enriched MORB (La/SmN ~3, 206Pb/204Pb ~20). The measured 206Pb/204Pb in the enriched samples are among the highest measured MORB values and are thought to represent a HIMU type mantle (high μ where μ is the U/Pb ratio). Therefore, the enriched samples provide a unique opportunity to characterize the heavy noble gas composition of the HIMU mantle. If HIMU mantle is related to recycled crust, then the noble gas measurements can also provide insights into recycling of atmospheric noble gases back into the mantle. Additionally, the depleted equatorial samples provide an opportunity to characterize the Ar and Xe composition of the N-MORB source for comparison to the 14°N E-MORB popping rock. Finally, the large variations in lithophile isotopes over a geographically short distance affords the opportunity to study the nature of coupling between the noble gases and lithophile tracers, and understand the origin of the heterogeneities in the MORB source. Stepwise crushing and rare gas analysis (He, Ne, Ar, Xe) was undertaken for both enriched and depleted samples. Many of the crushing steps yielded 20Ne/22Ne > 12, and good correlations between Ne, Ar, and Xe isotopes allow for mantle source compositions of Ar and Xe to be determined by extrapolating the measured values to a mantle 20Ne/22Ne of 12.5. The highest measured values of Ar and Xe in a depleted N-MORB are comparable to measured values of the E-MORB popping rock (40Ar/36Ar ~28,000, 129Xe/130Xe ~7.7). When extrapolated to a mantle 20Ne/22Ne of 12.5, the depleted MORB sample indicates a 40Ar/36Ar of ~43,000 (higher than popping rock) and 129Xe/130Xe of ~7.8. Enriched MORB samples from this suite, thought to represent the HIMU mantle, have the same He and Ne characteristics as HIMU basalts from the Cook and Austral Islands; more radiogenic He than MORBs is accompanied by less nucleogenic Ne than MORBs. Additionally, the enriched MORB samples also constrain the HIMU mantle 40Ar/36Ar to ~20,000 and 129Xe/130Xe ~7.3-7.5, significantly lower than the depleted MORBs. Like the HIMU basalts from the Cook and Austral Islands, a less degassed reservoir than the MORB source must be invoked to explain the He and Ne systematics in the HIMU-type MORBs. If HIMU represents recycled crust, then it must have entrained or been entrained by a less degassed mantle from the deep interior. This less degassed reservoir would also explain the good correspondence between low 21Ne/22Ne, low 40Ar/36Ar and low 129Xe/130Xe in the HIMU-type samples. While we cannot rule out recycling of atmospheric noble gases to explain the low 40Ar/36Ar and 129Xe/130Xe, involvement of a source less degassed in He and Ne would also be accompanied by a less degassed Ar and Xe isotopic signature. Therefore the simplest explanation of the covariation between the noble gases and lithophile isotopes involves a mixture of a less processed and hence more primitive component, a degassed recycled component, and depleted MORB mantle beneath the equatorial Mid-Atlantic Ridge.

Effects of recharge and discharge on delta2H and delta18O composition and chloride concentration of high arsenic/fluoride groundwater from the Datong Basin, northern China.

PubMed

Xie, Xianjun; Wang, Yanxin; Su, Chunli; Duan, Mengyu

2013-02-01

To better understand the effects of recharge and discharge on the hydrogeochemistry of high levels of arsenic (As) and fluoride (F) in groundwater, environmental isotopic composition (delta2H and delta18O) and chloride (Cl) concentrations were analyzed in 29 groundwater samples collected from the Datong Basin. High arsenic groundwater samples (As > 50 micog/L) were found to be enriched in lighter isotopic composition that ranged from -92 to -78 per thousand for deuterium (delta2H) and from -12.5 to -9.9 per thousand for oxygen-18 (delta18O). High F-containing groundwater (F > 1 mg/L) was relatively enriched in heavier isotopic composition and varied from -90 to -57 per thousand and from -12.2 to -6.7 per thousand for delta2H and delta18O, respectively. High chloride concentrations and delta18O values were primarily measured in groundwater samples from the northern and southwestern portions of the study area, indicating the effect of evaporation on groundwater. The observation of relatively homogenized and low delta18O values and chloride concentrations in groundwater samples from central part of the Datong Basin might be a result of fast recharge by irrigation returns, which suggests that irrigation using arsenic-contaminated groundwater affected the occurrence of high arsenic-containing groundwater in the basin.

Isotopic fingerprint of the middle Olt River basin, Romania.

PubMed

Popescu, Raluca; Costinel, Diana; Ionete, Roxana Elena; Axente, Damian

2014-01-01

One of the most important tributaries of the Danube River in Romania, the Olt River, was characterized in its middle catchment in terms of the isotopic composition using continuous flow-isotope ratio mass spectrometry (CF-IRMS). Throughout a period of 10 months, from November 2010 to August 2011, water samples from the Olt River and its more important tributaries were collected in order to investigate the seasonal and spatial isotope patterns of the basin waters. The results revealed a significant difference between the Olt River and its tributaries, by the fact that the Olt River waters show smaller seasonal variations in the stable isotopic composition and are more depleted in (18)O and (2)H. The waters present an overall enrichment in heavy isotopes during the warm seasons.

Effect of bolus fluid intake on energy expenditure values as determined by the doubly labeled water method

NASA Technical Reports Server (NTRS)

Drews, D.; Stein, T. P.

1992-01-01

The doubly labeled water (DLW, 2H(2)18O) method is a highly accurate method for measuring energy expenditure (EE). A possible source of error is bolus fluid intake before body water sampling. If there is bolus fluid intake immediately before body water sampling, the saliva may reflect the ingested water disproportionately, because the ingested water may not have had time to mix fully with the body water pool. To ascertain the magnitude of this problem, EE was measured over a 5-day period by the DLW method. Six subjects were dosed with 2H2(18)O. After the reference salivas for the two-point determination were obtained, subjects drank water (700-1,000 ml), and serial saliva samples were collected for the next 3 h. Expressing the postbolus saliva enrichments as a percentage of the prebolus value, we found 1) a minimum in the saliva isotopic enrichments were reached at approximately 30 min with the minimum for 2H (95.48 +/- 0.43%) being significantly lower than the minimum for 18O (97.55 +/- 0.44, P less than 0.05) and 2) EE values calculated using the postbolus isotopic enrichments are appreciably higher (19.9 +/- 7.5%) than the prebolus reference values. In conclusion, it is not advisable to collect saliva samples for DLW measurements within approximately 1 h of bolus fluid intake.

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.

Uncoupling between soil and xylem water isotopic composition: how to discriminate mobile and tightly-bound water?

NASA Astrophysics Data System (ADS)

Martín Gómez, Paula; Aguilera, Mònica; Pemán, Jesús; Gil Pelegrín, Eustaquio; Ferrio, Juan Pedro

2014-05-01

As a general rule, no isotopic fractionation occurs during water uptake and water transport, thus, xylem water reflects source water. However, this correspondence does not always happen. Isotopic enrichment of xylem water has been found in several cases and has been either associated to 'stem processes' like cuticular evaporation 1 and xylem-phloem communication under water stress 2,3 or to 'soil processes' such as species-specific use of contrasting water sources retained at different water potential forces in soil. In this regard, it has been demonstrated that mobile and tightly-bound water may show different isotopic signature 4,5. However, standard cryogenic distillation does not allow to separate different water pools within soil samples. Here, we carried out a study in a mixed adult forest (Pinus sylvestris, Quercus subpyrenaica and Buxus sempervirens) growing in a relatively deep loamy soil in the Pre-Pyrenees. During one year, we sampled xylem from twigs and soil at different depths (10, 30 and 50 cm). We also sampled xylem from trunk and bigger branches to assess whether xylem water was enriched in the distal parts of the tree. We found average deviations in the isotopic signature from xylem to soil of 4o 2o and 2.4o in δ18O and 18.3o 7.3o and 8.9o in δ2H, for P.sylvestris, Q.subpyrenaica and B.sempervirens respectively. Xylem water was always enriched compared to soil. In contrast, we did not find clear differences in isotopic composition between xylem samples along the tree. Declining the hypothesis that 'stem processes' would cause these uncoupling between soil and xylem isotopic values, we tested the possibility to separate mobile and tightly-bound water by centrifugation. Even though we could separate two water fractions in soils close to saturation, we could not recover a mobile fraction in drier soils. In this regard, we welcome suggestions on alternatives to separate different soil fractions in order to find the correspondence between soil and xylem water. References 1. Dawson, T. E. & Ehleringer, J. R. Isotopic enrichment of water in the 'woody' tissues of plants: Implications for plant water source, water uptake, and other studies which use the stable isotopic composition of cellulose. (1993). 2. Cernusak, L. a, Farquhar, G. D. & Pate, J. S. Environmental and physiological controls over oxygen and carbon isotope composition of Tasmanian blue gum, Eucalyptus globulus. Tree Physiol. 25, 129-46 (2005). 3. Bertrand, G. et al. Determination of spatiotemporal variability of tree water uptake using stable isotopes (δ 18 O, δ 2 H) in an alluvial system supplied by a high-altitude watershed, Pfyn forest, Switzerland. Ecohydrology (2012). doi:10.1002/eco.1347 4. Tang, K. & Feng, X. The effect of soil hydrology on the oxygen and hydrogen isotopic compositions of plants ' source water. 185, (2001). 5. Brooks, J. R., Barnard, H. R., Coulombe, R. & McDonnell, J. J. Ecohydrologic separation of water between trees and streams in a Mediterranean climate. Nat. Geosci. 3, 100-104 (2009). Acknowledgements This study was funded by RESILFOR project (AGL 2012-40039-C02-02) and FPU fellowship from the Spanish Ministry of Science and Innovation (FPU12/00648). We thank Instituto de Formación Agroambiental de Jaca and Unidad de Salud de los Bosques de Aragón for their support on field work and we feel very grateful to Miguel Ángel Lázaro for climbing the studied trees, José María Alcaire for one year of rain collection and Pilar Sopeña and Ma Josep Pau for laboratory analysis. Helpful comments by Jordi Voltas on statistical analysis have improved the quality of the work.

The metabolic fate of doubly stable isotope labelled heat-killed Lactobacillus johnsonii in humans.

PubMed

Wutzke, K D; Berg, D; Haffner, D

2008-02-01

In this study, heat-killed Lactobacillus johnsonii (La1), doubly labelled with (13)C and (15)N (hk-dlLa1), was used to follow the metabolic fate after oral administration in humans. Experimental study. University of Rostock, Children's Hospital, Research Laboratory. Ten healthy adults aged 23-26 years. The subjects received 74.6 mg/kg body weight hk-dlLa1 and 10 g alpha-D-raffinose together with breakfast. A sample of venous blood was taken after 2 h. Expired air samples were taken over 14 h, whereas urine and faeces were collected over a period of 48 h. (13)C- and (15)N-enrichments were measured by isotope ratio mass spectrometry. Hydrogen concentrations were measured by electrochemical detection. The orocaecal transit time (OCTT) was reached after 3.4 h. After 2 h, (13)C- and (15)N-enrichment of fibrinogen amounted to 2 and 25 p.p.m. excess, respectively. The (13)CO(2)-exhalation amounted to 9.2% of the ingested dose. The urinary excretion of (13)C and (15)N was 2.1 and 10.4% of the ingested dose, respectively, whereas the faecal excretion was 47.9 and 43.7% of the ingested dose, respectively. In comparison to OCTT of 3.4 h, both stable isotopes appear after 30 min in breath and urine, indicating that hk-dlLa1 is rapidly digested in the small bowel before reaching the caecum. This is confirmed by (13)C-and (15)N-enrichments of blood plasma fractions. The ingestion of hk-dlLa1 led to a (13)C- and (15)N-excretion of 59.2 and 54.1% of the ingested dose, respectively, of both stable isotopes.

Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea)

PubMed Central

Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

2015-01-01

Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ 15N, δ 13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ 13C and δ 15N and C/N atomic values. Chemical preservatives caused δ 13C enrichment as great as 1.5‰, and δ 15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ 15N depletion up to 1.8‰. Freezing depleted δ 13C and δ 15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets. PMID:26390400

Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea).

PubMed

Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

2015-01-01

Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ15N, δ13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ13C and δ15N and C/N atomic values. Chemical preservatives caused δ13C enrichment as great as 1.5‰, and δ15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ15N depletion up to 1.8‰. Freezing depleted δ13C and δ15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets.

The boron and lithium isotopic composition of mid-ocean ridge basalts and the mantle

NASA Astrophysics Data System (ADS)

Marschall, Horst R.; Wanless, V. Dorsey; Shimizu, Nobumichi; Pogge von Strandmann, Philip A. E.; Elliott, Tim; Monteleone, Brian D.

2017-06-01

A global selection of 56 mid-ocean ridge basalt (MORB) glasses were analysed for Li and B abundances and isotopic compositions. Analytical accuracy and precision of analyses constitute an improvement over previously published MORB data and allow a more detailed discussion of the Li and B systematics of the crust-mantle system. Refined estimates for primitive mantle abundances ([ Li ] = 1.39 ± 0.10 μg/g and [ B ] = 0.19 ± 0.02 μg/g) and depleted mantle abundances ([ Li ] = 1.20 ± 0.10 μg/g and [ B ] = 0.077 ± 0.010 μg/g) are presented based on mass balance and on partial melting models that utilise observed element ratios in MORB. Assimilation of seawater (or brine) or seawater-altered material beneath the ridge, identified by high Cl / K , causes significant elevation of MORB δ11 B and variable elevation in δ7 Li . The B isotope ratio is, hence, identified as a reliable indicator of assimilation in MORB and values higher than -6‰ are strongly indicative of shallow contamination of the magma. The global set of samples investigated here were produced at various degrees of partial melting and include depleted and enriched MORB from slow and fast-spreading ridge segments with a range of radiogenic isotope signatures and trace element compositions. Uncontaminated (low- Cl / K) MORB show no significant boron isotope variation at the current level of analytical precision, and hence a homogenous B isotopic composition of δ11 B = - 7.1 ± 0.9 ‰ (mean of six ridge segments; 2SD). Boron isotope fractionation during mantle melting and basalt fractionation likely is small, and this δ11 B value reflects the B isotopic composition of the depleted mantle and the bulk silicate Earth, probably within ±0.4‰. Our sample set shows a mean δ7 Li = + 3.5 ± 1.0 ‰ (mean of five ridge segments; 2SD), excluding high- Cl / K samples. A significant variation of 1.0-1.5‰ exists among various ridge segments and among samples within individual ridge segments, but this variation is unrelated to differentiation, assimilation or mantle source indicators, such as radiogenic isotopes or trace elements. It, therefore, seems likely that kinetic fractionation of Li isotopes during magma extraction, transport and storage may generate δ7 Li excursions in MORB. No mantle heterogeneities, such as those generated by deeply recycled subducted materials, are invoked in the interpretation of the Li and B isotope data presented here, in contrast to previous work on smaller data sets. Lithium and boron budgets for the silicate Earth are presented that are based on isotope and element mass balance. A refined estimate for the B isotopic composition of the bulk continental crust is given as δ11 B = - 9.1 ± 2.4 ‰ . Mass balance allows the existence of recycled B reservoirs in the deep mantle, but these are not required. However, mass balance among the crust, sediments and seawater shows enrichment of 6 Li in the surface reservoirs, which requires the existence of 7 Li -enriched material in the mantle. This may have formed by the subduction of altered oceanic crust since the Archaean.

Geochemistry of the Neoproterozoic metabasic rocks from the Negele area, southern Ethiopia: Tectonomagmatic implications

NASA Astrophysics Data System (ADS)

Yihunie, Tadesse; Adachi, Mamoru; Yamamoto, Koshi

2006-03-01

Neoproterozoic metabasic rocks along with metasediments and ultramafic rocks constitute the Kenticha and Bulbul lithotectonic domains in the Negele area. They occur as amphibolite and amphibole schist in the Kenticha, and amphibole schist and metabasalt in the Bulbul domains. These rocks are dominantly basaltic in composition and exhibit low-K tholeiitic characteristics. They are slightly enriched in large ion lithophile (LIL) and light rare earth (LRE) elements and depleted in high field strength (HFS) and heavy rare earth (HRE) elements. They exhibit chemical characteristics similar to back-arc basin and island-arc basalts, but include a few samples with slightly higher Y, Zr and Nb contents. Initial Sr isotopic ratios and ɛNd values for the Kenticha metabasic rocks range from 0.7048 to 0.7051 and from 4.7 to 9.6 whereas for the Bulbul metabasic rocks they range from 0.7032 to 0.7055 and from -0.1 to 5.5, respectively. The trace elements and Sr-Nd isotope compositions of samples from the Kenticha and Bulbul domains suggest similar, but isotopically heterogeneous magma sources. The magma is inferred to have derived from depleted source with a contribution from an enriched mantle source component.

Feasibility of a Fieldable Mass Spectrometer FY 2015 Year-end Report

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

Barinaga, Charles J.; Hager, George J.; Hoegg, Edward D.

Currently, the International Atomic Energy Agency (IAEA) monitors the production of enriched uranium hexafluoride (UF 6) at declared facilities by collecting a few grams of product in sample tubes that are then sent to central laboratories for processing and isotope ratio analysis by thermal ionization mass spectrometry. Analysis of results may not be available for some time after collection. In addition, new shipping regulations will make it more difficult to transport this amount of UF 6 to a laboratory. The IAEA is interested in an isotope ratio technique for uranium in UF 6 that can be moved to and operatedmore » at the enrichment facility itself. This report covers the tasks and activities of the Feasibility of a Fieldable Mass Spectrometer Project for FY 2015, which investigates the feasibility of an in-field isotope ratio technique— the forward deployment of a technique to the non-laboratory situation of a protected room with power and heat at the facility of interest. A variety of nontraditional elemental ionization techniques were considered. It was determined that only two of these should be moved forward for testing with the candidate in-field mass spectrometer and with the adsorbed UF 6 sample types.« less

Origin of enormous trace metal enrichments in weathering mantles of Jurassic carbonates: evidence from Sr, Nd and Pb isotopes

NASA Astrophysics Data System (ADS)

Hissler, C.; Stille, P.; Juilleret, J.; Iffly, J.; Perrone, T.; Morvan, G.

2013-12-01

Weathering mantels are widespread worldwide and include lateritic, sandy and kaolinite-rich saprolites and residuals of partially dissolved carbonate rocks. These old regolith systems have a complex history of formation and may present a polycyclic evolution due to successive geological and pedogenetic processes that affected the profile. Until now, only few studies highlighted the unusual content of associated trace elements in this type of weathering mantle. For instance, these enrichments can represent about five times the content of the underlying Bajocian to Oxfordian limestone/marl complexes, which have been relatively poorly studied compared to weathering mantle developed on magmatic bedrocks. Up to now, neither soil, nor saprolite formation has to our knowledge been geochemically elucidated. Therefore, the aim of this study was to examine more closely the soil forming dynamics and the relationship of the chemical soil composition to potential sources (saprolite, Bajocian silty marls and limestones, atmospheric particles deposition...). Of special interest has also been the origin of trace metals and the processes causing their enrichments. Especially Rare Earth Element (REE) distribution patterns and Sr, Nd and Pb isotope ratios are particularly well suited to identify trace element migration, to recognize origin and mixing processes and, in addition, to decipher possible anthropogenic and/or "natural" atmosphere-derived contributions to the soil. Moreover, leaching experiments shall help to identify mobile phases in the soil system. This may inform on the stability of trace elements and especially on their behaviour in these Fe-enriched carbonate systems. Trace metal migration and enrichments were studied on a cambisol developing on an underlying Jurassic limestone. The base is strongly enriched among others in rare earth elements (ΣREE: 2640ppm) or redox-sensitive elements such as Fe (44 wt.%), V (920ppm), Cr (700ppm), Zn (550ppm), As (260ppm), Co (45ppm) and Cd (2.4ppm). The underlying limestone and marl show, compared to average world carbonates, enrichments in the same elements and trace element distribution patterns similar to the soil suggesting their close genetic relationship. Pb, Sr and Nd isotope data allow to identify three principal components in the soil: a silicate-rich phase at close to the surface, a strongly trace metal enriched component at the bottom of the soil profile and an anthropogenic, atmosphere- derived component detected in the soil leachates. The isotopic mixing curves defined by the soil samples point to the close genetic connection between upper and lowermost soil horizons. The Nd isotopic composition of the leachates of all soil horizons are in contrast to the untreated soil and residual soil samples very homogeneous suggesting that the leachable phases of the upper and lower soil horizons are genetically connected. The downward migration of the trace metals is stopped at this soil level due to the presence of important secondary calcite precipitations, smectite and Fe-oxide accumulations. Mass balance calculations indicate that the enrichment process goes along with a volume increase relative to the bottom soil horizons.

A new approach to aid the characterisation and identification of metabolites of a model drug; partial isotope enrichment combined with novel formula elucidation software.

PubMed

Hobby, Kirsten; Gallagher, Richard T; Caldwell, Patrick; Wilson, Ian D

2009-01-01

This work describes the identification of 'isotopically enriched' metabolites of 4-cyanoaniline using the unique features of the software package 'Spectral Simplicity'. The software is capable of creating the theoretical mass spectra for partially isotope-enriched compounds, and subsequently performing an elemental composition analysis to give the elemental formula for the 'isotopically enriched' metabolite. A novel mass spectral correlation method, called 'FuzzyFit', was employed. 'FuzzyFit' utilises the expected experimental distribution of errors in both mass accuracy and isotope pattern and enables discrimination between statistically probable and improbable candidate formulae. The software correctly determined the molecular formulae of ten previously described metabolites of 4-cyanoaniline confirming the technique of partial isotope enrichment can produce results analogous to standard methodologies. Six previously unknown species were also identified, based on the presence of the unique 'designer' isotope ratio. Three of the unknowns were tentatively identified as N-acetylglutamine, O-methyl-N acetylglucuronide and a putative fatty acid conjugate. The discovery of a significant number of unknown species of a model drug with a comprehensive history of investigation highlights the potential for enhancement to the analytical process by the use of 'designer' isotope ratio compounds. The 'FuzzyFit' methodology significantly aided the elucidation of candidate formulae, by provision of a vastly simplified candidate formula data set. Copyright (c) 2008 John Wiley & Sons, Ltd.

Simultaneous Assay of Isotopic Enrichment and Concentration of Guanidinoacetate and Creatine by Gas Chromatography-Mass Spectrometry

PubMed Central

Kasumov, Takhar; Gruca, Lourdes L.; Dasarathy, Srinivasan; Kalhan, Satish C.

2012-01-01

A gas chromatographic-mass spectrometric (GC-MS) method for the simultaneous measurement of isotopic enrichment and concentration of guanidinoacetic acid and creatine in plasma sample for kinetic studies is reported. The method, based on preparation of the bis(trifluoromethyl)-pyrimidine methyl ester derivatives of guanidinoacetic acid and creatine, is robust and sensitive. The lowest measurable m1 and m3 enrichment for guanidinoacetic acid and creatine, respectively, was 0.3%. The calibration curves for measurements of concentration were linear over a range of 0.5-250 μM guanidinoacetic acid and 2-500 μM for creatine. The method was reliable for inter-assay and intra-assay precision, accuracy and linearity. The technique was applied in a healthy adult to determine in vivo fractional synthesis rate of creatine using primed- constant rate infusion of [1-13C]glycine. It was found that isotopic enrichment of guanidinoacetic acid reached plateau by 30 min of infusion of [1-13C]glycine, indicating either a small pool size or a rapid turnover rate or both, of guanidinoacetic acid. In contrast, tracer appearance in creatin was slow (slope: 0.00097), suggesting a large pool size and a slow rate of synthesis of creatine. This method can be used to estimate rate of synthesis of creatine in-vivo in human and animal studies. PMID:19646413

Determination of the isotopic composition and molar mass of a new 'Avogadro' crystal: homogeneity and enrichment-related uncertainty reduction

NASA Astrophysics Data System (ADS)

Pramann, Axel; Narukawa, Tomohiro; Rienitz, Olaf

2017-10-01

The molar mass M and isotopic composition (expressed in amount-of-substance fractions x( i Si) of the silicon isotopes 28Si, 29Si, and 30Si) of a new silicon crystal (notation: Si28-23Pr11) highly enriched in the 28Si isotope have been determined independently at PTB and NMIJ by measuring exactly the same sample solutions using both a high resolution multicollector-inductively coupled plasma mass spectrometer (MC-ICP-MS). This crystal will be used for the complementary determination of the Avogadro constant N A and thus providing one of many key parameters in the planned redefinition of the SI units kilogram and mole, using fundamental constants. Samples from three different axial positions in the crystal ingot, each divided into several radial positions were measured in order to probe possible variations of the molar mass and isotopic composition. Results obtained at PTB and NMIJ agreed within the limits of uncertainty. The application of the latest improved measurement techniques as well as an improved determination of the calibration factors (K) required to correct for mass bias effects resulted in an averaged M  =  27.976 942 666(40) g mol-1 with a relative combined uncertainty u c,rel(M)  =  1.4  ×  10-9. The course of M as a function of the origin of the measured samples suggests no significant inhomogeneity within the limits of the claimed uncertainty throughout the crystal supporting its applicability for the determination of a new N A. This extends to x(28Si) and x(29Si). Variations in x(30Si) as a function of the sample location were observed, but a systematic relation to physical origins cannot be claimed. Compared to the previous silicon crystal (‘AVO28’, notation: Si28-10Pr11) used for the latest determination of N A, the enrichment increases from x(28Si)  =  0.999 957 52(12) mol mol-1 (‘AVO28’) to x(28Si)  =  0.999 984 470(39) mol mol-1 (Si28-23Pr11, discussed in this paper) which is at least in part responsible for a reduction of the associated measurement uncertainty u(M).

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

PubMed

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

2003-06-01

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

Calcium and Oxygen Isotopic Composition of Calcium Carbonates

NASA Astrophysics Data System (ADS)

Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

2016-04-01

Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40Ca. On the other hand, 40Ca may desorb more easily, especially if the bond strength is lower as in the case of aragonite. For kinetic oxygen isotopic fractionation, the faster deprotonation of HC16O3- and the faster incorporation of C16O32- at the surfaces causes a smaller enrichment of 18O in all three polymorphs, which will be preserved at higher precipitation rates. In consequence to the different behavior of calcium and oxygen isotopes, they can be useful for multiproxy applications. Thereby calcium isotopes can be used to identify kinetic effects, especially if both aragonite and calcite, can be analyzed in one sample. Oxygen isotopes are more strongly related to temperature. [1]A. Niedermayr, S.J. Köhler and M. Dietzel (2013), Chemical Geology, 340, 105-120.

Compound-Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer.

PubMed

Clark, Justin A; Stotler, Randy L; Frape, Shaun K; Illman, Walter A

2017-01-01

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis-DCE compound-specific isotope analysis of carbon and chlorine collected over a 16-month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis-DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ 37 Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis-DCE. Carbon isotopic values range between -28.9 and -20.7‰ VPDB for TCE, and -26.5 and -11.8‰ VPDB for cis-DCE. In most wells, isotopic values remained steady over the 15-month study. Isotopic enrichment from TCE to cis-DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine-carbon isotopic enrichment ratios (ϵ Cl /ϵ C ) were 0.18 for TCE and 0.69 for cis-DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume. © 2016, National Ground Water Association.

Isotopic composition of a sample enriched in 93Zr

DOE PAGES

Fujii, Toshiyuki; Hori, Jun-ichi; Du, Miting; ...

2015-10-22

A project to determine the neutron-capture cross section of long lived fission products and minor actinides has been started by using a beam-line at Japan Proton Accelerator Research Complex (J-PARC). We prepared one of the target nuclides is Zr-93, which in Oak Ridge National Laboratory. Qualitative and quantitative analyses on the sample were performed at Kyoto University. The isotopic composition of (m) Zr (m 90, 91, 92, 93, 94, and 96) was precisely determined by multi-collector thermal ionization mass spectrometry with < 0.1 % of 2 sigma uncertainty. We determined that the atomic abundance of Zr-93 in the sample tomore » be 18.86 ± A 0.05 %.« less

Effect of 13C enrichment and sugar type on analysis of sugars by gas chromatography/combustion/isotope ratio mass spectrometry.

PubMed

Baumann, Karen; Dignac, Marie-France; Bardoux, Gérard; Rumpel, Cornelia

2012-09-15

The objective of this investigation was to test gas-chromatographic compound-specific analysis for studies on the isotopic composition of (13)C-enriched sugar molecules. The effects of (13)C enrichment and type of sugar (C5, C6) will provide valuable information on isotopic correction for future studies employing (13)C-enriched sugars. Five sugar solutions of xylose, mannose and glucose with (13)C enrichments ranging between 1.1 and 1.5 atom-% were prepared. The (13)C enrichments of the initial sugars were measured by elemental analyser/isotope ratio mass spectrometry (EA/IRMS); (13)C enrichments for derivatised sugars were obtained by gas chromatography/combustion/IRMS (GC/C/IRMS). The linear relationships between the (13)C enrichments of the initial sugars and the values for the derivatised sugars were sugar-type dependent. Corrections for GC/C/IRMS values took into account the kinetic isotope effect (KIE) of the derivatising agent associated with the coefficient (K(d)) and a newly introduced second coefficient (K(c)) associated with the KIE of the sugar. While K(d) was constant, K(c) varied with sugar type. During derivatisation acetate groups with (12)C and sugars with more (13)C reacted faster. Coefficients for the specific ranges of (13)C enrichments under study have to be assessed and the reactions of different sugar types have to be taken into account to avoid underestimation of (13)C enrichment of up to 9% (C5) or overestimation of up to 4% (C6). Copyright © 2012 John Wiley & Sons, Ltd.

Permian arc-back-arc basin development along the Ailaoshan tectonic zone: Geochemical, isotopic and geochronological evidence from the Mojiang volcanic rocks, Southwest China

NASA Astrophysics Data System (ADS)

Fan, Weiming; Wang, Yuejun; Zhang, Aimei; Zhang, Feifei; Zhang, Yuzhi

2010-10-01

This paper presents a set of new SHRIMP zircon U-Pb geochronological, elemental and Sr-Nd-Pb isotopic data for the Wusu and Yaxuanqiao basaltic rocks (the Mojiang area) along the Ailaoshan tectonic zone. The Wusu basaltic sequence is dominated by SiO 2-poor, MgO- and TiO 2-rich basalts with a major mineral assemblage of plagioclase + clinopyroxene. These rocks gave a SHRIMP zircon U-Pb age of 287 ± 5 Ma (MSWD = 0.58). In contrast, the Yaxuanqiao basaltic sequence is predominantly composed of high-Al basaltic andesite, which gave a SHRIMP zircon U-Pb age of 265 ± 7 Ma (MSWD = 0.34). The analyzed samples for both sequences exhibit significant enrichment in LILEs and depletion in HFSEs with (Nb/La)n of 0.38-0.81, similar to arc-like volcanics. They have positive ɛNd(t) values (+ 3.52 to + 5.54). In comparison with MORB-derived magmatic rocks, the Wusu basalts are more enriched in LILEs and REEs, and the Yaxuanqiao samples are more enriched in LILEs but variably depleted in Ti, Y and HREE. The Wusu samples show high Pb isotopic ratios, similar to the Tethyan basalts, whereas the Yaxuanqiao samples plot in the field of the global pelagic sediments. The geochemical and Sr-Nd-Pb isotopic characteristics suggest that the Wusu basalts originated from a MORB-like source metasomatised by slab-derived fluids, while the Yaxuanqiao rocks have a fluid-modified MORB source with the input of subducted sediments. The geochemical affinity to both MORB- and arc-like sources, together with other geological observations, appears to support the development of a Permian arc-back-arc basin along the Ailaoshan-Song Ma tectonic zone in response to the northward subduction of the Paleotethys main Ocean. The final closure of the arc-back-arc basin took place in the uppermost Triassic due to the diachronous amalgamation between the Yangtze and Simao-Indochina Blocks.

Non-chondritic iron isotope ratios in planetary mantles as a result of core formation

NASA Astrophysics Data System (ADS)

Elardo, Stephen M.; Shahar, Anat

2017-02-01

Information about the materials and conditions involved in planetary formation and differentiation in the early Solar System is recorded in iron isotope ratios. Samples from Earth, the Moon, Mars and the asteroid Vesta reveal significant variations in iron isotope ratios, but the sources of these variations remain uncertain. Here we present experiments that demonstrate that under the conditions of planetary core formation expected for the Moon, Mars and Vesta, iron isotopes fractionate between metal and silicate due to the presence of nickel, and enrich the bodies' mantles in isotopically light iron. However, the effect of nickel diminishes at higher temperatures: under conditions expected for Earth's core formation, we infer little fractionation of iron isotopes. From our experimental results and existing conceptual models of magma ocean crystallization and mantle partial melting, we find that nickel-induced fractionation can explain iron isotope variability found in planetary samples without invoking nebular or accretionary processes. We suggest that near-chondritic iron isotope ratios of basalts from Mars and Vesta, as well as the most primitive lunar basalts, were achieved by melting of isotopically light mantles, whereas the heavy iron isotope ratios of terrestrial ocean floor basalts are the result of melting of near-chondritic Earth mantle.

Stable Nickel Isotopes in Fusion Crusts from Iron Meteorites and from Metallic Particles in a Black Wabar Impact Glass

NASA Astrophysics Data System (ADS)

Xue, S.; Herzog, G. F.; Hall, G. S.

1993-07-01

Iron and nickel isotopes may undergo mass fractionation in systems subjected to high-temperature vaporization [1-3]. We report here a search for nickel fractionation in fusion crusts from iron meteorites and in metal-rich material separated from Wabar impact glasses. Fusion-crust bearing samples of Bogou (IA), N'Goureyma (I-an), and Pitts (IB) were potted in epoxy and were "shaved" with a milling machine. Microscopic examination of the shavings showed the presence of some material from the interior of the meteorites as well as from the fusion crust. A fourth meteorite, Cape of Good Hope (IVB), was prepared for use as a reference standard. About 1.4 mg of magnetic material was collected from a 2-g sample of black Wabar impact glass ground in a Spex mill; microscopic examination indicated that adhering silicates comprised ~5% of the sample. These (terrestrial) silicates contain relatively little Ni [4] so their presence does not interfere with the nickel analysis. Nickel was separated from all samples and its isotopic composition determined as in [2]. Results and Discussion: Nickel isotopic abundances are given in Table 1 both as delta values and as an average fractionation, PHI, where PHI is the slope of a plot of delta vs. mass for each sample. Within the precision of our measurements (from 0.3 to 1.5%, depending on the isotope) all the samples had normal (i.e., terrestrial) isotopic abundances of Ni. Clayton et al. [5] reported that delta-18O in fusion crust is lower than in the atmosphere, probably as a result of a kinetic isotope effect, while in metallic deep-sea spheres, heavy oxygen isotopes are enriched. They inferred that the metallic spheres are not the ablation products of larger meteorites. Similarly, the Ni isotopic abundances in fusion crust are normal, while those in deep-sea metallic spheres are enriched in the heavier isotopes [1]. We note, however, that material ablated from the surface of an iron could have undergone fractionation after separation from the incoming meteorite (see [4]). Horz et al. [6] found variable Fe/Ni ratios (from 0.1 to 222) in black melt glasses associated with the Wabar impact. The Fe/Ni ratio in our metal sample is 2, which is considerably lower than that in the bulk meteorite (~12.4). Several lines of evidence suggest that vapor fractionation is to be expected in samples that have Fe/Ni ratios greater than those in the bulk impactor [2-6]. Thus it is not surprising that our first results for Wabar impactites show no Ni isotopic fractionation. Isotopic analyses of Wabar impactites with high Fe/Ni ratios should be made to test the importance of vapor fractionation. References: [1] Herzog G. F. et al. (1992) LPSC XXIII, 527-528. [2] Xue S. et al. (1993) LPSC XXIV, 1547-1548. [3] Davis A. et al. (1993) LPSC XXIV, 373- 374. [4] Mittlefehldt D. W. et al. (1992) Meteoritics, 27, 361-370. [5] Clayton R. N. et al. (1986) EPSL, 79, 235-240. [6] Horz F. et al. (1989) Proc. LPSC 19th, 697-710. Table 1, which appears in the hard copy, shows delta (permil) and average isotope fractionation PHI (%/amu) for Ni isotopes in iron meteorites and black Wabar impact glass.

13 C dynamic nuclear polarization using isotopically enriched 4-oxo-TEMPO free radicals.

PubMed

Niedbalski, Peter; Parish, Christopher; Kiswandhi, Andhika; Lumata, Lloyd

2016-12-01

The nitroxide-based free radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) is a widely used polarizing agent in NMR signal amplification via dissolution dynamic nuclear polarization (DNP). In this study, we have thoroughly investigated the effects of 15 N and/or 2 H isotopic labeling of 4-oxo-TEMPO free radical on 13 C DNP of 3 M [1- 13 C] sodium acetate samples in 1 : 1 v/v glycerol : water at 3.35 T and 1.2 K. Four variants of this free radical were used for 13 C DNP: 4-oxo-TEMPO, 4-oxo-TEMPO- 15 N, 4-oxo-TEMPO-d 16 and 4-oxo-TEMPO- 15 N,d 16 . Our results indicate that, despite the striking differences seen in the electron spin resonance (ESR) spectral features, the 13 C DNP efficiency of these 15 N and/or 2 H-enriched 4-oxo-TEMPO free radicals are relatively the same compared with 13 C DNP performance of the regular 4-oxo-TEMPO. Furthermore, when fully deuterated glassing solvents were used, the 13 C DNP signals of these samples all doubled in the same manner, and the 13 C polarization buildup was faster by a factor of 2 for all samples. The data here suggest that the hyperfine coupling contributions of these isotopically enriched 4-oxo-TEMPO free radicals have negligible effects on the 13 C DNP efficiency at 3.35 T and 1.2 K. These results are discussed in light of the spin temperature model of DNP. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

The micro-scale synthesis of (117)Sn-enriched tributyltin chloride and its characterization by GC-ICP-MS and NMR techniques.

PubMed

Peeters, Kelly; Iskra, Jernej; Zuliani, Tea; Ščančar, Janez; Milačič, Radmila

2014-07-01

Organotin compounds (OTCs) are among the most toxic substances ever introduced to the environment by man. They are common pollutants in marine ecosystems, but are also present in the terrestrial environment, accumulated mainly in sewage sludge and landfill leachates. In investigations of the degradation and methylation processes of OTC in environmental samples, the use of enriched isotopic tracers represents a powerful analytical tool. Sn-enriched OTC are also necessary in application of the isotope dilution mass spectrometry technique for their accurate quantification. Since Sn-enriched monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) are not commercially available as single species, "in house" synthesis of individual butyltin-enriched species is necessary. In the present work, the preparation of the most toxic butyltin, namely TBT, was performed via a simple synthetic path, starting with bromination of metallic Sn, followed by butylation with butyl lithium. The tetrabutyltin (TeBT) formed was transformed to tributyltin chloride (TBTCl) using concentrated hydrochloric acid (HCl). The purity of the synthesized TBT was verified by speciation analysis using the techniques of gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) and nuclear magnetic resonance (NMR). The results showed that TBT had a purity of more than 97%. The remaining 3% corresponded to DBT. TBT was quantified by reverse isotope dilution GC-ICP-MS. The synthesis yield was around 60%. The advantage of this procedure over those previously reported lies in its possibility to be applied on a micro-scale (starting with 10mg of metallic Sn). This feature is of crucial importance, since enriched metallic Sn is extremely expensive. The procedure is simple and repeatable, and was successfully applied for the preparation of (117)Sn-enriched TBTCl from (117)Sn-enriched metal. Copyright © 2014 Elsevier Ltd. All rights reserved.

Persistence of fertile and hydrous lithospheric mantle beneath the northwestern Ethiopian plateau: Evidence from modal, trace element and Sr-Nd-Hf isotopic compositions of amphibole-bearing mantle xenoliths

NASA Astrophysics Data System (ADS)

Alemayehu, Melesse; Zhang, Hong-Fu; Aulbach, Sonja

2017-07-01

We present new trace element compositions of amphiboles, Sr-Nd-Hf isotope compositions of clinopyroxenes and mineral modes for spinel peridotite xenoliths that were entrained in a Miocene alkali basalt (Gundeweyn, northwestern Ethiopian plateau), in order to understand the geochemical evolution and variation occurring within the continental lithospheric mantle (CLM) in close proximity to the East African Rift system, and its dynamic implications. With the exception of a single amphibole-bearing sample that is depleted in LREE (La/YbN = 0.45 × Cl), amphiboles in lherzolites and in one harzburgite show variable degrees of LREE enrichment (La/YbN = 2.5-12.1 × Cl) with flat HREE (Dy/YbN = 1.5-2.1 × Cl). Lherzolitic clinoyroxenes have 87Sr/86Sr (0.70227 to 0.70357), 143Nd/144Nd (0.51285 to 0.51346), and 176Hf/177Hf (0.28297 to 0.28360) ranging between depleted lithosphere and enriched mantle. LREE-enriched clinopyroxenes generally have more enriched isotope compositions than depleted ones. While lherzolites with isotope compositions similar to those of the Afar plume result from the most recent metasomatic overprint, isotope compositions more depleted than present-day MORB can be explained by an older melt extraction and/or isotopic rehomogenisation event, possibly related to the Pan-African orogeny. Several generations of amphibole are recognized in accord with this multi-stage evolution. Texturally unequilibrated amphibole occurring within the peridotite matrix and in melt pockets attest to continued hydration and refertilization of the lithospheric mantle subsequent to Oligocene flood basalt magmatism, during which an earlier-emplaced inventory of amphibole was likely largely consumed. However, a single harzburgite contains amphibole with the highest Mg# and lowest TiO2 content, which is interpreted as sampling a volumetrically subordinate mantle region beneath the Ethiopian plateau that was not tapped during flood basalt magmatism. Strikingly, both trace-element enriched and depleted lherzolites have high clinopyroxene and orthopyroxene and low olivine contents (median 15, 24 and 56 vol.%), combined with primitive olivine Mg# (median 89.5), indicating the presence of refertilized mantle beneath Gundeweyn. Despite its fertility and FeO-rich character (hence high inferred density), and impingement by the Afar plume, the CLM beneath the Ethiopian plateau, though apparently thinned through thermochemical erosion, has so far resisted whole-sale delamination or dripping. This is tentatively ascribed to insufficient stress and density contrasts at the periphery of the Afar plume, which reached its greatest thermochemical buoyancy in the Afar region, northeast of Gundeweyn.

Fine-Scale Spatial Variability of Precipitation, Soil, and Plant Water Isotopes

NASA Astrophysics Data System (ADS)

Goldsmith, G. R.; Braun, S.; Romero, C.; Engbersen, N.; Gessler, A.; Siegwolf, R. T.; Schmid, L.

2015-12-01

Introduction: The measurement of stable isotope ratios of water has become fundamental in advancing our understanding of environmental patterns and processes, particularly with respect to understanding the movement of water within the soil-plant-atmosphere continuum. While considerable research has explored the temporal variation in stable isotope ratios of water in the environment, our understanding of the spatial variability of these isotopes remains poorly understood. Methods: We collected spatially explicit samples of throughfall and soil water (n=150 locations) from a 1 ha plot delineated in a mixed deciduous forest in the northern Alps of Switzerland. We complemented this with fully sunlit branch and leaf samples (n = 60 individuals) collected from Picea abies and Fagus sylvatica between 14:00 and 16:00 on the same day by means of a helicopter. Soil and plant waters were extracted using cryogenic vacuum distillation and all samples were analyzed for δ18O using an isotope ratio mass spectrometer. Results: The mean δ18O of throughfall (-3.3 ± 0.8‰) indicated some evaporative enrichment associated with passage through the canopy, but this did not significantly differ from the precipitation collected in nearby open sites (-4.05‰). However, soil was depleted (-7.0 ± 1.8‰) compared to throughfall and there was no significant relationship between the two, suggesting that the sampling for precipitation inputs did not capture all the sources (e.g. stream water, which was -11.5‰) contributing to soil water δ18O ratios. Evaporative enrichment of δ18O was higher in leaves of Fagus (14.8 ± 1.8‰) than in leaves of Picea (11.8 ± 1.7‰). Sampling within crowns of each species (n = 5 branches each from 5 individuals) indicated that variability in a single individual is similar to that among individuals. Discussion: Stable isotopes of water are frequently engaged for studies of ecohydrology, plant ecophysiology, and paleoclimatology. Our results help constrain the variability within different water sources across space (e.g. when vizualized as isoscapes), as well as the extent of fractionation among those sources as water moves through the critical zone. In doing so, we also provide insight into how environment shapes this fine-scale variation in order to inform future applications of water isotopes.

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.

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.

Magnesium stable isotope ecology using mammal tooth enamel

NASA Astrophysics Data System (ADS)

Martin, Jeremy E.; Vance, Derek; Balter, Vincent

2015-01-01

Geochemical inferences on ancient diet using bone and enamel apatite rely mainly on carbon isotope ratios (δ13C) and to a lesser extent on strontium/calcium (Sr/Ca) and barium/calcium (Ba/Ca) elemental ratios. Recent developments in nontraditional stable isotopes provide an unprecedented opportunity to use additional paleodietary proxies to disentangle complex diets such as omnivory. Of particular relevance for paleodietary reconstruction are metals present in large quantity in bone and enamel apatite, providing that biologically mediated fractionation processes are constrained. Calcium isotope ratios (δ44Ca) meet these criteria but exhibit complex ecological patterning. Stable magnesium isotope ratios (δ26Mg) also meet these criteria but a comprehensive understanding of its variability awaits new isotopic data. Here, 11 extant mammal species of known ecology from a single locality in equatorial Africa were sampled for tooth enamel and, together with vegetation and feces, analyzed for δ26Mg, δ13C, Sr/Ca, and Ba/Ca ratios. The results demonstrate that δ26Mg incorporated in tooth enamel becomes heavier from strict herbivores to omnivores/faunivores. Using data from experimentally raised sheep, we suggest that this 26Mg enrichment up the trophic chain is due to a 26Mg enrichment in muscle relative to bone. Notably, it is possible to distinguish omnivores from herbivores, using δ26Mg coupled to Ba/Ca ratios. The potential effects of metabolic and dietary changes on the enamel δ26Mg composition remain to be explored but, in the future, multiproxy approaches would permit a substantial refinement of dietary behaviors or enable accurate trophic reconstruction despite specimen-limited sampling, as is often the case for fossil assemblages.

Estimates of groundwater recharge rates and sources in the East Mountain area, Eastern Bernalillo County, New Mexico, 2005-12

USGS Publications Warehouse

Rice, Steven E.; Crilley, Dianna M.

2014-01-01

Stable isotope data from springs and snowpacks sampled in the East Mountain area were compared with local, regional, and global meteoric water lines and were analyzed along with values representing the stable isotope composition of winter precipitation and summer monsoonal rains. Results of the stable isotope analysis from springs in this study suggested that winter precipitation is the primary source of groundwater recharge to the aquifers supplying the springs, but there is a component of more isotopically enriched precipitation being recharged as well, likely from summer monsoonal rains. Specific conductance, groundwater-level hydrographs, snowpack chemistry, and snow-water equivalent data were used to inform the analyses and corroborate the findings of the CMB and stable isotope results.

Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

NASA Astrophysics Data System (ADS)

Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

2014-09-01

Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment, employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e., equivalent to ~8 ng of amino sugar carbon. Compound-specific stable carbon isotopic analysis of amino sugars obtained from marine sediment extracts indicated that glucosamine and galactosamine were mainly derived from organic detritus, whereas muramic acid showed isotopic imprints from indigenous bacterial activities. The δ13C analysis of amino sugars provides a valuable addition to the biomarker-based characterization of microbial metabolism in the deep marine biosphere, which so far has been lipid oriented and biased towards the detection of archaeal signals.

An isotopic study of biogeochemical relationships between carbonates and organic carbon in the Greenhorn Formation

NASA Technical Reports Server (NTRS)

Hayes, J. M.; Popp, Brian N.; Takigiku, Ray; Johnson, Marcus W.

1989-01-01

Carbon-isotopic compositions of total carbonate, inoceramid carbonate, micritic carbonate, secondary cements, total organic carbon, and geoporphyrins have been measured in 76 different beds within a 17-m interval of a core through the Greenhorn Formation, an interbedded limestone and calcareous shale unit of Cretaceous age from the Western Interior Seaway of North America. Results are considered in terms of variations in the processes of primary production and in secondary processes. It is shown that the porphyrin isotopic record reflects primary isotopic variations more closely than the TOC isotopic record and that, in these sediments, TOC is enriched in C-13 relative to its primary precursor by 0.6 to 2.8 percent. This enrichment is attributed to isotope effects within the consumer foodweb and is associated with respiratory heterotrophy. Variation in this secondary enrichment are correlated with variations in the isotopic composition of marine carbonate.

Chlorine in Lunar Basalts

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Anand, M.; Franchi, I. A.

2017-01-01

In the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs, and P, collectively called KREEP, and in its primitive form - urKREEP, [1]), given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO (e.g., [2]). When compared to chondritic meteorites and terrestrial rocks (e.g., [3-4]), lunar samples often display heavy chlorine isotope compositions [5-9]. Boyce et al. [8] found a correlation between delta Cl-37 (sub Ap) and bulk-rock incompatible trace elements (ITEs) in lunar basalts, and used this to propose that early degassing of Cl (likely as metal chlorides) from the LMO led to progressive enrichment in remaining LMO melt in Cl-37over Cl-35- the early degassing model. Barnes et al. [9] suggested that relatively late degassing of chlorine from urKREEP (to yield delta Cl-37 (sub urKREEP greater than +25 per mille) followed by variable mixing between KREEPy melts and mantle cumulates (characterized by delta Cl-370 per mille) could explain the majority of Cl isotope data from igneous lunar samples. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed an in situ study of chlorine isotopes and abundances of volatiles in lunar apatite from a diverse suite of lunar basalts spanning a range of geochemical types.

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.

Isotopic constraints on the origin of meteoritic organic matter

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1991-01-01

Salient features of the isotopic distribution of H, C and N in the organic material found in carbonaceous meteorites are noted. Most organic fractions are strongly enriched in D with respect to the D/H ratio characteristic of H2 in the protosolar system; substantial variations in C-13/C-12 ratio are found among different molecular species, with oxidised species tending to be C-13 enriched relative to reduced species; some homologous series reveal systematic decrease in C-13/C-12 with increasing C number; considerable variation in N-15/N-14 ratio is observed within organic matter, though no systematic pattern to its distribution has yet emerged; no interelement correlations have been observed between isotope enrichments for the different biogenic elements. The isotopic complexity echoes the molecular diversity observed in meteoritic organic matter and suggests that the organic matter was formed by multiple processes and/or from multiple sources. However, existence of a few systematic patterns points towards survival of isotopic signatures characteristic of one or more specific processes. The widespread D enrichment implies either survival of many species of interstellar molecule or synthesis from a reservoir containing a significant interstellar component. Several of the questions raised above can be addressed by more detailed determination of the distribution of the H, C and N isotopes among different well-characterized molecular fractions. Thus, the present study is aimed at discovering whether the different amino acids have comparable D enrichments, which would imply local synthesis from a D-enriched reservoir, or very viable D enrichments, which would imply survival of some interstellar amino acids. The same approach is also being applied to polycyclic aromatic hydrocarbons. Because the analytical technique employed (secondary ion mass spectrometry) can acquire data for all three isotopic systems from each molecular fraction, any presently obscured interelement isotopic correlation should also be revealed, which will aid in identifying pertinent synthetic processes.

Isotopic Enrichment of Boron in the Sputtering of Boron Nitride with Xenon Ions

NASA Technical Reports Server (NTRS)

Ray, P. K.; Shutthanandan, V.

1998-01-01

An experimental study is described to measure the isotopic enrichment of boron. Xenon ions from 100 eV to 1.5 keV were used to sputter a boron nitride target. An ion gun was used to generate the ion beam. The ion current density at the target surface was approximately 30 microA/sq cm. Xenon ions impinged on the target surface at 50 deg angle to the surface normal. Since boron nitride is an insulator, a flood electron gun was used in our experiments to neutralize the positive charge buildup on the target surface. The sputtered secondary ions of boron were detected by a quadrupole mass spectrometer. The spectrometer entrance aperture was located perpendicular to the ion beam direction and 10 mm away from the target surface. The secondary ion flux was observed to be enriched in the heavy isotopes at lower ion energies. The proportion of heavy isotopes in the sputtered secondary ion flux was found to decrease with increasing primary ion energy from 100 to 350 eV. Beyond 350 eV, light isotopes were sputtered preferentially. The light isotope enrichment factor was observed to reach an asymptotic value of 1.27 at 1.5 keV. This trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

Stellar Origins of C-13 and N-15-Enriched Presolar SiC Grains

NASA Technical Reports Server (NTRS)

Liu, Nan; Nittler, Larry R.; Alexander, Conel M. O’D.; Wang, Jianhua; Pignatari, Marco; Jose, Jordi; Nguyen, Ann

2016-01-01

Extreme excesses of 13 C ( C (12 C/ 13 C<10) and 15 N ( N (14 N/ 15 N< 20) in rare presolar SiC 20) in rare presolar SiClar SiC grains have been considered diagnostic of an origin in classical novae [1], though an origin in core-collapse supernovae (CCSNe) has also been proposed [2]. We report multi-element isotopic data for 19 13 C- and 15 N-enriched presolar SiC grains(12 C/13 C<16 and 14 N/ 15 N<150) from an acid resistant residue of the Murchison meteorite. These grains are enriched in 13 C and15 N, but with quite diverse Si isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures.

Process for producing enriched uranium having a .sup.235 U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

DOEpatents

Horton, James A.; Hayden, Jr., Howard W.

1995-01-01

An uranium enrichment process capable of producing an enriched uranium, having a .sup.235 U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower .sup.235 U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF.sub.6 tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a .sup.235 U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % .sup.235 U; fluorinating this enriched metallic uranium isotopic mixture to form UF.sub.6 ; processing the resultant isotopic mixture of UF.sub.6 in a gaseous diffusion process to produce a final enriched uranium product having a .sup.235 U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low .sup.235 U content UF.sub.6 having a .sup.235 U content of about 0.71 wt. % of the total uranium content of the low .sup.235 U content UF.sub.6 ; and converting this low .sup.235 U content UF.sub.6 to metallic uranium for recycle to the atomic vapor laser isotope separation process.

Process for producing enriched uranium having a {sup 235}U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

DOEpatents

Horton, J.A.; Hayden, H.W. Jr.

1995-05-30

An uranium enrichment process capable of producing an enriched uranium, having a {sup 235}U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower {sup 235}U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF{sub 6} tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a {sup 235} U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % {sup 235} U; fluorinating this enriched metallic uranium isotopic mixture to form UF{sub 6}; processing the resultant isotopic mixture of UF{sub 6} in a gaseous diffusion process to produce a final enriched uranium product having a {sup 235}U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low {sup 235}U content UF{sub 6} having a {sup 235}U content of about 0.71 wt. % of the total uranium content of the low {sup 235}U content UF{sub 6}; and converting this low {sup 235}U content UF{sub 6} to metallic uranium for recycle to the atomic vapor laser isotope separation process. 4 figs.

Large volume recycling of oceanic lithosphere over short time scales: geochemical constraints from the Caribbean Large Igneous Province

NASA Astrophysics Data System (ADS)

Hauff, F.; Hoernle, K.; Tilton, G.; Graham, D. W.; Kerr, A. C.

2000-01-01

Oceanic flood basalts are poorly understood, short-term expressions of highly increased heat flux and mass flow within the convecting mantle. The uniqueness of the Caribbean Large Igneous Province (CLIP, 92-74 Ma) with respect to other Cretaceous oceanic plateaus is its extensive sub-aerial exposures, providing an excellent basis to investigate the temporal and compositional relationships within a starting plume head. We present major element, trace element and initial Sr-Nd-Pb isotope composition of 40 extrusive rocks from the Caribbean Plateau, including onland sections in Costa Rica, Colombia and Curaçao as well as DSDP Sites in the Central Caribbean. Even though the lavas were erupted over an area of ˜3×10 6 km 2, the majority have strikingly uniform incompatible element patterns (La/Yb=0.96±0.16, n=64 out of 79 samples, 2σ) and initial Nd-Pb isotopic compositions (e.g. 143Nd/ 144Nd in=0.51291±3, ɛNdi=7.3±0.6, 206Pb/ 204Pb in=18.86±0.12, n=54 out of 66, 2σ). Lavas with endmember compositions have only been sampled at the DSDP Sites, Gorgona Island (Colombia) and the 65-60 Ma accreted Quepos and Osa igneous complexes (Costa Rica) of the subsequent hotspot track. Despite the relatively uniform composition of most lavas, linear correlations exist between isotope ratios and between isotope and highly incompatible trace element ratios. The Sr-Nd-Pb isotope and trace element signatures of the chemically enriched lavas are compatible with derivation from recycled oceanic crust, while the depleted lavas are derived from a highly residual source. This source could represent either oceanic lithospheric mantle left after ocean crust formation or gabbros with interlayered ultramafic cumulates of the lower oceanic crust. High 3He/ 4He in olivines of enriched picrites at Quepos are ˜12 times higher than the atmospheric ratio suggesting that the enriched component may have once resided in the lower mantle. Evaluation of the Sm-Nd and U-Pb isotope systematics on isochron diagrams suggests that the age of separation of enriched and depleted components from the depleted MORB source mantle could have been ≤500 Ma before CLIP formation and interpreted to reflect the recycling time of the CLIP source. Mantle plume heads may provide a mechanism for transporting large volumes of possibly young recycled oceanic lithosphere residing in the lower mantle back into the shallow MORB source mantle.

Combined Li-He isotopes in Iceland and Jan Mayen basalts and constraints on the nature of the North Atlantic mantle

NASA Astrophysics Data System (ADS)

Magna, T.; Wiechert, U.; Stuart, F. M.; Halliday, A. N.; Harrison, D.

2011-02-01

Lithium (Li) isotopes are thought to provide a powerful proxy for the recycling of crustal material, affected by low temperature alteration, through the mantle. We present Li isotope compositions for basaltic volcanic rocks from Hengill, Iceland, and Jan Mayen in order to examine possible links between ocean island volcanism and recycled oceanic crust and to address recent suggestions that mantle 3He/ 4He is also related to recycling of ancient slabs. Basaltic glasses spanning a range of chemical enrichment from the Hengill fissure system define an inverse correlation between δ 7Li (3.8-6.9‰) and 3He/ 4He (12-20 RA). The high- 3He/ 4He basalts have low δ 18O as well as excess Eu and high Nb/U, but carry no Li isotope evidence of being the product of recycling of altered slab or wedge material. In fact, there is no clear correlation between Li or He isotopes on the one hand and any of the other fingerprints of recycled slab components. The low- 3He/ 4He samples do have elevated Nb/U, Sr/Nd, positive Eu anomalies and high δ 7Li (˜6.9‰), providing evidence of a cumulate-enriched source that could be part of an ancient altered ocean floor slab. Basalts from Jan Mayen are characterized by large degrees of enrichment in incompatible trace elements typical of EM-like basalts but have homogeneous δ 7Li typical of depleted mantle (3.9-4.7‰) providing evidence for a third mantle source in the North Atlantic. It appears that oceanic basalts can display a wide range in isotope and trace element compositions associated with recycled components whilst exhibiting no sign of modern surface-altered slab or wedge material from the Li isotope composition.

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

NASA Astrophysics Data System (ADS)

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

1999-03-01

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

Highly enriched multiply-labeled stable isotopic compounds as atmospheric tracers

DOEpatents

Goldblatt, M.; McInteer, B.B.

1974-01-29

Compounds multiply-labeled with stable isotopes and highly enriched in these isotopes are readily capable of detection in tracer experiments involving high dilutions. Thus, for example, /sup 13/C/sup 18/O/sub 2/ provides a useful tracer for following atmospheric pol lution produced as a result of fossil fuel burning. (Official Gazette)

Isotopic modeling of the sub-cloud evaporation effect in precipitation.

PubMed

Salamalikis, V; Argiriou, A A; Dotsika, E

2016-02-15

In dry and warm environments sub-cloud evaporation influences the falling raindrops modifying their final stable isotopic content. During their descent from the cloud base towards the ground surface, through the unsaturated atmosphere, hydrometeors are subjected to evaporation whereas the kinetic fractionation results to less depleted or enriched isotopic signatures compared to the initial isotopic composition of the raindrops at cloud base. Nowadays the development of Generalized Climate Models (GCMs) that include isotopic content calculation modules are of great interest for the isotopic tracing of the global hydrological cycle. Therefore the accurate description of the underlying processes affecting stable isotopic content can improve the performance of iso-GCMs. The aim of this study is to model the sub-cloud evaporation effect using a) mixing and b) numerical isotope evaporation models. The isotope-mixing evaporation model simulates the isotopic enrichment (difference between the ground and the cloud base isotopic composition of raindrops) in terms of raindrop size, ambient temperature and relative humidity (RH) at ground level. The isotopic enrichment (Δδ) varies linearly with the evaporated raindrops mass fraction of the raindrop resulting to higher values at drier atmospheres and for smaller raindrops. The relationship between Δδ and RH is described by a 'heat capacity' model providing high correlation coefficients for both isotopes (R(2)>80%) indicating that RH is an ideal indicator of the sub-cloud evaporation effect. Vertical distribution of stable isotopes in falling raindrops is also investigated using a numerical isotope-evaporation model. Temperature and humidity dependence of the vertical isotopic variation is clearly described by the numerical isotopic model showing an increase in the isotopic values with increasing temperature and decreasing RH. At an almost saturated atmosphere (RH=95%) sub-cloud evaporation is negligible and the isotopic composition hardly changes even at high temperatures while at drier and warm conditions the enrichment of (18)Ο reaches up to 20‰, depending on the raindrop size and the initial meteorological conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

A Summary of Actinide Enrichment Technologies and Capability Gaps

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

Patton, Bradley D.; Robinson, Sharon M.

2017-01-01

The evaluation performed in this study indicates that a new program is needed to efficiently provide a national actinide radioisotope enrichment capability to produce milligram-to-gram quantities of unique materials for user communities. This program should leverage past actinide enrichment, the recent advances in stable isotope enrichment, and assessments of the future requirements to cost effectively develop this capability while establishing an experience base for a new generation of researchers in this vital area. Preliminary evaluations indicate that an electromagnetic isotope separation (EMIS) device would have the capability to meet the future needs of the user community for enriched actinides. Themore » EMIS technology could be potentially coupled with other enrichment technologies, such as irradiation, as pre-enrichment and/or post-enrichment systems to increase the throughput, reduce losses of material, and/or reduce operational costs of the base EMIS system. Past actinide enrichment experience and advances in the EMIS technology applied in stable isotope separations should be leveraged with this new evaluation information to assist in the establishment of a domestic actinide radioisotope enrichment capability.« less

Mercury isotope fractionation during ore retorting in the Almadén mining district, Spain

USGS Publications Warehouse

Gray, John E.; Pribil, Michael J.; Higueras, Pablo L.

2013-01-01

Almadén, Spain, is the world's largest mercury (Hg) mining district, which has produced over 250,000 metric tons of Hg representing about 30% of the historical Hg produced worldwide. The objective of this study was to measure Hg isotopic compositions of cinnabar ore, mine waste calcine (retorted ore), elemental Hg (Hg0(L)), and elemental Hg gas (Hg0(g)), to evaluate potential Hg isotopic fractionation. Almadén cinnabar ore δ202Hg varied from − 0.92 to 0.15‰ (mean of − 0.56‰, σ = 0.35‰, n = 7), whereas calcine was isotopically heavier and δ202Hg ranged from − 0.03‰ to 1.01‰ (mean of 0.43‰, σ = 0.44‰, n = 8). The average δ202Hg enrichment of 0.99‰ between cinnabar ore and calcines generated during ore retorting indicated Hg isotopic mass dependent fractionation (MDF). Mass independent fractionation (MIF) was not observed in any of the samples in this study. Laboratory retorting experiments of cinnabar also were carried out to evaluate Hg isotopic fractionation of products generated during retorting such as calcine, Hg0(L), and Hg0(g). Calcine and Hg0(L) generated during these retorting experiments showed an enrichment in δ202Hg of as much as 1.90‰ and 0.67‰, respectively, compared to the original cinnabar ore. The δ202Hg for Hg0(g) generated during the retorting experiments was as much as 1.16‰ isotopically lighter compared to cinnabar, thus, when cinnabar ore was roasted, the resultant calcines formed were isotopically heavier, whereas the Hg0(g) generated was isotopically lighter in Hg isotopes.

Sulphur and oxygen isotope analysis to identify sources of sulphur in gypsum-rich black crusts developed on granites.

PubMed

Rivas, T; Pozo, S; Paz, M

2014-06-01

We describe the results of sulphur and oxygen isotope analyses used to identify sources of the gypsum present in black crusts that grow on the granite of historical buildings. The crusts were sampled at various locations in and near the city of Vigo (NW Spain) and were analysed for their sulphur content and δ(34)S and δ(18)O isotope ratios. Sampled crusts had δ(34)S values of 7.3‰ to 12.9‰ and δ(18)O values of 6.56‰ to 12.51‰. Sampled as potential sulphur sources were bulk depositions, seawater, foundation, ashlar and construction materials and combustion residues. The results indicated marine and, to a lesser extent, anthropogenic, origins for the sulphur and ruled out the contribution of sub-soil sulphates by capillary rise from building foundations. Isotope analyses would indicate that cement and mortar were enriched in sulphur after their application in buildings. The fact that facade orientation (towards the sea or fossil fuel pollution sources) was correlated with sulphur isotope distribution pointed to various contributions to black crust formation. Copyright © 2014 Elsevier B.V. All rights reserved.

Water-quality data for the Russian River Basin, Mendocino and Sonoma Counties, California, 2005-2010

USGS Publications Warehouse

Anders, Robert; Davidek, Karl; Stoeckel, Donald M.

2011-01-01

Field measurements included discharge, barometric pressure, dissolved oxygen, pH, specific conductance, temperature, and turbidity. All samples were analyzed for nutrients, major ions, trace metals, total and dissolved organic carbon, organic wastewater compounds, standard bacterial indicators, and the stable isotopes of hydrogen and oxygen. Standard bacterial indicators included total coliform, Escherichia coli, enterococci, and Clostridium perfringens for the period 2005 through 2007, and total and fecal coliform, and enterococci for 2010. In addition, enrichment of enterococci was performed on all surface-water samples collected during summer 2006, for detection of the human-associated enterococcal surface protein in Enterococcus faecium to assess the presence of sewage effluent in the Russian River. Other analyses included organic wastewater compounds of bed sediment samples collected from four Russian River sites during 2005; carbon-13 isotopic values of the dissolved inorganic carbon for surface-water and groundwater samples collected during 2006; human-use pharmaceuticals on Russian River samples collected during 2007 and 2010; and the radiogenic isotopes tritium and carbon-14 for groundwater samples collected during 2008.

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.

Solar, planetary, and other inert gases in two sieve fractions of a disaggregated Allende sample - A study by stepwise heating extraction

NASA Technical Reports Server (NTRS)

Palma, R. L.; Heymann, D.

1988-01-01

Inert gases released by stepwise heating of unaltered, strongly magnetic, and weakly magnetic samples from the 0-64 micron and the 105-250 micron fractions of a disaggregated and sieved sample of the Allende meteorite reveal the occurrence of both solar and planetary neon. The origin of the solar neon is thought to be implantation of solar wind ions. The origin of the planetary neon remains unresolved. Heavy isotope enriched components of krypton and xenon have been detected and there are some indications that a light krypton component may also be present. Other than a larger concentration of Xe-129 in the weakly magnetic samples, the signatures of the magnetic separates are isotopically very similar.

The Great White Guppy: Top Predator

NASA Astrophysics Data System (ADS)

Michalski, G. M.

2011-12-01

Nitrogen isotopes are often used to trace the trophic level of members of an ecosystem. As part of a stable isotope biogeochemistry and forensics course at Purdue University, students are introduced to this concept by analyzing nitrogen isotopes in sea food purchased from local grocery stores. There is a systematic increase in 15N/14N ratios going from kelp to clams/shrimp, to sardines, to tuna and finally to shark. These enrichments demonstrate how nitrogen is enriched in biomass as predators consume prey. Some of the highest nitrogen isotope enrichments observed, however, are in the common guppy. We investigated a number of aquarium fish foods and find they typically have high nitrogen isotope ratios because they are made form fish meal that is produced primarily from the remains of predator fish such as tuna. From, a isotope perspective, the guppy is the top of the food chain, more ferocious than even the Great White shark.

Separation of sulfur isotopes

DOEpatents

DeWitt, Robert; Jepson, Bernhart E.; Schwind, Roger A.

1976-06-22

Sulfur isotopes are continuously separated and enriched using a closed loop reflux system wherein sulfur dioxide (SO.sub.2) is reacted with sodium hydroxide (NaOH) or the like to form sodium hydrogen sulfite (NaHSO.sub.3). Heavier sulfur isotopes are preferentially attracted to the NaHSO.sub.3, and subsequently reacted with sulfuric acid (H.sub.2 SO.sub.4) forming sodium hydrogen sulfate (NaHSO.sub.4) and SO.sub.2 gas which contains increased concentrations of the heavier sulfur isotopes. This heavy isotope enriched SO.sub.2 gas is subsequently separated and the NaHSO.sub.4 is reacted with NaOH to form sodium sulfate (Na.sub.2 SO.sub.4) which is subsequently decomposed in an electrodialysis unit to form the NaOH and H.sub.2 SO.sub.4 components which are used in the aforesaid reactions thereby effecting sulfur isotope separation and enrichment without objectionable loss of feed materials.

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.

Isotope dilution ICP-MS with laser-assisted sample introduction for direct determination of sulfur in petroleum products.

PubMed

Boulyga, Sergei F; Heilmann, Jens; Heumann, Klaus G

2005-08-01

Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with direct laser-assisted introduction of isotope-diluted samples into the plasma, using a laser ablation system with high ablation rates, was developed for accurate sulfur determinations in different petroleum products such as 'sulfur-free' premium gasoline, diesel fuel, and heating oil. Two certified gas oil reference materials were analyzed for method validation. Two different 34S-enriched spike compounds, namely, elementary sulfur dissolved in xylene and dibenzothiophene in hexane, were synthesized and tested for their usefulness in this isotope dilution technique. The isotope-diluted sample was adsorbed on a filter-paper-like material, which was fixed in a special holder for irradiation by the laser beam. Under these conditions no time-dependent spike/analyte fractionation was only observed for the dibenzothiophene spike during the laser ablation process, which means that the measured 34S/32S isotope ratio of the isotope-diluted sample remained constant-a necessary precondition for accurate results with the isotope dilution technique. A comparison of LA-ICP-IDMS results with the certified values of the gas oil reference materials and with results obtained from ICP-IDMS analyses with wet sample digestion demonstrated the accuracy of the new LA-ICP-IDMS method in the concentration range of 9.2 microg g(-1) ('sulfur-free' premium gasoline) to 10.4 mg g(-1) (gas oil reference material BCR 107). The detection limit for sulfur by LA-ICP-IDMS is 0.04 microg g(-1) and the analysis time is only about 10 min, which therefore also qualifies this method for accurate determinations of low sulfur contents in petroleum products on a routine level.

Scoping study to expedite development of a field deployable and portable instrument for UF6 enrichment assay

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

Chan, George; Valentine, John D.; Russo, Richard E.

The primary objective of the present study is to identity the most promising, viable technologies that are likely to culminate in an expedited development of the next-generation, field-deployable instrument for providing rapid, accurate, and precise enrichment assay of uranium hexafluoride (UF6). UF6 is typically involved, and is arguably the most important uranium compound, in uranium enrichment processes. As the first line of defense against proliferation, accurate analytical techniques to determine the uranium isotopic distribution in UF6 are critical for materials verification, accounting, and safeguards at enrichment plants. As nuclear fuel cycle technology becomes more prevalent around the world, international nuclearmore » safeguards and interest in UF6 enrichment assay has been growing. At present, laboratory-based mass spectrometry (MS), which offers the highest attainable analytical accuracy and precision, is the technique of choice for the analysis of stable and long-lived isotopes. Currently, the International Atomic Energy Agency (IAEA) monitors the production of enriched UF6 at declared facilities by collecting a small amount (between 1 to 10 g) of gaseous UF6 into a sample bottle, which is then shipped under chain of custody to a central laboratory (IAEA’s Nuclear Materials Analysis Laboratory) for high-precision isotopic assay by MS. The logistics are cumbersome and new shipping regulations are making it more difficult to transport UF6. Furthermore, the analysis is costly, and results are not available for some time after sample collection. Hence, the IAEA is challenged to develop effective safeguards approaches at enrichment plants. In-field isotopic analysis of UF6 has the potential to substantially reduce the time, logistics and expense of sample handling. However, current laboratory-based MS techniques require too much infrastructure and operator expertise for field deployment and operation. As outlined in the IAEA Department of Safeguards Long-Term R&D Plan, 2012–2023, one of the IAEA long-term R&D needs is to “develop tools and techniques to enable timely, potentially real-time, detection of HEU (Highly Enriched Uranium) production in LEU (Lowly Enriched Uranium) enrichment facilities” (Milestone 5.2). Because it is common that the next generation of analytical instruments is driven by technologies that are either currently available or just now emerging, one reasonable and practical approach to project the next generation of chemical instrumentation is to track the recent trends and to extrapolate them. This study adopted a similar approach, and an extensive literature review on existing and emerging technologies for UF6 enrichment assay was performed. The competitive advantages and current limitations of different analytical techniques for in-field UF6 enrichment assay were then compared, and the main gaps between needs and capabilities for their field use were examined. Subsequently, based on these results, technologies for the next-generation field-deployable instrument for UF6 enrichment assay were recommended. The study was organized in a way that a suite of assessment metric was first identified. Criteria used in this evaluation are presented in Section 1 of this report, and the most important ones are described briefly in the next few paragraphs. Because one driving force for in-field UF6 enrichment assay is related to the demanding transportation regulation for gaseous UF6, Section 2 contains a review of solid sorbents that convert and immobilized gaseous UF6 to a solid state, which is regarded as more transportation friendly and is less regulated. Furthermore, candidate solid sorbents, which show promise in mating with existing and emerging assay technologies, also factor into technology recommendations. Extensive literature reviews on existing and emerging technologies for UF6 enrichment assay, covering their scientific principles, instrument options, and current limitations are detailed in Sections 3 and 4, respectively. In Section 5, the technological gaps as well as start-of-the-art and commercial off-the-shelf components that can be adopted to expedite the development of a fieldable or portable UF6 enrichment-assay instrument are identified and discussed. Finally, based on the results of the review, requirements and recommendations for developing the next-generation field-deployable instrument for UF6 enrichment assay are presented in Section 6.« less

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 trace and Pb isotope chemistry of the Jan Mayen Fracture Zone and the extinct Aegir Ridge

NASA Astrophysics Data System (ADS)

Sayit, K.; Hanan, B. B.; Ito, G.; Howell, S. M.; Vogt, P. R.; Breivik, A. J.; Mjelde, R.; Pedersen, R.

2012-12-01

The extinct Aegir Ridge (AR) was active during the early opening of the N-Atlantic, 54 to 25 Ma, when spreading jumped to the Kolbeinsey Ridge. Crustal thickness produced by the AR is low (3.5 to 6 km), and the magmatically starved Norway Basin appears as a hole in the surrounding excess volcanism of the Iceland hotspot. Two possible alternatives are; either the lithospheric structure of the Jan Mayen micro-continent (JMMC) blocked the plume flow to the AR, and/or Iceland plume material reaching the ridge experienced a previous melt extraction, leading to relatively low melt production. We report the trace element and Pb isotope systematics of the mafic rocks dredged from the AR ~64-69° N and adjacent Jan Mayen FZ. On the basis of the immobile trace element chemistry, several groups are identified, with a large range of Zr/Nb (2.7-60.7). A very-depleted group ([Ce/Yb]N = 0.3) was found in the Jan Mayen FZ, while the most enriched, OIB-like group ([Ce/Yb]N = 12.4) was recovered from the ridge flank scarps. A notable feature of the Aegir samples is variable Th enrichment relative Nb (Th/Nb = 0.07-0.49), similar to subduction zone signatures. In terms of Pb isotopes, the samples show significant variations that correlate with trace element chemistry (206Pb/204Pb: 207Pb/204Pb: 208Pb/204Pb = 16.63-18.81:15.16-15.55:36.67-38.62). The Pb systematics of the Aegir rocks are compatible with a three-component mixing model with mixing trends between the C-like Iceland plume component and a mixture that is composed of EM-1-type material and depleted MORB asthenosphere. The presence of the C-like isotope compositions in the Aegir samples from the Jan Mayen FZ and ridge flank scarps suggests that Iceland plume material has been tapped. However, the very-depleted trace element signatures indicate that the plume component was previously melt depleted. Apparently, the JMMC impeaded flow of enriched plume material to the AR. The Aegir rocks Pb isotope signature may represent pollution of the NA MORB source, during early opening of the ocean basin, by material dispersed during interaction of the Iceland plume and the continental lithosphere.

First-principles Calculations of Equilibrium Calcium Isotope Fractionation among Ca-bearing Minerals

NASA Astrophysics Data System (ADS)

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

2016-12-01

Calcium isotope fractionation factors of Ca-bearing minerals are investigated with the first principle calculations based on density functional theory (DFT). The sequence of heavy Ca isotope enrichment is forsterite > grossular > butschliite > lime > fluorite > tremolite diopside > anhydrite dolomite titanite > anorthite > perovskite gehlenite aragonite richterite > akermanite > oldhamite. This order is consistent with variation of Ca-O bond lengths, indicating that Ca-O bond energy plays an overwhelming role on the fractionations of Ca isotopes. Our study provides important insights into the Ca isotopic data of meteorites. Our calculation predicts that oldhamites (CaS) are enriched in light Ca isotopes relative to silicate phase if they are in equilibrium, contrast with the observations in Valdes et al (2014). Therefore, oldhamite and silicate phase in the meteorites should be in disequilibrium for Ca isotopes. Our results can also be used to understand Ca isotopic composition of the Moon. Δ44/40Ca between olivine (with CaO content of 2.48 wt%) and diopside is up to 0.41‰ and Δ44/40Cagrossular-diopside is 0.26‰ at 1500K. Feng et al. (2014) calculated that Δ44/40Ca between opx with CaO content of 1.74 wt% and cpx is about 0.27‰ at 1500 K. According to the Lunar Magma Ocean (LMO) model, the modern Moon is chemically stratified (Snyder et al., 1992; Elardo et al., 2011). Assuming that the lower cumulate and upper residual melt are in isotopic equilibrium during the evolution of Lunar Magma Ocean where the cumulate may be mainly composed of olivine and orthopyroxene or garnet/spinel, δ44/40Ca of the Moon could be underestimated by 0.05‰ to 0.25‰ if the shallow lunar samples are used to represent the bulk Moon.

A cost-effective approach to produce 15N-labelled amino acids employing Chlamydomonas reinhardtii CC503.

PubMed

Nicolás Carcelén, Jesús; Marchante-Gayón, Juan Manuel; González, Pablo Rodríguez; Valledor, Luis; Cañal, María Jesús; Alonso, José Ignacio García

2017-08-18

The use of enriched stable isotopes is of outstanding importance in chemical metrology as it allows the application of isotope dilution mass spectrometry (IDMS). Primary methods based on IDMS ensure the quality of the analytical measurements and traceability of the results to the international system of units. However, the synthesis of isotopically labelled molecules from enriched stable isotopes is an expensive and a difficult task. Either chemical and biochemical methods to produce labelled molecules have been proposed, but so far, few cost-effective methods have been described. The aim of this study was to use the microalgae Chlamydomonas reinhardtii to produce, at laboratory scale, 15 N-labelled amino acids with a high isotopic enrichment. To do that, a culture media containing 15 NH 4 Cl was used. No kinetic isotope effect (KIE) was observed. The labelled proteins biosynthesized by the microorganism were extracted from the biomass and the 15 N-labelled amino acids were obtained after a protein hydrolysis with HCl. The use of the wall deficient strain CC503 cw92 mt+ is fit for purpose, as it only assimilates ammonia as nitrogen source, avoiding isotope contamination with nitrogen from the atmosphere or the reagents used in the culture medium, and enhancing the protein extraction efficiency compared to cell-walled wild type Chlamydomonas. The isotopic enrichment of the labelled amino acids was calculated from their isotopic composition measured by gas chromatography mass spectrometry (GC-MS). The average isotopic enrichment for the 16 amino acids characterized was 99.56 ± 0.05% and the concentration of the amino acids in the hydrolysate ranged from 18 to 90 µg/mL. Previously reported biochemical methods to produce isotopically labelled proteins have been applied in the fields of proteomics and fluxomics. For these approaches, low amounts of products are required and the isotopic enrichment of the molecules has never been properly determined. So far, only 13 C-labelled fatty acids have been isolated from labelled microalga biomass as valuable industrial products. In this study, we propose Chlamydomonas reinhardtii CC503 as a feasible microorganism and strain to produce labelled biomass from which a standard containing sixteen 15 N-labelled amino acids could be obtained.

Sulfur and Oxygen Isotopic Analysis of a Cosmic Symplectite from a Comet Wild 2 Stardust Terminal Particle

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Berger, E. L.; Nakamura-Messenger, K.; Messenger, S.

2015-01-01

Introduction: Analyses of comet 81P/Wild 2 samples re-turned from the Stardust mission have uncovered surprising simi-larities to meteoritic material, including the identification of inner solar system grains [1-3]. The TEM characterization of terminal particle (TP) 4 from Stardust track #147 revealed an assemblage consisting of symplectically intergrown pentlandite and nanocrys-talline maghemite coexisting with high-Ca pyroxene [4]. Mineral-ogically similar cosmic symplectites (COS) containing pentlandite and magnetite in the primitive Acfer 094 meteorite are highly de-pleted in 16O (?17O, ?18O 180 per mille) [5-7]. This isotopic signature is proposed to record alteration with primordial solar nebula water. Conversely, the normal O isotopic composition of the Stardust COS indicates alteration by a different aqueous reservoir, perhaps on the comet [8]. In this study, we analyzed the Wild 2 COS for S isotopes to further constrain its origin. Experimental: Thin sections of TP4 (12 ?m) were produced and their mineralogy was thoroughly characterized by TEM. Two of the sections were analyzed for O isotopes by isotopic imaging in the JSC NanoSIMS 50L. The sample in one of the slices was completely consumed. The remaining material in the adjacent slice was analyzed simultaneously for 16O, 32S, 33S, 34S, and 56Fe16O in electron multipliers using a Cs+ primary ion beam. Quasi-simulta-neous arrival (QSA) can have a significant effect on S isotopic ra-tios when using electron multipliers, resulting in undercounting of 32S [9]. Canyon Diablo troilite (CDT) was measured numerous times to deduce a correction factor for QSA and ensure measure-ment reproducibility. Isotopic ratios are reported relative to CDT. Results and Discussion: The Wild 2 COS is enriched in the heavy S isotopes relative to CDT (?33S = 6.5 +/- 1.6 per mille; ?34S = 5.1 +/- 0.7 per mille; 1?). The degree of 33S enrichment indicates mass-inde-pendent fractionation (MIF) with ?33S = 3.9 +/- 1.7 per mille. MIF of S has been observed in some chondrules (?33S up to 0.11per mille) [10], but this effect has not been identified in sulfides from carbonaceous chondrites [11] or IDPs [12]. S isotopic analysis of Stardust impact craters also did not reveal MIF or anomalies, save for one potential 32S-rich presolar sulfide [13]. Measurement errors on these impact craters were much larger than those in this study, however. MIF of S has been proposed to result from heterogeneities in the solar neb-ula from nucleosynthetic components [14] or photochemical irra-diation of solar nebula gas [10]. Presolar SiC grains are observed to have 32S enrichments [15, 16] contrary to the S isotopic compo-sition of the cometary COS. The S isotopic composition more likely reflects irradiation of nebular gas.

Fractionated Mercury Isotopes in Fish: The Effects of Nuclear Mass, Spin, and Volume

NASA Astrophysics Data System (ADS)

Das, R.; Odom, A. L.

2007-12-01

Mercury is long known as a common environmental contaminant. In methylated form it is even more toxic and the methylation process is facilitated by microbial activities. Methyl mercury easily crosses cell membrane and accumulates in soft tissues of fishes and finally biomagnifies with increasing trophic levels. Natural variations in the isotopic composition of mercury have been reported and such variations have emphasized mass dependent fractionations, while theory and laboratory experiments indicate that mass-independent isotopic fractionation (MIF) effects are likely to be found as well. This study focuses on the MIF of mercury isotopes in the soft tissues of fishes. Samples include both fresh water and marine fish, from different continents and oceans. Approximately 1 gm of fish soft tissue was dissolved in 5 ml of conc. aqua regia for 24 hrs and filtered through a ¬¬¬100 μm filter paper and diluted with DI water. Hg is measured as a gaseous phase generated by reduction of the sample with SnCl2 in a continuous- flow cold-vapor generator connected to a Thermo-Finnigan Neptune MC-ICPMS. To minimize instrumental fractionation isotope ratios were measured by sample standard bracketing and reported as δ‰ relative to NIST SRM 3133 Hg standard where δAHg = [(A Hg/202Hg)sample/(A Hg/202Hg)NIST313] -1 ×1000‰. In this study we have measured the isotope ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg and 204Hg/202Hg. In all the fish samples δ198Hg, δ200Hg, δ202Hg, δ204Hg define a mass- dependent fractionation sequence, where as the δ199Hg and δ201Hg depart from the mass- dependent fractionation line and indicate an excess of the odd-N isotopes. The magnitude of the deviation (ΔAHg where A=199 or 201) as obtained by difference between the measured δ199Hg and δ201Hg of the samples and the value obtained by linear scaling defined by the even-N isotopes ranges from approximately 0.2 ‰ to 3‰. The ratios of Δ199Hg /Δ201Hg range from 0.8 to 1.3, and thus more than one mass-independent isotope effect is inferred. MIF of mercury can be caused by the nuclear volume effect. Schauble, 2007 has calculated nuclear volume fractionation scaling factors for a number of common mercury chemical species in equilibrium with Hg° vapor. From his calculations the nuclear field shift effect is larger in Δ199Hg than in Δ201Hg by approximately a factor of two. The predominant mercury chemical species in fish is methylmercury cysteine. From the experimental studies of Buchachenko and others (2004) on the reaction of methylmercury chloride with creatine kinase it seems reasonable to predicted that the thiol functional groups of cysteine gets enriched in 199Hg and 201Hg. Here the magnetic isotope effect (MIE) produces a kinetic partial separation of isotopes with non-zero nuclear spin quantum numbers from the even-N isotopes. The ratio of enrichment of Δ201Hg /Δ199Hg is predicted from theory to be 1.11, which is the ratio of the magnetic moments of 199Hg and 201Hg. Because mercury possesses two odd-N isotopes, it is possible to detect and evaluate the effects of two distinct, mass-independent isotope fractionating processes. From the data obtained on fish samples, we can deconvolute the contributions of the isotope effects of nuclear mass, spin and volume. For these samples the role of spin or the magnetic isotope effect is the most dominant.

Stable isotope composition (δ(13)C and δ(15)N values) of slime molds: placing bacterivorous soil protozoans in the food web context.

PubMed

Tiunov, Alexei V; Semenina, Eugenia E; Aleksandrova, Alina V; Tsurikov, Sergey M; Anichkin, Alexander E; Novozhilov, Yuri K

2015-08-30

Data on the bulk stable isotope composition of soil bacteria and bacterivorous soil animals are required to estimate the nutrient and energy fluxes via bacterial channels within detrital food webs. We measured the isotopic composition of slime molds (Myxogastria, Amoebozoa), a group of soil protozoans forming macroscopic spore-bearing fruiting bodies. An analysis of largely bacterivorous slime molds can provide information on the bulk stable isotope composition of soil bacteria. Fruiting bodies of slime molds were collected in a monsoon tropical forest of Cat Tien National Park, Vietnam, and analyzed by continuous-flow isotope ratio mass spectrometry. Prior to stable isotope analysis, carbonates were removed from a subset of samples by acidification. To estimate the trophic position of slime molds, their δ(13) C and δ(15) N values were compared with those of plant debris, soil, microbial destructors (litter-decomposing, humus-decomposing, and ectomycorrhizal fungi) and members of higher trophic levels (oribatid mites, termites, predatory macroinvertebrates). Eight species of slime molds represented by at least three independent samples were 3-6‰ enriched in (13) C and (15) N relative to plant litter. A small but significant difference in the δ(13) C and δ(15) N values suggests that different species of myxomycetes can differ in feeding behavior. The slime molds were enriched in (15) N compared with litter-decomposing fungi, and depleted in (15) N compared with mycorrhizal or humus-decomposing fungi. Slime mold sporocarps and plasmodia largely overlapped with oribatid mites in the isotopic bi-plot, but were depleted in (15) N compared with predatory invertebrates and humiphagous termites. A comparison with reference groups of soil organisms suggests strong trophic links of slime molds to saprotrophic microorganisms which decompose plant litter, but not to humus-decomposing microorganisms or to mycorrhizal fungi. Under the assumption that slime molds are primarily feeding on bacteria, the isotopic similarity of slime molds and mycophagous soil animals indicates that saprotrophic soil bacteria and fungi are similar in bulk isotopic composition. Copyright © 2015 John Wiley & Sons, Ltd.

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Assessment of the U-Th-Pb system in two Archean metabasalts - Deciphering the complex histories of sulfides and silicates using acid leaching methods

NASA Astrophysics Data System (ADS)

Smith, Patrick E.; Farquhar, Ronald M.; Tatsumoto, Mitsunobo

1989-08-01

A detailed U-Th-Pb isotopic study of two Archean basalts from two greenstone belts in the eastern Wawa Subprovince of the Canadian shield was carried out on samples that were either dissolved at once or leached in either 1N HNO3, 2N HCl, or 6N HCl. The abundances and isotopic compositions from these samples suggest that variable disturbances had occurred in both rock systems, which can be attributed to Pb mobility, particularly in the form of sulphide addition at various times, and, in one case, by recent Pb loss. The Pb isotopic compositions of the sulphides record late events which affected the greenstone terrains. The results also indicate that the sulphides and silicate rocks could have originated from a common source. The isotopic compositions of the basalt suggest that, in the Archean, both depleted and enriched mantle sources existed beneath the Wawa Subprovince.

Comparison of femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for uranium isotopic measurements

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

Havrilla, George Joseph; McIntosh, Kathryn Gallagher; Judge, Elizabeth

2016-10-20

Feasibility tests were conducted using femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for rapid uranium isotopic measurements. The samples used in this study consisted of a range of pg quantities of known 235/238 U solutions as dried spot residues of 300 pL drops on silicon substrates. The samples spanned the following enrichments of 235U: 0.5, 1.5, 2, 3, and 15.1%. In this direct comparison using these particular samples both pulse durations demonstrated near equivalent data can be produced on either system with respect to accuracy and precision. There is no question that either LA-ICP-MS method offers themore » potential for rapid, accurate and precise isotopic measurements of U10Mo materials whether DU, LEU or HEU. The LA-ICP-MS equipment used for this work is commercially available. The program is in the process of validating this work for large samples using center samples strips from Y-12 MP-1 LEU-Mo Casting #1.« less

Biomedical research applications of electromagnetically separated enriched stable isotopes

NASA Astrophysics Data System (ADS)

Lambrecht, R. M.

The current and projected annual requirements through 1985 for stable isotopes enriched by electromagnetic separation methods were reviewed for applications in various types of biomedical research: (1) medical radiosiotope production, labeled compounds, and potential radio-pharmaceuticals; (2) nutrition, food science, and pharmacology: (3) metallobiochemistry and environmental toxicology; (4) nuclear magnetic resonance, electron paramagnetic resonance, and moessbauer spectroscopy in biochemical, biophysical, and biomedical research; and (5) miscellaneous advances in radioactive and nonradioactive tracer technology. Radioisotopes available from commercial sources or routinely used in clinical nuclear medicine were excluded. Current requirements for enriched stable isotopes in biomedical research are not being satisfied. Severe shortages exist for Mg 26, Ca 43, Zn 70, Se 76, Se 77, Se 78, Pd 102, Cd 111, Cd 113, and Os 190. Many interesting and potentially important investigations in biomedical research require small quantities of specific elements at high isotopic enrichments.

Barium isotope geochemistry of subduction-zone magmas

NASA Astrophysics Data System (ADS)

Yu, H.; Nan, X.; Huang, J.; Wörner, G.; Huang, F.

2017-12-01

Subduction zones are crucial tectonic setting to study material exchange between crust and mantle, mantle partial melting with fluid addition, and formation of ore-deposits1-3. The geochemical characteristics of arc lavas from subduction zones are different from magmas erupted at mid-ocean ridges4, because there are addition of fluids/melts from subducted AOC and its overlying sediments into their source regions in the sub-arc mantle4. Ba is highly incompatible during mantle melting5, and it is enriched in crust (456 ppm)6 relative to the mantle (7.0 ppm)7. The subducted sediments are also enriched in Ba (776 ppm of GLOSS)8. Moreover, because Ba is fluid soluble during subduction, it has been used to track contributions of subduction-related fluids to arc magmas9 or recycled sediments to the mantle10-11. To study the Ba isotope fractionation behavior during subduction process, we analyzed well-characterized, chemically-diverse arc lavas from Central American, Kamchatka, Central-Eastern Aleutian, and Southern Lesser Antilles. The δ137/134Ba of Central American arc lavas range from -0.13 to 0.24‰, and have larger variation than the arc samples from other locations. Except one sample from Central-Eastern Aleutian arc with obviously heavy δ137/134Ba values (0.27‰), all other samples from Kamchatka, Central-Eastern Aleutian, Southern Lesser Antilles arcs are within the range of OIB. The δ137/134Ba is not correlated with the distance to trench, partial melting degrees (Mg#), or subducting slab-derived components. The samples enriched with heavy Ba isotopes have low Ba contents, indicating that Ba isotopes can be fractionated at the beginning of dehydration process with small amount of Ba releasing to the mantle wedge. With the dehydration degree increasing, more Ba of the subducted slab can be added to the source of arc lavas, likely homogenizing the Ba isotope signatures. 1. Rudnick, R., 1995 Nature; 2. Tatsumi, Y. & Kogiso, T., 2003; 3. Sun, W., et al., 2015 Ore Geol. Rev.; 4. Pearce, J., & Peate, D., 1995 Annu. Rev. Earth Planet. Sci.; 5. Pilet, S., et al., 2011 J. Petrol.; 6. Sun S. & McDonough, W., 1989; 7. Rudnick, R. & Gao, S., 2003 Treatise on geochem.; 8. Plank, T. & Langmuir, C., 1998, CG; 9. Hawkesworth, C. & Norry, M., 1983 Shiva Pub.; 10. Murphy, D., et al., 2002 J. Petrol.; 11. Kuritani, T., et al., 2011 Nat. Geosci.

Compound Specific Isotope Analysis of Fatty Acids in Southern African Aerosols

NASA Astrophysics Data System (ADS)

Billmark, K. A.; Macko, S. A.; Swap, R. J.

2003-12-01

This study, conducted as a part of the Southern African Regional Science Initiative (SAFARI 2000), applied compound specific isotope analysis to describe aerosols at source regions and rural locations. Stable carbon isotopic compositions of individual fatty acids were determined for aerosol samples collected at four sites throughout southern Africa. Mongu, Zambia and Skukuza, South Africa were chosen for their location within intense seasonal Miombo woodland savanna and bushveld savanna biomass burning source regions, respectively. Urban aerosols were collected at Johannesburg, South Africa and rural samples were collected at Sua Pan, Botswana. Fatty acid isotopic compositions varied temporally. Urban aerosols showed significant isotopic enrichment of selected short chain fatty acids (C < 20) compared to aerosols produced during biomass combustion. Sua Pan short chain fatty acid signatures were significantly different from the other non-urban sites, which suggests that sources other than biomass combustion products, such as organic eolian material, impact the Sua Pan aerosol profile. However, a high degree of correlation between Sua Pan and Skukuza long chain fatty acid δ 13C values confirm atmospheric linkages between the two areas and that isotopic signatures of combusted fatty acids are unaltered during atmospheric transport highlighting their potential for use as a conservative tracer.

Evaluation of sulfur isotopic enrichment of urine metabolites for the differentiation of healthy and prostate cancer mice after the administration of 34S labelled yeast.

PubMed

Galilea San Blas, Oscar; Moreno Sanz, Fernando; Herrero Espílez, Pilar; Sainz Menéndez, Rosa María; Mayo Barallo, Juan Carlos; Marchante-Gayón, Juan Manuel; García Alonso, José Ignacio

2017-01-01

Sulfur isotopic enrichment of urine metabolites in healthy and prostate cancer mice using 34 S enriched yeast and High Performance Liquid Chromatography coupled to Multicollector Inductively Coupled Plasma Mass Spectrometry (HPLC-MC-ICP-MS) has been evaluated. A 30 weeks experiment (since the eleventh to the fortieth week of life) was carried out collecting the urine of three healthy mice and three transgenic mice with prostate cancer during 24h after a single oral administration of a 34 S enriched yeast slurry. The isotopic enrichment of different sulphur metabolites was monitored by coupling a C18 reverse phase HPLC column with a multicollector ICP-MS using a membrane desolvating system. Quantification of sulfur in the chromatographic peaks was carried out by post-column isotope dilution using a 33 S enriched spike. Differences between the 34 S enrichment in the urine metabolites of healthy and prostate cancer mice were found from the beginning of the disease. Both populations could be differentiated using a principal component analysis (PCA). Finally, 7 unknown mice were correctly classified in each population using a linear discriminant analysis. Copyright © 2016 Elsevier GmbH. All rights reserved.

[Research progress on food sources and food web structure of wetlands based on stable isotopes].

PubMed

Chen, Zhan Yan; Wu, Hai Tao; Wang, Yun Biao; Lyu, Xian Guo

2017-07-18

The trophic dynamics of wetland organisms is the basis of assessing wetland structure and function. Stable isotopes of carbon and nitrogen have been widely applied to identify trophic relationships in food source, food composition and food web transport in wetland ecosystem studies. This paper provided an overall review about the current methodology of isotope mixing model and trophic level in wetland ecosystems, and discussed the standards of trophic fractionation and baseline. Moreover, we characterized the typical food sources and isotopic compositions of wetland ecosystems, summarized the food sources in different trophic levels of herbivores, omnivores and carnivores based on stable isotopic analyses. We also discussed the limitations of stable isotopes in tra-cing food sources and in constructing food webs. Based on the current results, development trends and upcoming requirements, future studies should focus on sample treatment, conservation and trophic enrichment measurement in the wetland food web, as well as on combing a variety of methodologies including traditional stomach stuffing, molecular markers, and multiple isotopes.

Nitrogen isotope fractionation during archaeal ammonia oxidation: Coupled estimates from isotopic measurements of ammonium and nitrite

NASA Astrophysics Data System (ADS)

Mooshammer, Maria; Stieglmeier, Michaela; Bayer, Barbara; Jochum, Lara; Melcher, Michael; Wanek, Wolfgang

2014-05-01

Ammonia-oxidizing archaea (AOA) are ubiquitous in marine and terrestrial environments and knowledge about the nitrogen (N) isotope effect associated with their ammonia oxidation activity will allow a better understanding of natural abundance isotope ratios, and therefore N transformation processes, in the environment. Here we examine the kinetic isotope effect for ammonia oxidation in a pure soil AOA culture (Ca. Nitrososphaera viennensis) and a marine AOA enrichment culture. We estimated the isotope effect from both isotopic signatures of ammonium and nitrite over the course of ammonia oxidation. Estimates of the isotope effect based on the change in the isotopic signature of ammonium give valuable insight, because these estimates are not subject to the same concerns (e.g., accumulation of an intermediate) as estimates based on isotopic measurements of nitrite. Our results show that both the pure soil AOA culture and a marine AOA enrichment culture have similar but substantial isotope effect during ammonia consumption (31-34 per mill; based on ammonium) and nitrite production (43-45 per mill; based on nitrite). The 15N fractionation factors of both cultures tested fell in the upper range of the reported isotope effects for archaeal and bacterial ammonia oxidation (10-41 per mill) or were even higher than those. The isotope fractionation for nitrite production was significantly larger than for ammonium consumption, indicating that (1) some intermediate (e.g., hydroxylamine) of ammonia oxidation accumulates, allowing for a second 15N fractionation step to be expressed, (2) a fraction of ammonia oxidized is lost via gaseous N forms (e.g., NO or N2O), which is 15N-enriched or (3) a fraction of ammonium is assimilated into AOA biomass, biomass becoming 15N-enriched. The significance of these mechanisms will be explored in more detail for the soil AOA culture, based on isotope modeling and isotopic measurements of biomass and N2O.

Leaf water 18 O and 2 H enrichment along vertical canopy profiles in a broadleaved and a conifer forest tree.

PubMed

Bögelein, Rebekka; Thomas, Frank M; Kahmen, Ansgar

2017-07-01

Distinguishing meteorological and plant-mediated drivers of leaf water isotopic enrichment is prerequisite for ecological interpretations of stable hydrogen and oxygen isotopes in plant tissue. We measured input and leaf water δ 2 H and δ 18 O as well as micrometeorological and leaf morpho-physiological variables along a vertical gradient in a mature angiosperm (European beech) and gymnosperm (Douglas fir) tree. We used these variables and different enrichment models to quantify the influence of Péclet and non-steady state effects and of the biophysical drivers on leaf water enrichment. The two-pool model accurately described the diurnal variation of leaf water enrichment. The estimated unenriched water fraction was linked to leaf dry matter content across the canopy heights. Non-steady state effects and reduced stomatal conductance caused a higher enrichment of Douglas fir compared to beech leaf water. A dynamic effect analyses revealed that the light-induced vertical gradients of stomatal conductance and leaf temperature outbalanced each other in their effects on evaporative enrichment. We conclude that neither vertical canopy gradients nor the Péclet effect is important for estimates and interpretation of isotopic leaf water enrichment in hypostomatous trees. Contrarily, species-specific non-steady state effects and leaf temperatures as well as the water vapour isotope composition need careful consideration. © 2017 John Wiley & Sons Ltd.

Compound-specific nitrogen and carbon isotope analysis of nitroaromatic compounds in aqueous samples using solid-phase microextraction coupled to GC/IRMS.

PubMed

Berg, Michael; Bolotin, Jakov; Hofstetter, Thomas B

2007-03-15

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry was used to determine the delta15N and delta13C signatures of selected nitroaromatic contaminants such as the explosive 2,4,6-trinitrotoluene (TNT) for derivation of isotopic enrichment factors of contaminant transformation. Parameters for efficient extraction of nitroaromatic compounds (NACs) and substituted anilines from water samples were evaluated by SPME-GC/MS. delta13C signatures determined by SPME-GC/IRMS and elemental analyzer IRMS (EA-IRMS) were in good agreement, generally within +/-0.7 per thousand, except for 2,4-dinitrotoluene (2,4-DNT) and TNT, which showed slight deviations (<1.3 per thousand). Limits of detection (LODs) for delta13C analysis by SPME-GC/IRMS were between 73 and 780 microg L-1 and correlated with the extraction efficiencies of the compounds determined by SPME-GC/MS. Nitrogen isotope measurements by SPME-GC/IRMS were of similar precision (standard deviations <0.8 per thousand) for all NACs except for TNT. delta15N signatures matched the reference values obtained by EA-IRMS within +/-1.3 per thousand (+2.5 per thousand for TNT), but no systematic trend was found for the deviations. LODs of delta15N measurements ranged from 1.6 to 9.6 mg L-1 for nitrotoluenes, chlorinated NACs and DNTs (22 mg L-1 for TNT). The SPME-GC/IRMS method is well suited for the determination of isotopic enrichment factors of various NAC transformation processes and provides so far unexplored possibilities to elucidate behavior and degradation mechanisms of nitroaromatic contaminants in soils and groundwaters.

A Formation Timescale of the Galactic Halo from Mg Isotopes in Dwarf Stars

NASA Astrophysics Data System (ADS)

Carlos, Marília; Karakas, Amanda I.; Cohen, Judith G.; Kobayashi, Chiaki; Meléndez, Jorge

2018-04-01

We determine magnesium isotopic abundances of metal-poor dwarf stars from the galactic halo, to shed light on the onset of asymptotic giant branch (AGB) star nucleosynthesis in the galactic halo and constrain the timescale of its formation. We observed a sample of eight new halo K dwarfs in a metallicity range of ‑1.9 < [Fe/H] < ‑0.9 and 4200 < T eff(K) < 4950, using the HIRES spectrograph at the Keck Observatory (R ≈ 105 and 200 ≤ S/N ≤ 300). We obtain magnesium isotopic abundances by spectral synthesis on three MgH features and compare our results with galactic chemical evolution models. With the current sample, we almost double the number of metal-poor stars with Mg isotopes determined from the literature. The new data allow us to determine the metallicity when the 26Mg abundances start to become important, [Fe/H] ∼ ‑1.4 ± 0.1. The data with [Fe/H] > ‑1.4 are somewhat higher (1–3σ) than previous chemical evolution model predictions, indicating perhaps higher yields of the neutron-rich isotopes. Our results using only AGB star enrichment suggest a timescale for formation for the galactic halo of about 0.3 Gyr, but considering also supernova enrichment, the upper limit for the timescale formation is about 1.5 Gyr. The data presented herein were obtained at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California and the National Aeronautics and Space Administration. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

The Fine Geochemical Structure of the Hawaiian Mantle Plume: Relation to the Earth's Lowermost Mantle

NASA Astrophysics Data System (ADS)

Weis, D.; Harrison, L.

2017-12-01

The Hawaiian mantle plume has been active for >80 Ma with the highest magmatic flux, also distinctly increasing with time. The identification of two clear geochemical trends (Loa-Kea) among Hawaiian volcanoes in all isotope systems has implications for the dynamics and internal structure of the plume conduit and source in the deep mantle. A compilation of modern isotopic data on Hawaiian shield volcanoes and from the Northwest Hawaiian Ridge (NWHR), focusing specifically on high-precision Pb isotopes integrated with Sr, Nd and Hf isotopes, indicates the presence of source differences for Loa- and Kea-trend volcanoes that are maintained throughout the 1 Ma activity of each volcano. These differences extend back in time on all the Hawaiian Islands ( 5 Ma), and as far back as 47 Ma on the NWHR. In all isotope systems, the Loa-trend basalts are more heterogeneous by a factor of 1.5 than the Kea-trend basalts. The Hawaiian mantle plume overlies the boundary between ambient Pacific lower mantle on the Kea side and the Pacific LLSVP on the Loa side. Geochemical differences between Kea and Loa trends reflect preferential sampling of these two distinct sources of deep mantle material, with additional contribution of ULVZ material sporadically on the Loa side. Plume movement up the gently sloping edge of the LLSVP resulted in entrainment of greater amounts of LLSVP-enriched material over time, and explains why the Hawaiian mantle plume dramatically strengthens over time, contrary to plume models. Similar indications of preferential sampling at the edges of the African LLSVP are found in Kerguelen and Tristan da Cunha basalts in the Indian and Atlantic oceans, respectively. The anomalous low-velocity zones at the core-mantle boundary store geochemical heterogeneities that are enriched in recycled material (EM-I type) with different compositions under the Pacific and under Africa, and that are sampled by strong mantle plumes such as Hawaii and Kerguelen.

Back arc basalts from Patagonia: sediment input in a distal subduction domain

NASA Astrophysics Data System (ADS)

Hesse, A.; Mandeville, C.; Varekamp, J. C.

2007-12-01

Cinder cones and lava flows from the Loncopue graben in N Patagonia (37 S) were sampled over a 180 km N-S transect. These mainly basaltic and trachybasaltic lava flows carry olivine with Cr-Al-rich spinel inclusions, while some more evolved flows carry clinopyroxene and plagioclase. Most of these rocks have between 5-8 percent MgO, and show highly variable K and LIL trace element concentrations. The rocks have up to 180 ppm Ni and 250 ppm Cr. Relative trace element abundance diagrams show negative Ta-Nb anomalies in most rocks, although their depths vary strongly. The REE patterns show LREE enrichment and most rocks have no Eu anomalies, indicating the absence of significant plagioclase fractionation. The basalts have constant U/Th values (~0.25) that are similar to those found in the nearby Copahue-Caviahue arc volcanics. Microprobe analyses of the main phases show olivine with Mg # of 80-87 and up to 2600 ppm Ni. Simulations with the Melts-pMelts programs and application of mineral-melt geothermometers suggest that most olivine phenocrysts crystallized at ~8-10 kbar pressure at temperatures of 1170-1220 oC and with 1-3 percent H2O in the melt. The Sr isotope compositions of 9 samples show a range from 0.7033 - 0.7043, which are negatively correlated with Nd isotope ratios (0.51273- 0.51292). Surprisingly, the most MgO-rich basalt has the most radiogenic Sr isotope ratio. The Pb isotope ratios, well outside the DMM range, correlate very poorly with either Sr isotope ratios or in Pb-Pb isotope graphs. The lack of correlation between degree of evolution and Sr isotope ratios as well as the primitive nature of the rocks and crystals suggest that crustal assimilation was not a major process impacting the composition of these small magma volumes. Incompatible trace element patterns of several samples resemble those of detrital sediment samples from the Pacific, which together with the isotopic data suggest that these magmas may carry a subducted sediment component. Trace element concentrations and ratios do not correlate with radiogenic isotope ratios, suggesting that more than one contaminant source impacted the mantle domain, e.g., fluids as well as sediment melts. Isotope and trace element ratios vary considerably between cinder cones that are only 10-15 km apart, suggesting that the underlying mantle is highly heterogeneous, enriched in subducted components in thin veins and patches. The Loncopue basalts seem to be transitional in composition between the very voluminous S-Patagonia back-arc basalts and the Copahue-Caviahue arc rocks to the north.

Multiple metasomatic events recorded in Kilbourne Hole peridotite xenoliths: the relative contribution of host basalt interaction vs. silicate metasomatic glass

NASA Astrophysics Data System (ADS)

Hammond, S. J.; Yoshikawa, M.; Harvey, J.; Burton, K. W.

2010-12-01

Stark differences between bulk-rock lithophile trace element budgets and the sum of the contributions from their constituent minerals are common, if not ubiquitous in peridotite xenoliths [1]. In the absence of modal metasomatism this discrepancy is often attributed to the “catch-all”, yet often vague process of cryptic metasomatism. This study presents comprehensive Sr-Nd isotope ratios for variably metasomatized bulk-rock peridotites, host basalts, constituent peridotite mineral phases and interstitial glass from 13 spinel lherzolite and harzburgite xenoliths from the Kilbourne Hole volcanic maar, New Mexico, USA. Similar measurements were also made on hand-picked interstitial glass from one of the most highly metasomatized samples (KH03-16) in an attempt to unravel the effects of multiple metasomatic events. In all Kilbourne Hole peridotites analysed, hand-picked, optically clean clinopyroxenes preserve a more primitive Sr isotope signature than the corresponding bulk-rock; a pattern preserved in all but one sample for Nd isotope measurements. Reaction textures, avoided during hand-picking, around clinopyroxene grains are evident in the most metasomatized samples and accompanied by films of high-SiO2 interstitial glass. The margins of primary minerals appear partially resorbed and trails of glassy melt inclusions similar in appearance to those previously reported from the same locality [2], terminate in these films. Hand-picked glass from KH03-16 reveals the most enriched 87Sr/86Sr of any component recovered from these xenoliths (87Sr/86Sr = 0.708043 ± 0.00009; [Sr] = 81 ppm). Similarly, the 143Nd/144Nd of the glass is amongst the most enriched of the peridotite components (143Nd/144Nd = 0.512893 ± 0.000012; [Nd] = 10 ppm). However, the host basalt (87Sr/86Sr = 0.703953 ± 0.00012; 143Nd/144Nd = 0.512873 ± 0.000013), similar in composition to nearby contemporaneous Potrillo Volcanic Field basalts [3], contains nearly an order of magnitude more Sr and more than three times more Nd ([Sr] = 655 ppm; [Nd] = 34 ppm) than the interstitial glass. While the enriched nature of the host basalt, combined with high [Sr] and [Nd], makes it the most likely candidate for the enrichment of the peridotite bulk rocks, mixing between clinopyroxenes and the host basalt cannot account for the full range of bulk-rock Sr-Nd isotope ratios and nearly half of the xenoliths require an additional component that could involve varying amounts of interstitial glass. Moreover, three bulk-rock samples require a further, as yet unidentified component in order to explain the bulk-rock Sr-Nd isotope composition fully, implying that at least three episodes of metasomatism/refertilization must have occurred prior to the arrival of the xenoliths at the surface in their host lava. References: [1] Bedini & Bodinier (1999) Geochim. Cosmochim. Acta 63, 3883-3900. [2] Schiano & Clocchiatti (1994) Nature 368, 622-624. [3] Thompson et al., (2005) J. Petrol. 46, 1603-1643.

Zn isotope study of atmospheric emissions and dry depositions within a 5 km radius of a Pb-Zn refinery

NASA Astrophysics Data System (ADS)

Mattielli, Nadine; Petit, Jérôme C. J.; Deboudt, Karine; Flament, Pascal; Perdrix, Esperanza; Taillez, Aurélien; Rimetz-Planchon, Juliette; Weis, Dominique

The present paper examines the use of zinc isotopes as tracers of atmospheric sources and focuses on the potential fractionation of Zn isotopes through anthropogenic processes. In order to do so, Zn isotopic ratios are measured in enriched ores and airborne particles associated with pyrometallurgical activities of one of the major Pb-Zn refineries in France. Supporting the isotopic investigation, this paper also compares morphological and chemical characteristics of Zn particles collected on dry deposition plates ("environmental samples") placed within a 5 km radius of the smelter, with those of Zn particles collected inside the plant ("process samples"), i.e. dust collected from the main exhaust system of the plant. To ensure a constant isotopic "supply", the refinery processed a specific set of ores during the sampling campaigns, as agreed with the executive staff of the plant. Enriched ores and dust produced by the successive Zn extraction steps show strong isotope fractionation (from -0.66 to +0.22‰) mainly related to evaporation processes within the blast furnaces. Dust from the main chimney displays a δ 66Zn value of -0.67‰. Application of the Rayleigh equation to evaluate the fractionation factor associated with the Zn vapor produced after a free evaporation gives a range of αore/vapor from 1.0004 to 1.0008. The dry deposits, collected on plates downwind of the refinery, display δ 66Zn variations of up to +0.7‰. However, it is to be noted that between 190 and 1250 m from the main chimney of the refinery, the dry deposits show a high level of large (>10 μm) Zn, S, Fe and O bearing aggregates characterized by positive δ 66Zn values (+0.02 to +0.19‰). These airborne particles probably derive from the re-suspension of slag heaps and local emissions from the working-units. In contrast, from 1720 to 4560 m, the dry deposits are comprised of small (PM10) particles, including spherical Zn-bearing aggregates, showing negative δ 66Zn values (-0.52 to -0.02‰). Our results suggest that the source of the distal dry fallouts is the main chimney plume, whose light Zn isotopic signature they preserve. Based on Zn isotopic analysis in combination with morphological and chemical characteristics of airborne particles, the present study suggests the traceability of smelter dusts by Zn isotopes.

Measurement of the Isotopic Signature of Soil Carbon Dioxide: Methods Development and Initial Field Results

NASA Astrophysics Data System (ADS)

Kayler, Z.; Rugh, W.; Mix, A. C.; Bond, B. J.; Sulzman, E. W.

2005-12-01

Soil respiration is a significant component of ecosystem respiration and its isotopic composition is likely to lend insight into ecosystem processes. We have designed probes to determine the isotopic signature of soil-respired CO2 using a two end-member mixing model approach (i.e., Keeling plot). Each probe consists of three 35 ml PVC chambers cased in fiberglass mesh and connected to the soil surface via stainless steel tubing with a septa-lined swagelok fitting. Chambers are vertically connected such that they sample gases at depth intervals centered on 5, 15, and 30 cm. Gases are sampled via a hand vacuum pump equipped with a two-way valve, which allows vials pre-filled with N2 gas in the laboratory to be evacuated and re-filled with only a single septa puncture in the field. Data indicate samples can be stored reliably for up to three days if punctured septa are coated in silicone sealant. To test whether this field sampling method was robust, we constructed a carbon-free sand column out of PVC pipe into which we plumbed a tank of known CO2 concentration and isotopic composition. We have tested the effects of wetting and flow rate on our ability to reproduce tank values. A linear model (geometric mean regression) yielded a more negative isotopic value than the actual gas, but a simple polynomial curve fit the tank value. After laboratory testing, the probes were established in a steep drainage in the H.J. Andrews LTER site in the Cascade Mountains of western Oregon (as part of the Andrews Airshed project). We established a transect of five 10 m2 plots with four soil probes and a companion respiration collar and measured soil CO2 efflux and soil δ13CO2 values biweekly from June-Sept. Results indicate there is a clear difference in isotopic and respiration flux patterns between the north- and south-facing slopes, with the north facing slope exhibiting higher fluxes and more 13C enriched respiration. The temporal pattern of respiration correlates well with decreasing soil moisture over the summer. In addition, flux and isotopic samples collected every 4 hours over a 24 hour period suggested strong diel patterns in both measures, with more enriched δ13C respired from soils in early morning and more δ13C depleted values during the day, suggesting that photosynthetic uptake and CO2 recycling by the aboveground vegetation influence soil-respired CO2 values.

Evidence for extreme Ti-50 enrichments in primitive meteorites

NASA Technical Reports Server (NTRS)

Fahey, A.; Mckeegan, K. D.; Zinner, E.; Goswami, J. N.

1985-01-01

The results of the first high mass resolution ion microprobe study of Ti isotopic compositions in individual refractory grains from primitive carbonaceous meteorites are reported. One hibonite from the Murray carbonaceous chondrite has a 10 percent excess of Ti-50, 25 times higher than the maximum value previously reported for bulk samples of refractory inclusions from carbonaceous chondrites. The variation of the Ti compositions between different hibonite grains, and among pyroxenes from a single Allende refractory inclusion, indicates isotopic inhomogeneities over small scale lengths in the solar nebula and emphasizes the importance of the analysis of small individual phases. This heterogeneity makes it unlikely that the isotopic anomalies were carried into the solar system in the gas phase.

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.

Characterization of a new candidate isotopic reference material for natural Pb using primary measurement method.

PubMed

Nonose, Naoko; Suzuki, Toshihiro; Shin, Ki-Cheol; Miura, Tsutomu; Hioki, Akiharu

2017-06-29

A lead isotopic standard solution with natural abundance has been developed by applying a mixture of a solution of enriched 208 Pb and a solution of enriched 204 Pb ( 208 Pb- 204 Pb double spike solution) as bracketing method. The amount-of-substance ratio of 208 Pb: 204 Pb in this solution is accurately measured by applying EDTA titrimetry, which is one of the primary measurement methods, to each enriched Pb isotope solution. Also metal impurities affecting EDTA titration and minor lead isotopes contained in each enriched Pb isotope solution are quantified by ICP-SF-MS. The amount-of-substance ratio of 208 Pb: 204 Pb in the 208 Pb- 204 Pb double spike solution is 0.961959 ± 0.000056 (combined standard uncertainty; k = 1). Both the measurement of lead isotope ratios in a candidate isotopic standard solution and the correction of mass discrimination in MC-ICP-MS are carried out by coupling of a bracketing method with the 208 Pb- 204 Pb double spike solution and a thallium internal addition method, where thallium solution is added to the standard and the sample. The measured lead isotope ratios and their expanded uncertainties (k = 2) in the candidate isotopic standard solution are 18.0900 ± 0.0046 for 206 Pb: 204 Pb, 15.6278 ± 0.0036 for 207 Pb: 204 Pb, 38.0626 ± 0.0089 for 208 Pb: 204 Pb, 2.104406 ± 0.00013 for 208 Pb: 206 Pb, and 0.863888 ± 0.000036 for 207 Pb: 206 Pb. The expanded uncertainties are about one half of the stated uncertainty for NIST SRM 981, for 208 Pb: 204 Pb, 207 Pb: 204 Pb and 206 Pb: 204 Pb, or one eighth, for 208 Pb: 206 Pb and 207 Pb: 206 Pb, The combined uncertainty consists of the uncertainties due to lead isotope ratio measurements and the remaining time-drift effect of mass discrimination in MC-ICP-MS, which is not removed by the coupled correction method. In the measurement of 208 Pb: 204 Pb, 207 Pb: 204 Pb and 206 Pb: 204 Pb, the latter contribution is two or three times larger than the former. When the coupling of a bracketing method with the 208 Pb- 204 Pb double spike solution and a thallium internal addition method is applied to the analysis of NIST SRM 981, the measured lead isotope ratios are in good agreement with its certified values. This proves that the developed method is not only consistent with the conventional one by NIST SRM 981 but also enables measurement of the lead isotope ratios with higher precision. Copyright © 2017 Elsevier B.V. All rights reserved.

Potassium isotopic evidence for a high-energy giant impact origin of the Moon.

PubMed

Wang, Kun; Jacobsen, Stein B

2016-10-27

The Earth-Moon system has unique chemical and isotopic signatures compared with other planetary bodies; any successful model for the origin of this system therefore has to satisfy these chemical and isotopic constraints. The Moon is substantially depleted in volatile elements such as potassium compared with the Earth and the bulk solar composition, and it has long been thought to be the result of a catastrophic Moon-forming giant impact event. Volatile-element-depleted bodies such as the Moon were expected to be enriched in heavy potassium isotopes during the loss of volatiles; however such enrichment was never found. Here we report new high-precision potassium isotope data for the Earth, the Moon and chondritic meteorites. We found that the lunar rocks are significantly (>2σ) enriched in the heavy isotopes of potassium compared to the Earth and chondrites (by around 0.4 parts per thousand). The enrichment of the heavy isotope of potassium in lunar rocks compared with those of the Earth and chondrites can be best explained as the result of the incomplete condensation of a bulk silicate Earth vapour at an ambient pressure that is higher than 10 bar. We used these coupled constraints of the chemical loss and isotopic fractionation of K to compare two recent dynamic models that were used to explain the identical non-mass-dependent isotope composition of the Earth and the Moon. Our K isotope result is inconsistent with the low-energy disk equilibration model, but supports the high-energy, high-angular-momentum giant impact model for the origin of the Moon. High-precision potassium isotope data can also be used as a 'palaeo-barometer' to reveal the physical conditions during the Moon-forming event.

Pb concentrations and isotopic record preserved in northwest Greenland snow.

PubMed

Kang, Jung-Ho; Hwang, Heejin; Han, Changhee; Hur, Soon Do; Kim, Seong-Joong; Hong, Sungmin

2017-11-01

We present high-resolution lead (Pb) concentrations and isotopic ratios from a northwest Greenland snow pit covering a six-year period between 2003 and 2009. Pb concentrations ranged widely from 2.7 pg g -1 to 97.3 pg g -1 , with a mean concentration of 21.6 pg g -1 . These values are higher than those recorded for the pre-industrial period. Pb concentrations exhibit seasonal spikes in winter-spring layers. Crustal Pb enrichment factors (EF) suggest that the northwest Greenland snow pit is highly enriched with Pb of predominantly anthropogenic origin. The 206 Pb/ 207 Pb ratios ranged from 1.144 to 1.169 with a mean value of 1.156, which fall between less radiogenic Eurasian-type and more radiogenic Canadian-type signatures. This result suggests that several potential source areas of Pb impact on northwest Greenland. Abrupt changes in Pb concentrations and Pb isotope ratios were observed and related to seasonal shifts in source regions of aerosol transport. The 206 Pb/ 207 Pb isotope ratio increased gradually between 2003 and 2009. The similarity of the three-isotope plot ( 206 Pb/ 207 Pb versus 208 Pb/ 207 Pb) between some of our samples and Chinese urban aerosols suggests a steadily increasing contribution of Chinese Pb to northwest Greenland snow. Copyright © 2017. Published by Elsevier Ltd.

Noble gases in submarine pillow basalt glasses from Loihi and Kilauea, Hawaii: A solar component in the Earth

USGS Publications Warehouse

Honda, M.; McDougall, I.; Patterson, D.B.; Doulgeris, A.; Clague, D.A.

1993-01-01

Noble gas elemental and isotopic abundances have been analysed in twenty-two samples of basaltic glass dredged from the submarine flanks of two currently active Hawaiian volcanoes, Loihi Seamount and Kilauea. Neon isotopic ratios are enriched in 20Ne and 21Ne by as much as 16% with respect to atmospheric ratios. All the Hawaiian basalt glass samples show relatively high 3He 4He ratios. The high 20Ne 22Ne values in some of the Hawaiian samples, together with correlations between neon and helium systematics, suggest the presence of a solar component in the source regions of the Hawaiian mantle plume. The solar hypothesis for the Earth's primordial noble gas composition can account for helium and neon isotopic ratios observed in basaltic glasses from both plume and spreading systems, in fluids in continental hydrothermal systems, in CO2 well gases, and in ancient diamonds. These results provide new insights into the origin and evolution of the Earth's atmosphere. ?? 1993.

Visualizing Single Cell Biology: Nanosims Studies of Carbon and Nitrogen Metabolism in Diazotrophic Cyanobacteria

NASA Astrophysics Data System (ADS)

Pett-Ridge, J.; Finzi, J. A.; Capone, D. G.; Popa, R.; Nealson, K. H.; Ng, W.; Spormann, A. M.; Hutcheon, I. D.; Weber, P. K.

2007-12-01

Filamentous nitrogen fixing (diazotrophic) cyanobacteria are key players in global nutrient cycling, but the relationship between CO2- and N2-fixation and intercellular exchange of these elements remains poorly understood in many genera. These bacteria are faced with the challenge of isolating regions of N-fixation (O2 inhibited) and photosynthetic (O2 producing) activity. We used isotope labeling in conjunction with a high-resolution isotope and elemental mapping technique (NanoSIMS) to quantitatively describe 13C and 15N uptake and transport in two aquatic cyanobacteria grown on NaH13CO3 and 15N2. The technical challenges of tracing isotopes within individual bacteria can be overcome with high resolution Secondary Ion Mass Spectrometry (NanoSIMS). In NanoSIMS analysis, samples are sputtered with an energetic primary beam (Cs+, O-) liberating secondary ions that are separated by the mass spectrometer and detected in a suite of electron multipliers. Five isotopic species may be analyzed concurrently with spatial resolution as fine as 50nm. A high sensitivity isotope ratio 'map' can then be generated for the analyzed area. Using sequentially harvested cyanobacteria in conjunction with enriched H13CO3 and 15N2 incubations, we measured temporal enrichment patterns that evolve over the course of a day's growth and suggest tightly regulated changes in fixation kinetics. With a combination of TEM, SEM and NanoSIMS analyses, we also mapped the distribution of C, N and Mo (a critical nitrogenase co-factor) isotopes in intact cells. Our results suggest that NanoSIMS mapping of metal enzyme co-factors may be a powerful method of identifying physiological and morphological characteristics within individual bacterial cells, and could be used to provide a 3-dimensional context for more traditional analyses such as immunogold labeling. Finally, we resolved patterns of isotope enrichment at multiple spatial scales: sub-cellular variation, cell-cell differences along filaments, inter-species transfers (with Rhizobium epibionts), and within-cell depth profiles. Spatial enrichment patterns were correlated with morphological features evidenced in TEM images of microtomed filaments. These features indicate how 15N and 13C "hotspots" are dispersed throughout individual cells in different species, and may indicate isolated locations of increased N2 fixation, sites of amino acid/protein synthesis, or cyanophycin storage granules. This combination of Nano-Secondary Ion Mass Spectrometry (NanoSIMS) analysis and high resolution microscopy allows isotopic analysis to be linked to morphological features and holds great promise for fine-scale studies of bacteria metabolism.

St Paul fracture zone intratransform ridge basalts (Equatorial Atlantic): Insight within the mantle source diversity

NASA Astrophysics Data System (ADS)

Hemond, C.; Brunelli, D.; Maia, M.; Prigent, S.; Sichel, S. E.

2017-12-01

The St Paul Transform System offsets by 630 km the Equatorial Mid Atlantic Ridge at 1° N. It consists of four Major faults separating three intra transform ridge axes. Volcanic glassy samples were collected inside two intratransform ridge (ITR) segments during the COLMEIA cruise (Maia et al ; 2016) and samples from the third ITR available from a previous cruise ST PAUL (Hékinian et al. 2000). Major, trace elements and Hf, Pb, Sr and Nd isotopes were determined on selected hand picked glass chips. Few glassy samples recovered and analysed from abyssal hill samples open a time window of about 4.5 million years in the chemistry of the northern ITR. Results show that all samples are basaltic in composition but trace elements display contrasting images for the three ITR. The northern ITR samples are all light REE and highly incompatible enriched and are E-MORB; the central ITR samples display rather flat REE pattern with a level on enrichment of the HREE higher than the other two ITR and are T-MORB. Southern ITR samples are more heterogeneous N-MORB to T-MORB with a lower level of HREE. Isotopes reveal that the ITRs sample distinct mantle sources. In various isotope plans, the northern ITR samples plot together with published results from the MAR directly north of the St Paul F.Z. Therefore they exhibit some flavor of the Sierra Leone hotspot interacting with the MAR at 1.7°N. Central and southern ITR samples have very distinct composition from the northern ITR but resemble each other. However, for identical 206Pb/204Pb ratios, central ITR has slightly but significantly higher 207Pb/204Pb and 208Pb/204Pb, also higher 143Nd/144Nd for a given 87Sr/86Sr. Southern ITR is in chemical continuity of the MAR southward. So that central ITR samples display a rather specific composition. Off axis samples corresponding to the activity of the northern ITR up to 4.6 m.y. show that the hotspot contribution was even bigger on the spreading axis than today and might be fading with time as the MAR gets away from the Hotspot. It remains to explain how the flow of enriched material derived from the Sierra Leone hotspot passed through the large transform fault that limits the St Paul zone to the north. It is also of interest to explain the peculiar compositions of the central ITR samples that reflect neither the northern adjacent MAR composition nor the southern one.

Mars Atmospheric Escape Recorded by H, C and O Isotope Ratios in Carbon Dioxide and Water Measured by the Sam Tunable Laser Spectrometer on the Curiosity Rover

NASA Technical Reports Server (NTRS)

Webster, C. R.; Mahaffy, P. R.; Leshin, L. A.; Atreya, S. K.; Flesch, G. J.; Stern, J.; Christensen, L. E.; Vasavada, A. R.; Owen, T.; Niles, P. B.;

The study of trace metal absoption using stable isotopes and mass spectrometry

NASA Astrophysics Data System (ADS)

Fennessey, P. V.; Lloyd-Kindstrand, L.; Hambidge, K. M.

1991-12-01

The absorption and excretion of zinc stable isotopes have been followed in more than 120 human subjects. The isotope enrichment determinations were made using a standard VG 7070E HF mass spectrometer. A fast atom gun (FAB) was used to form the ions from a dry residue on a pure silver probe tip. Isotope ratio measurements were found to have a precision of better than 2% (relative standard deviation) and required a sample size of 1-5 [mu]g. The average true absorption of zinc was found to be 73 ± 12% (2[sigma]) when the metal was taken in a fasting state. This absorption figure was corrected for tracer that had been absorbed and secreted into the gastrointestinal (GI) tract over the time course of the study. The average time for a majority of the stable isotope tracer to pass through the GI tract was 4.7 ± 1.9 (2[sigma]) days.

Dual pressure-dual temperature isotope exchange process

DOEpatents

Babcock, D.F.

1974-02-12

A liquid and a gas stream, each containing a desired isotope, flow countercurrently through two liquid-gas contacting towers maintained at different temperatures and pressures. The liquid is enriched in the isotope in one tower while the gas is enriched within the other and a portion of at least one of the enriched streams is withdrawn from the system for use or further enrichment. The tower operated at the lower temperature is also maintained at the lower pressure to prevent formation of solid solvates. Gas flow between the towers passes through an expander-compressor apparatas to recover work from the expansion of gas to the lower pressure and thereby compress the gas returning to the tower of higher pressure. (Official Gazette)

Spin-State-Dependent Ion-Molecule Chemistry as the Origin of N-15 and D Isotopic Anomalies in Primitive Matter.

NASA Technical Reports Server (NTRS)

Wirstrom, E. S.; Charnley, S. B.; Cordiner, M. A.; Milam, S. N.

2012-01-01

Many meteoritic and interplanetary dust particle (IDP) samples contain bulk enhancements and hotspots rich in N-15. Similarly low C(14)N/C(15)N ratios have been observed in numerous comets, An almost constant enrichment factor in comets from disti'nct formation zones in the nebular disk (i.e. both Jupiter Family and Oort Cloud comets), strongly suggests that this fractionation is primordial and was set in the protsolar cloud core. Deuterium enrichment is observed in both meteorites and IDPs

Stable-isotope ratios of hydrogen and oxygen in precipitation at Norman, Oklahoma, 1996-2008

USGS Publications Warehouse

Jaeschke, Jeanne B.; Scholl, Martha A.; Cozzarelli, Isabelle M.; Masoner, Jason R.; Christenson, Scott; Qi, Haiping

2011-01-01

Precipitation samples for measurement of stable-isotope ratios of hydrogen (delta2H) and oxygen (delta18O) were collected at the Norman Landfill Research Site in Norman, Oklahoma, from May 1996 to October 2008. Rainfall amounts also were measured at the site (U.S. Geological Survey gaging station 07229053) during the collection period. The delta2H of precipitation samples ranged from -121.9 to +8.3 per mil, and the delta18O of precipitation ranged from -16.96 to +0.50 per mil. The volume-weighted average values for delta2H and delta18O of precipitation over the 12-year measurement period were -31.13 per mil for delta2H and -5.57 per mil for delta18O. Average summer-season delta2H and delta18O values of precipitation usually were more positive (enriched in the heavier isotopes) than winter values.

New search for double electron capture in {sup 106}Cd decay with the TGV-2 spectrometer

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

Briançon, Ch.; Brudanin, V. B.; Egorov, V. G.

2015-09-15

A new experiment devoted to searches for double electron capture in {sup 106}Cd decay is being performed at the Modane underground laboratory (4800 mwe) with the 32-detector TGV-2 spectrometer. The limit T{sub 1/2}(2νEC/EC) > 2.0×10{sup 20} yr at a 90%confidence level (C.L.) was obtained from a preliminary analysis of data obtained over 2250 h of measurements with about 23.2 g sample enriched in the isotope {sup 106}Cd to 99.57%. The limits T{sub 1/2}(KL, 2741 keV) > 0.9 × 10{sup 20} yr and T{sub 1/2}(KK, 2718 keV) ≫ 1.4 × 10{sup 20} yr at a 90% C.L. on the neutrinoless decaymore » of {sup 106}Cd were obtained from measurements performed with the Obelix low-background spectrometer from high-purity germanium (HPGe spectrometer) for a sample of mass about 23.2 g enriched in the isotope {sup 106}Cd.« less

Amino Acid Isotopic Trophic Enrichment in Mesozooplankton: Is Alanine a Better Predictor of Protistan Grazer Steps?

NASA Astrophysics Data System (ADS)

Decima, M.; Landry, M. R.; Bradley, C. J.; Fogel, M. L.

2016-02-01

Food-web studies within marine environments are increasingly reliant upon results from compound-specific isotope analysis of amino acids (CSIA-AA). The approach is advantageous because it allows consumer trophic positions to be estimated without sampling the dynamic primary producers. The baseline signal in the source AA phenylalanine is preserved, and a constant enrichment in glutamic acid at each trophic step is assumed, regardless of consumer type or diet. However, a number of recent studies challenge the assumption of universal and invariant isotopic fractionation of glutamic acid for all trophic levels, as well as its specific applicability to the main grazers in the ocean: the protistan microzooplankton. We present results from both laboratory and field studies that further explore this issue. Experiments include six 2-stage chemostats, using two different microzooplankton-phytoplankton pairs and one copepod-phytoplankton pair, and one 3-stage experiment using a copepod-microzooplankton-phytoplankton chain. We confirm previous observations of negligible fractionation of glutamic acid in protistan consumers when nutrients are limiting. In contrast, a consistent trophic enrichment effect was observed for alanine, with increasing δ15N values by trophic level for both metazoan and protistan consumers. A re-analysis of published CSIA-AA data of zooplankton species show that an index using alanine and phenylalanine gives trophic level estimates closer to expected given current understanding of the linkages within microbial food webs. Our results examine the details of isotopic fractionation of alanine within defined food chains and generally support its potential use as a trophic level indicator that includes the protistan contribution to mesozooplankton diet.

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.

Correlated Si isotope anomalies and large C-13 enrichments in a family of exotic SiC grains

NASA Technical Reports Server (NTRS)

Stone, J.; Hutcheon, I. D.; Epstein, S.; Wasserburg, G. J.

1991-01-01

A hypothesis is presented to the effect that the distinctive morphological characteristics and comparatively simple Si isotope systematics identify the platy SiC crystals as a genetically related family, formed around a single isotopically heterogeneous presolar star on an association of related stars. The enrichments in C-13 and the Si isotope systematics of the platy SiC are broadly consistent with theoretical models of nucleosynthesis in low-mass, carbon stars on the ASG. The Si isotope array most plausibly reflects mixing between (Si-28)-rich material, inherited from a previous generation of stars, and material enriched in Si-29 and Si-30, produced in intershell regions by neutron capture during He-burning. The absence of a correlation between the Si and C isotopic compositions of the SiC suggests either episodic condensation of SiC, extending over several thermal pulses, in the atmosphere of a single star, or the derivation of the SiC from several stars characterized by different rates of C-13 production.

The fate of moderately volatile elements during planetary formation in the inner Solar System

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.

2017-12-01

Moderately volatile element abundances are variable among inner Solar System bodies, with differing degrees of depletion compared to chondrites. These variations are a consequence of the processes of planetary formation. The conditions and the specific mechanisms of planetary accretion and differentiation can be investigated by analyzing the stable isotope compositions of terrestrial and extraterrestrial samples. The moderately volatile lithophile elements are particularly useful to distinguish between the effects of accretion and those of core formation. Recent work has shown isotope variations in inner Solar System bodies for the moderately volatile elements Zn and K. The purely lithophile nature of Rb (in contrast to Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to further study moderately volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. Terrestrial rocks define a narrow range in Rb isotope composition, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). Larger Rb isotope variations are observed in extraterrestrial materials. Carbonaceous chondrites display a trend toward lighter Rb isotope composition coupled with decreasing Rb/Sr, opposite to the effect expected if their volatile element variations were caused by evaporative loss of Rb. This relationship indicates that the volatile element abundance variations in carbonaceous chondrites are not due to evaporation or condensation, but rather are due to the mixing of chemically and isotopically distinct primordial reservoirs. In contrast, there is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. Significant heavy isotope enrichments (up to several per mil for 87Rb/85Rb) are found for volatile-depleted planetesimals, including eucrites. In addition, lunar rocks also display heavy Rb isotope enrichments compared to the BSE. The most likely cause of these variations is Rb isotope fractionation due to evaporation during accretion.

Silicon isotopes reveal recycled altered oceanic crust in the mantle sources of Ocean Island Basalts

NASA Astrophysics Data System (ADS)

Pringle, Emily A.; Moynier, Frédéric; Savage, Paul S.; Jackson, Matthew G.; Moreira, Manuel; Day, James M. D.

2016-09-01

The study of silicon (Si) isotopes in Ocean Island Basalts (OIB) has the potential to discern between different models for the origins of geochemical heterogeneities in the mantle. Relatively large (∼several per mil per atomic mass unit) Si isotope fractionation occurs in low-temperature environments during biochemical and geochemical precipitation of dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes relative to the dissolved Si. In contrast, only a limited range (∼tenths of a per mil) of Si isotope fractionation has been observed from high-temperature igneous processes. Therefore, Si isotopes may be useful as tracers for the presence of crustal material within OIB mantle source regions that experienced relatively low-temperature surface processes in a manner similar to other stable isotope systems, such as oxygen. Characterizing the isotopic composition of the mantle is also of central importance to the use of the Si isotope system as a basis for comparisons with other planetary bodies (e.g., Moon, Mars, asteroids). Here we present the first comprehensive suite of high-precision Si isotope data obtained by MC-ICP-MS for a diverse suite of OIB. Samples originate from ocean islands in the Pacific, Atlantic, and Indian Ocean basins and include representative end-members for the EM-1, EM-2, and HIMU mantle components. On average, δ30Si values for OIB (-0.32 ± 0.09‰, 2 sd) are in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth (-0.29 ± 0.07‰, 2 sd; Savage et al., 2014). Nonetheless, some small systematic variations are present; specifically, most HIMU-type (Mangaia; Cape Verde; La Palma, Canary Islands) and Iceland OIB are enriched in the lighter isotopes of Si (δ30Si values lower than MORB), consistent with recycled altered oceanic crust and lithospheric mantle in their mantle sources.

Variations in microbial carbon sources and cycling in the deep continental subsurface

NASA Astrophysics Data System (ADS)

Simkus, Danielle N.; Slater, Greg F.; Lollar, Barbara Sherwood; Wilkie, Kenna; Kieft, Thomas L.; Magnabosco, Cara; Lau, Maggie C. Y.; Pullin, Michael J.; Hendrickson, Sarah B.; Wommack, K. Eric; Sakowski, Eric G.; van Heerden, Esta; Kuloyo, Olukayode; Linage, Borja; Borgonie, Gaetan; Onstott, Tullis C.

2016-01-01

Deep continental subsurface fracture water systems, ranging from 1.1 to 3.3 km below land surface (kmbls), were investigated to characterize the indigenous microorganisms and elucidate microbial carbon sources and their cycling. Analysis of phospholipid fatty acid (PLFA) abundances and direct cell counts detected varying biomass that was not correlated with depth. Compound-specific carbon isotope analyses (δ13C and Δ14C) of the phospholipid fatty acids (PLFAs) and carbon substrates combined with genomic analyses did identify, however, distinct carbon sources and cycles between the two depth ranges studied. In the shallower boreholes at circa 1 kmbls, isotopic evidence indicated microbial incorporation of biogenic CH4 by the in situ microbial community. At the shallowest site, 1.05 kmbls in Driefontein mine, this process clearly dominated the isotopic signal. At slightly deeper depths, 1.34 kmbls in Beatrix mine, the isotopic data indicated the incorporation of both biogenic CH4 and dissolved inorganic carbon (DIC) derived from CH4 oxidation. In both of these cases, molecular genetic analysis indicated that methanogenic and methanotrophic organisms together comprised a small component (<5%) of the microbial community. Thus, it appears that a relatively minor component of the prokaryotic community is supporting a much larger overall bacterial community in these samples. In the samples collected from >3 kmbls in Tau Tona mine (TT107, TT109 Bh2), the CH4 had an isotopic signature suggesting a predominantly abiogenic origin with minor inputs from microbial methanogenesis. In these samples, the isotopic enrichments (δ13C and Δ14C) of the PLFAs relative to CH4 were consistent with little incorporation of CH4 into the biomass. The most 13C-enriched PLFAs were observed in TT107 where the dominant CO2-fixation pathway was the acetyl-CoA pathway by non-acetogenic bacteria. The differences in the δ13C of the PLFAs and the DIC and DOC for TT109 Bh2 were ∼-24‰ and 0‰, respectively. The dominant CO2-fixation pathways were 3-HP/4-HB cycle > acetyl-CoA pathway > reductive pentose phosphate cycle.

Formation and Preservation of the Depleted and Enriched Shergottite Isotopic Reservoirs in a Convecting Martian Mantle

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Jones, John H.

2015-01-01

There is compelling isotopic and crater density evidence for geologically recent volcanism on Mars, in the last 100-200 million years and possibly in the last 50 million years. This volcanism is due to adiabatic decompression melting and thus requires some type of present-day convective upwelling in the martian mantle. On the other hand, martian meteorites preserve evidence for at least 3 distinct radiogenic isotopic reservoirs. Anomalies in short-lived isotopic systems (Sm-146, Nd-142, Hf-182, W-182) require that these reservoirs must have developed in the first 50 to 100 million years of Solar System history. The long-term preservation of chemically distinct reservoirs has sometimes been interpreted as evidence for the absence of mantle convection and convective mixing on Mars for most of martian history, a conclusion which is at odds with the evidence for young volcanism. This apparent paradox can be resolved by recognizing that a variety of processes, including both inefficient mantle mixing and geographic separation of isotopic reservoirs, may preserve isotopic heterogeneity on Mars in an actively convecting mantle. Here, we focus on the formation and preservation of the depleted and enriched isotopic and trace element reservoirs in the shergottites. In particular, we explore the possible roles of processes such as chemical diffusion and metasomatism in dikes and magma chambers for creating the isotopically enriched shergottites. We also consider processes that may preserve the enriched reservoir against convective mixing for most of martian history.

Rapid two-dimensional ALSOFAST-HSQC experiment for metabolomics and fluxomics studies: application to a 13C-enriched cancer cell model treated with gold nanoparticles.

PubMed

Schätzlein, Martina Palomino; Becker, Johanna; Schulze-Sünninghausen, David; Pineda-Lucena, Antonio; Herance, José Raul; Luy, Burkhard

2018-04-01

Isotope labeling enables the use of 13 C-based metabolomics techniques with strongly improved resolution for a better identification of relevant metabolites and tracing of metabolic fluxes in cell and animal models, as required in fluxomics studies. However, even at high NMR-active isotope abundance, the acquisition of one-dimensional 13 C and classical two-dimensional 1 H, 13 C-HSQC experiments remains time consuming. With the aim to provide a shorter, more efficient alternative, herein we explored the ALSOFAST-HSQC experiment with its rapid acquisition scheme for the analysis of 13 C-labeled metabolites in complex biological mixtures. As an initial step, the parameters of the pulse sequence were optimized to take into account the specific characteristics of the complex samples. We then applied the fast two-dimensional experiment to study the effect of different kinds of antioxidant gold nanoparticles on a HeLa cancer cell model grown on 13 C glucose-enriched medium. As a result, 1 H, 13 C-2D correlations could be obtained in a couple of seconds to few minutes, allowing a simple and reliable identification of various 13 C-enriched metabolites and the determination of specific variations between the different sample groups. Thus, it was possible to monitor glucose metabolism in the cell model and study the antioxidant effect of the coated gold nanoparticles in detail. Finally, with an experiment time of only half an hour, highly resolved 1 H, 13 C-HSQC spectra using the ALSOFAST-HSQC pulse sequence were acquired, revealing the isotope-position-patterns of the corresponding 13 C-nuclei from carbon multiplets. Graphical abstract Fast NMR applied to metabolomics and fluxomics studies with gold nanoparticles.

Mechanisms linking metabolism of Helicobacter pylori to 18O and 13C-isotopes of human breath CO2

PubMed Central

Som, Suman; De, Anulekha; Banik, Gourab Dutta; Maity, Abhijit; Ghosh, Chiranjit; Pal, Mithun; Daschakraborty, Sunil B.; Chaudhuri, Sujit; Jana, Subhra; Pradhan, Manik

2015-01-01

The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 (18O) and carbon-13 (13C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of 18O/16O and 13C/12C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of 18O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of 18O in breath CO2 were manifested in individuals without the infections. In contrast, the 13C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to 13C-enriched glucose uptake, whereas a distinguishable change of breath 13C/12C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the 18O and 13C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath 12C18O16O and 13C16O16O can be used as potential molecular biomarkers to distinctively track the pathogenesis of Helicobacter pylori and also for eradication purposes and thus may open new perspectives into the pathogen’s physiology along with isotope-specific non-invasive diagnosis of the infection. PMID:26039789

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.

102Pd(n, {gamma}) Cross Section Measurement Using DANCE

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

Hatarik, R.; Alpizar-Vicente, A. M.; Los Alamos National Laboratory, Los Alamos, NM 87545

2006-03-13

The neutron capture cross section of the proton rich nucleus 102Pd was measured with the Detector for Advanced Neutron Capture Experiments (DANCE) at the Los Alamos Neutron Science Center. The target was a 2 mg Pd foil with 78% enriched 102Pd. It was held by a 0.9 {mu}m thick Mylar bag which was selected after comparing different thicknesses of Kapton and Mylar for their scattering background. To identify the contribution of the other Pd isotopes the data of a natural Pd sample was compared to the data of the 102Pd enriched sample. A 12C sample was used to determine themore » scattering background. The 102Pd(n, {gamma}) rate is of importance for the p-process nucleosynthesis.« less

Compositions of HIMU, EM1, and EM2 from Global Trends between Radiogenic Isotopes and Major Elements in Ocean Island Basalts

NASA Astrophysics Data System (ADS)

Jackson, M. G.; Dasgupta, R.

2008-12-01

Sr and Pb isotopes exhibit global trends with the concentrations of major elements (SiO2, TiO2, FeO, Al2O3 and K2O) and major elements ratios (CaO/Al2O3 and K2O/TiO2) in the shield-stage lavas from 18 oceanic hotspots (including Hawaii, Iceland, Galapagos, Cook-Australs, St. Helena, Cape Verde, Cameroon, Canary, Madeira, Comoros, Azores, Samoa, Society, Marquesas, Mascarene, Kerguelen, Pitcairn, and Selvagen). Based on the relationships between major elements and isotopes in ocean island basalts (OIBs), we find that the lavas derived from the mantle end members, HIMU (or high 'ì' = 238U/204Pb), EM1 (enriched mantle 1), EM2 (enriched mantle 2), and DMM (depleted MORB [mid-ocean ridge basalt] mantle) exhibit distinct major element characteristics: When compared to oceanic hotspots globally, the hotspots with a HIMU (radiogenic Pb-isotopes and low 87Sr/86Sr) component, such as St. Helena and Cook-Australs, exhibit high CaO/Al2O3, FeOT, and TiO2 and low SiO2 and Al2O3. EM1 (enriched mantle 1; intermediate 87Sr/86Sr and low 206Pb/204Pb; sampled by hotspots like Pitcairn and Kerguelen) and EM2 (enriched mantle 2; high 87Sr/86Sr and intermediate 206Pb/204Pb; sampled by hotspots like Samoa and Societies) exhibit higher K2O concentrations and K2O/TiO2 weight ratios than HIMU lavas. EM1 lavas exhibit the lowest CaO/Al2O3 in the OIB dataset, and this sets EM1 apart from EM2. A plot of CaO/Al2O3 vs K2O/TiO2 perfectly resolves the four mantle end member lavas. Melting processes (pressure, temperature and degree of melting) fail to provide an explanation for the full spectrum of major element concentrations in OIBs. Such processes also fail to explain the correlations between major elements and radiogenic isotopes. Instead, a long, time integrated history of various parent- daughter elements appears to be coupled to major element and/or volatile heterogeneity in the mantle source. End member lava compositions are compared with experimental partial melt compositions to place constraints on the lithological characteristics of the mantle end members.

Compositions of HIMU, EM1, and EM2 from global trends between radiogenic isotopes and major elements in ocean island basalts

NASA Astrophysics Data System (ADS)

Jackson, Matthew G.; Dasgupta, Rajdeep

2008-11-01

Sr and Pb isotopes exhibit global trends with the concentrations of major elements (SiO 2, TiO 2, FeO, Al 2O 3 and K 2O) and major elements ratios (CaO/Al 2O 3 and K 2O/TiO 2) in the shield-stage lavas from 18 oceanic hotspots (including Hawaii, Iceland, Galapagos, Cook-Australs, St. Helena, Cape Verde, Cameroon, Canary, Madeira, Comoros, Azores, Samoa, Society, Marquesas, Mascarene, Kerguelen, Pitcairn, and Selvagen). Based on the relationships between major elements and isotopes in ocean island basalts (OIBs), we find that the lavas derived from the mantle end members, HIMU (or high 'μ' = 238U/ 204Pb), EM1 (enriched mantle 1), EM2 (enriched mantle 2), and DMM (depleted MORB [mid-ocean ridge basalt] mantle) exhibit distinct major element characteristics: When compared to oceanic hotspots globally, the hotspots with a HIMU (radiogenic Pb-isotopes and low 87Sr/ 86Sr) component, such as St. Helena and Cook-Australs, exhibit high CaO/Al 2O 3, FeO T, and TiO 2 and low SiO 2 and Al 2O 3. EM1 (enriched mantle 1; intermediate 87Sr/ 86Sr and low 206Pb/ 204Pb; sampled by hotspots like Pitcairn and Kerguelen) and EM2 (enriched mantle 2; high 87Sr/ 86Sr and intermediate 206Pb/ 204Pb; sampled by hotspots like Samoa and Societies) exhibit higher K 2O concentrations and K 2O/TiO 2 weight ratios than HIMU lavas. EM1 lavas exhibit the lowest CaO/Al 2O 3 in the OIB dataset, and this sets EM1 apart from EM2. A plot of CaO/Al 2O 3 vs K 2O/TiO 2 perfectly resolves the four mantle end member lavas. Melting processes (pressure, temperature and degree of melting) fail to provide an explanation for the full spectrum of major element concentrations in OIBs. Such processes also fail to explain the correlations between major elements and radiogenic isotopes. Instead, a long, time integrated history of various parent-daughter elements appears to be coupled to major element and/or volatile heterogeneity in the mantle source. End member lava compositions are compared with experimental partial melt compositions to place constraints on the lithological characteristics of the mantle end members.

Production of highly-enriched 134Ba for a reference material for isotope dilution mass spectrometry measurements

DOE PAGES

Horkley, J. J.; Carney, K. P.; Gantz, E. M.; ...

2015-03-17

Isotope dilution mass spectrometry (IDMS) is an analytical technique capable of providing accurate and precise quantitation of trace isotope abundance and assay providing measurement uncertainties below 1 %. To achieve these low uncertainties, the IDMS method ideally utilizes chemically pure “spike” solutions that consist of a single highly enriched isotope that is well-characterized relating to the abundance of companion isotopes and concentration in solution. To address a current demand for accurate 137Cs/137Ba ratio measurements for “age” determination of radioactive 137Cs sources, Idaho National Laboratory (INL) is producing enriched 134Ba isotopes that are tobe used for IDMS spikes to accurately determinemore » 137Ba accumulation from the decay of 137Cs. The final objective of this work it to provide a homogenous set of reference materials that the National Institute of Standards and Technology can certify as standard reference materials used for IDMS. The process that was developed at INL for the separation and isolation of Ba isotopes, chemical purification of the isotopes in solution, and the encapsulation of the materials will be described.« less

Kinetic 15N-isotope effects on algal growth

NASA Astrophysics Data System (ADS)

Andriukonis, Eivydas; Gorokhova, Elena

2017-03-01

Stable isotope labeling is a standard technique for tracing material transfer in molecular, ecological and biogeochemical studies. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism metabolism and growth, which is not consistent with current theoretical and empirical knowledge on kinetic isotope effects. Here, we demonstrate profound changes in growth dynamics of the green alga Raphidocelis subcapitata grown in 15N-enriched media. With increasing 15N concentration (0.37 to 50 at%), the lag phase increased, whereas maximal growth rate and total yield decreased; moreover, there was a negative relationship between the growth and the lag phase across the treatments. The latter suggests that a trade-off between growth rate and the ability to adapt to the high 15N environment may exist. Remarkably, the lag-phase response at 3.5 at% 15N was the shortest and deviated from the overall trend, thus providing partial support to the recently proposed Isotopic Resonance hypothesis, which predicts that certain isotopic composition is particularly favorable for living organisms. These findings confirm the occurrence of KIE in isotopically enriched algae and underline the importance of considering these effects when using stable isotope labeling in field and experimental studies.

Thallium isotopes track fluctuations in global manganese oxide burial during the Ediacaran Period

NASA Astrophysics Data System (ADS)

Ostrander, C. M.; Nielsen, S.; Owens, J. D.; Jiang, G.; Planavsky, N.; Sahoo, S. K.; Zhang, F.; Lyons, T. W.; Anbar, A. D.

2017-12-01

Complex marine ecosystems appear in the geologic record for the first time during the Ediacaran (635 - 541 Ma), after the Marinoan Glaciation but before the Cambrian Explosion. Much debate surrounds the redox-state of global oceans during this diversification, with some arguing for pervasive anoxic conditions and others for increased oxygenation, including the possibility of episodic oxygen increases. Here, we use thallium (Tl) isotopes preserved in organic-rich shales from a deep-water section at Wuhe, South China, to track large-scale perturbations in Mn oxide burial during the Ediacaran. Changes to the Tl isotope composition of seawater over geologic timescales are driven dominantly by fluctuations in global Mn oxide burial, which require persistent O2 at the sediment-water interface. Importantly, the suite of sedimentary rocks analyzed is thought to have been deposited beneath persistent localized euxinia, which is an environment shown to effectively capture the Tl isotope composition of seawater. Within samples previously suggested to host oceanic oxygenation episodes (OOEs) because of high redox-sensitive element (RSE) enrichments (Sahoo et al. 2016, Geobiology), we find Tl isotope values as light as -5 epsilon units, which are indicative of removal of heavy Tl by Mn oxides elsewhere in the Ediacaran ocean and in-line with the presence of deep-marine O2. Intriguingly, between these events, during periods previously viewed as dominantly anoxic, we find Tl isotope excursions to values that are even lighter than during the OOEs (less than -10 epsilon units). To first order, these results imply that an even larger Mn oxide sink was present between the OOEs, which would require pervasive oceanic oxygenation. This interpretation is in direct conflict with interpretations of low RSE enrichments in these same samples, which invoke reservoir drawdown due to widespread anoxia—as well as many other data that suggest dominantly anoxic deep marine conditions through the Ediacaran (e.g. Sperling et al. 2015, Nature). Further work is needed to interpret this paradox.

Nitrogen control of 13C enrichment in heterotrophic organs relative to leaves in a landscape-building desert plant species

DOE PAGES

Zhang, J.; Gu, L.; Bao, F.; ...

2015-01-01

A longstanding puzzle in isotope studies of C 3 plant species is that heterotrophic plant organs (e.g., stems, roots, seeds, and fruits) tend to be enriched in 13C compared to the autotrophic organ (leaves) that provides them with photosynthate. Our inability to explain this puzzle suggests key deficiencies in understanding post-photosynthetic metabolic processes. It also limits the effectiveness of applications of stable carbon isotope analyses in a variety of scientific disciplines ranging from plant physiology to global carbon cycle studies. To gain insight into this puzzle, we excavated whole plant architectures of Nitraria tangutorum Bobrov, a C 3 species thatmore » has an exceptional capability of fixing sands and building sand dunes, in two deserts in northwestern China. We systematically and simultaneously measured carbon isotope ratios and nitrogen and phosphorous contents of different parts of the excavated plants. We also determined the seasonal variations in leaf carbon isotope ratios on nearby intact plants of N. tangutorum. We found, for the first time, that higher nitrogen contents in heterotrophic organs were significantly correlated with increased heterotrophic 13C enrichment compared to leaves. However, phosphorous contents had no effect on the enrichment. In addition, new leaves had carbon isotope ratios similar to roots but were progressively depleted in 13C as they matured. We concluded that a nitrogen-mediated process, hypothesized to be the refixation of respiratory CO 2 by phosphoenolpyruvate (PEP) carboxylase, was responsible for the differences in 13C enrichment among different heterotrophic organs, while processes such as fractionating foliar metabolism and preferentially loading into phloem of 13C-enriched sugars may contribute to the overall autotrophic–heterotrophic difference in carbon isotope compositions.« less

Trace elements and Pb isotopes in soils and sediments impacted by uranium mining.

PubMed

Cuvier, A; Pourcelot, L; Probst, A; Prunier, J; Le Roux, G

2016-10-01

The purpose of this study is to evaluate the contamination in As, Ba, Co, Cu, Mn, Ni, Sr, V, Zn and REE, in a high uranium activity (up to 21,000Bq∙kg(-1)) area, downstream of a former uranium mine. Different geochemical proxies like enrichment factor and fractions from a sequential extraction procedure are used to evaluate the level of contamination, the mobility and the availability of the potential contaminants. Pb isotope ratios are determined in the total samples and in the sequential leachates to identify the sources of the contaminants and to determine the mobility of radiogenic Pb in the context of uranium mining. In spite of the large uranium contamination measured in the soils and the sediments (EF≫40), trace element contamination is low to moderate (2

Seeking excellence: An evaluation of 235 international laboratories conducting water isotope analyses by isotope-ratio and laser-absorption spectrometry.

PubMed

Wassenaar, L I; Terzer-Wassmuth, S; Douence, C; Araguas-Araguas, L; Aggarwal, P K; Coplen, T B

2018-03-15

Water stable isotope ratios (δ 2 H and δ 18 O values) are widely used tracers in environmental studies; hence, accurate and precise assays are required for providing sound scientific information. We tested the analytical performance of 235 international laboratories conducting water isotope analyses using dual-inlet and continuous-flow isotope ratio mass spectrometers and laser spectrometers through a water isotope inter-comparison test. Eight test water samples were distributed by the IAEA to international stable isotope laboratories. These consisted of a core set of five samples spanning the common δ-range of natural waters, and three optional samples (highly depleted, enriched, and saline). The fifth core sample contained unrevealed trace methanol to assess analyst vigilance to the impact of organic contamination on water isotopic measurements made by all instrument technologies. For the core and optional samples ~73 % of laboratories gave acceptable results within 0.2 ‰ and 1.5 ‰ of the reference values for δ 18 O and δ 2 H, respectively; ~27 % produced unacceptable results. Top performance for δ 18 O values was dominated by dual-inlet IRMS laboratories; top performance for δ 2 H values was led by laser spectrometer laboratories. Continuous-flow instruments yielded comparatively intermediate results. Trace methanol contamination of water resulted in extreme outlier δ-values for laser instruments, but also affected reactor-based continuous-flow IRMS systems; however, dual-inlet IRMS δ-values were unaffected. Analysis of the laboratory results and their metadata suggested inaccurate or imprecise performance stemmed mainly from skill- and knowledge-based errors including: calculation mistakes, inappropriate or compromised laboratory calibration standards, poorly performing instrumentation, lack of vigilance to contamination, or inattention to unreasonable isotopic outcomes. To counteract common errors, we recommend that laboratories include 1-2 'known' control standards in all autoruns; laser laboratories should screen each autorun for spectral contamination; and all laboratories should evaluate whether derived d-excess values are realistic when both isotope ratios are measured. Combined, these data evaluation strategies should immediately inform the laboratory about fundamental mistakes or compromised samples. Copyright © 2018 John Wiley & Sons, Ltd.

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.

Seeking excellence: An evaluation of 235 international laboratories conducting water isotope analyses by isotope-ratio and laser-absorption spectrometry

USGS Publications Warehouse

Wassenaar, L. I.; Terzer-Wassmuth, S.; Douence, C.; Araguas-Araguas, L.; Aggarwal, P. K.; Coplen, Tyler B.

2018-01-01

RationaleWater stable isotope ratios (δ2H and δ18O values) are widely used tracers in environmental studies; hence, accurate and precise assays are required for providing sound scientific information. We tested the analytical performance of 235 international laboratories conducting water isotope analyses using dual-inlet and continuous-flow isotope ratio mass spectrometers and laser spectrometers through a water isotope inter-comparison test.MethodsEight test water samples were distributed by the IAEA to international stable isotope laboratories. These consisted of a core set of five samples spanning the common δ-range of natural waters, and three optional samples (highly depleted, enriched, and saline). The fifth core sample contained unrevealed trace methanol to assess analyst vigilance to the impact of organic contamination on water isotopic measurements made by all instrument technologies.ResultsFor the core and optional samples ~73 % of laboratories gave acceptable results within 0.2 ‰ and 1.5 ‰ of the reference values for δ18O and δ2H, respectively; ~27 % produced unacceptable results. Top performance for δ18O values was dominated by dual-inlet IRMS laboratories; top performance for δ2H values was led by laser spectrometer laboratories. Continuous-flow instruments yielded comparatively intermediate results. Trace methanol contamination of water resulted in extreme outlier δ-values for laser instruments, but also affected reactor-based continuous-flow IRMS systems; however, dual-inlet IRMS δ-values were unaffected.ConclusionsAnalysis of the laboratory results and their metadata suggested inaccurate or imprecise performance stemmed mainly from skill- and knowledge-based errors including: calculation mistakes, inappropriate or compromised laboratory calibration standards, poorly performing instrumentation, lack of vigilance to contamination, or inattention to unreasonable isotopic outcomes. To counteract common errors, we recommend that laboratories include 1–2 'known' control standards in all autoruns; laser laboratories should screen each autorun for spectral contamination; and all laboratories should evaluate whether derived d-excess values are realistic when both isotope ratios are measured. Combined, these data evaluation strategies should immediately inform the laboratory about fundamental mistakes or compromised samples.

Hydrogen isotope ratios of terrestrial leaf wax n-alkanes from the Tibetan Plateau: Controls on apparent enrichment factors, effect of vapor sources and implication for altimetry

NASA Astrophysics Data System (ADS)

Zhang, Xiaolong; Xu, Baiqing; Günther, Franziska; Mügler, Ines; Lange, Markus; Zhao, Huabiao; Li, Jiule; Gleixner, Gerd

2017-08-01

Empirical evidence suggested that the altitudinal dependence of hydrogen isotope ratios of leaf wax n-alkanes (δDwax) can be used to estimate paleoaltitudinal changes. However, the application of δDwax-based paleoaltimetry remains difficult, as the impacts of evaporative, transpirative and biosynthetic processes on hydrogen isotope fractionations in changing environments and the influence of likely changing water vapor sources are not well explored. For this study, we sampled stream waters, soils and plant leaves along two transects spanning large gradients of altitude, precipitation amount, vapor source, temperature and vegetation type on the Tibetan Plateau (TP). δD values of stream water (as an approximation for δDp), soil water (δDsw) and plant leaf water (δDlw) as well as leaf wax n-alkanes were measured in order to quantify isotopic fractionations in the formation of leaf waxes. Most interestingly, we found a strong negative correlation between the evapotranspirative enrichment of leaf water against precipitation (εlw-p), which combines the effects of soil evaporation and leaf transpiration, and the biosynthetic hydrogen isotope fractionation (εwax-lw), which describes isotopic enrichment between leaf wax and leaf water. The relationship yields a steady apparent isotopic enrichment factor (εwax-p) between leaf wax and precipitation, which is independent from climatic parameters and has an average value of -107 ± 26‰ for grasses (monocotyledons) and -77 ± 22‰ for trees (dicotyledons). Since the terrestrial n-alkanes, especially n-C27 and n-C29, in sediments are derived from trees and grasses, the likely change of the vegetation type in the uplift of mountains can change the isotopic estimates by about ±30‰, which corresponds to an altitudinal change of ∼1600 m. We, therefore, suggest that hydrogen isotope ratio of sedimentary n-C31 alkane, which is mainly derived from grasses might be better proxies to reconstruct paleoaltitudes. Our large dataset of δDwax from trees and grasses that aimed to mirror the variability of environmental factors over geological time frames showed the lapse rates were significant, but much smaller than in previous studies. Most importantly our result demonstrated that the lapse rate significantly differed for both transects (p = 0.0068), i.e. 0.87 ± 0.71‰/100 m (R2 = 0.28, p = 0.2841, n = 6) and 2.28 ± 0.82‰/100 m (R2 = 0.34, p = 0.0135, n = 17) for Indian monsoon and Westerly dominated areas, respectively. This suggests that different moisture sources might strongly affected the observed lapse rates. In consequences altitude reconstructions are strongly complicated in areas with likely changing air masses like the Tibetan Plateau.

Process for recovering evolved hydrogen enriched with at least one heavy hydrogen isotope

DOEpatents

Tanaka, John; Reilly, Jr., James J.

1978-01-01

This invention relates to a separation means and method for enriching a hydrogen atmosphere with at least one heavy hydrogen isotope by using a solid titaniun alloy hydride. To this end, the titanium alloy hydride containing at least one metal selected from the group consisting of vanadium, chromium, manganese, molybdenum, iron, cobalt and nickel is contacted with a circulating gaseous flow of hydrogen containing at least one heavy hydrogen isotope at a temperature in the range of -20.degree. to +40.degree. C and at a pressure above the dissociation pressure of the hydrided alloy selectively to concentrate at least one of the isotopes of hydrogen in the hydrided metal alloy. The contacting is continued until equilibrium is reached, and then the gaseous flow is isolated while the temperature and pressure of the enriched hydride remain undisturbed selectively to isolate the hydride. Thereafter, the enriched hydrogen is selectively recovered in accordance with the separation factor (S.F.) of the alloy hydride employed.

Evolution of the upper mantle beneath the southern Baikal rift zone: an Sr-Nd isotope study of xenoliths from the Bartoy volcanoes

NASA Astrophysics Data System (ADS)

Ionov, D. A.; Kramm, U.; Stosch, H.-G.

1992-06-01

Anhydrous and amphibole-bearing peridotite xenoliths occur in roughly equal quantitites in the Bartoy volcanic field about 100 km south of the southern tip of Lake Baikal in Siberia (Russia). Whole-rock samples and pure mineral separates from nine xenoliths have been analyzed for Sr and Nd isotopes in order to characterize the upper mantle beneath the southern Baikal rift zone. In an Sr-Nd isotope diagram both dry and hydrous xenoliths from Bartoy plot at the junction between the fields of MORB and ocean island basalts. This contrasts with data available on two other localities around Lake Baikal (Tariat and Vitim) where peridotites typically have Sr-Nd isotope compositions indicative of strong long-term depletion in incompatible elements. Our data indicate significant chemical and isotopic heterogeneity in the mantle beneath Bartoy that may be attributed to its position close to an ancient suture zone separating the Siberian Platform from the Mongol-Okhotsk mobile belt and occupied now by the Baikal rift. Two peridotites have clinopyroxenes depleted in light rare earth elements (LREE) with Sr and Nd model ages of about 2 Ga and seem to retain the trace element and isotopic signatures of old depleted lithospheric mantle, while all other xenoliths show different degrees of LREE-enrichment. Amphiboles and clinopyroxenes in the hydrous peridotites are in Sr-Nd isotopic disequilibrium. If this reflects in situ decay of 147Sm and 87Rb rather than heterogeneities produced by recent metasomatic formation of amphiboles then 300 400 Ma have passed since the minerals were last in equilibrium. This age range then indicates an old enrichment episode or repeated events during the Paleozoic in the lithospheric mantle initially depleted maybe ˜2 Ga ago. The Bartoy hydrous and enriched dry peridotites, therefore, are unlikely to represent fragments of a young asthenospheric bulge which, according to seismic reflection studies, reached the Moho at the axis of the Baikal rift zone a few Ma ago. By contrast, hydrous veins in peridotites may be associated with rift formation processes.

Evidence of hydraulic lift for pre-rainy season leaf out and dry-season stem water enrichment in Sclerocarya birrea, a tropical agroforestry tree

NASA Astrophysics Data System (ADS)

Ceperley, Natalie; Mande, Theophile; Rinaldo, Andrea; Parlange, Marc B.

2014-05-01

We use stable isotopes of water as tracers to follow water use by five Sclerocarya birrea trees in a catchment in South Eastern Burkina Faso interspersed with millet fields, gallery forest, Sudanian savanna, and fallow fields. Isotopic ratios were determined from water extracted from stems of the trees and sub-canopy soil of two of them, while nearby ground water, precipitation, and surface water was sampled weekly. A unique configuration of sensors connected with a wireless sensor network of meteorological stations measured sub-canopy shading, the temperature and humidity in the canopy, through-fall, and soil moisture under two of the trees. Both water extracted from sap and water extracted from soil is extremely enriched in the dry season, but drop to levels close to the ground water in February or March, which coincides with the growth of leaves. Dates of leaf out were confirmed by changes in δDH and δO18 concentrations of water, photographic documentation & pixel analysis, and analysis of sub-canopy radiation and proceeded the rise in humidity and flow that was later detected in the sub-canopy soil, the trunk of the tree (sap-flow), and atmosphere (canopy VPD). Examination of the isotopic signature suggests that size of tree plays an important role in duration and timing of this leaf-out as well as the degree of enrichment during the peak of the dry season. Further examination of the isotopic signatures of the roots suggested that the trees are performing hydraulic redistribution, or lifting the ground water and "sharing it" with the soil in the rooting zone in the dry season. The enriched level of xylem in this case is a product of water loss, and enrichment, along the travel path of the water from the roots to the tip of the stem, as evidenced by the variation according to size of tree. Vapor pressure deficit, soil water, and soil moisture interactions support this picture of interacting controls, separate from hydrologic triggers on the water movement in the tree.

Accelerator-based method of producing isotopes

DOEpatents

Nolen, Jr., Jerry A.; Gomes, Itacil C.

2015-11-03

The invention provides a method using accelerators to produce radio-isotopes in high quantities. The method comprises: supplying a "core" of low-enrichment fissile material arranged in a spherical array of LEU combined with water moderator. The array is surrounded by substrates which serve as multipliers and moderators as well as neutron shielding substrates. A flux of neutrons enters the low-enrichment fissile material and causes fissions therein for a time sufficient to generate desired quantities of isotopes from the fissile material. The radio-isotopes are extracted from said fissile material by chemical processing or other means.

Mantle metasomatism above subduction zones: Trace-element and radiogenic isotope characteristics of peridotite xenoliths from Batan Island (Philippines)

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

Vidal, Ph.; Dupuy, C.; Maury, R.

1989-12-01

Trace-element abundances and radiogenic isotope ratios have been determined for a suite of upper mantle-derived xenoliths collected from Pliocene-Quaternary andesitic lavas on Batan Island, northernmost Philippines. The xenoliths exhibit mineralogical changes and large ion lithophile enrichment indicative of metasomatism involving H{sub 2}O-rich fluids. Strontium and neodymium isotopes in the xenoliths are not totally consistent with those in host lavas, but a common signature is indicated by the fact that all samples plot below the mantle array. The flux of fluids in the mantle wedge probably occurred over a long period of time. The flux induced large but variable changes inmore » mineral and trace and isotopic compositions, and ultimately resulted in the melting of the peridotites and production of island-arc lavas.« less

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.

HIGH ARSENIC CONCENTRATIONS AND ENRICHED SULFUR AND OXYGEN ISOTOPES IN A FRACTURED-BEDROCK GROUND-WATER SYSTEM

EPA Science Inventory

Elevated arsenic concentrations are coincident with enriched sulfur and oxygen isotopes of sulfate in bedrock ground water within Kelly's Cove watershed, Northport, Maine, USA. Interpretation of the data is complicated by the lack of correlations between sulfate concentrations an...

Large fractionations of C and H isotopes related to methane oxidation in Arctic lakes

NASA Astrophysics Data System (ADS)

Cadieux, Sarah B.; White, Jeffrey R.; Sauer, Peter E.; Peng, Yongbo; Goldman, Amy E.; Pratt, Lisa M.

2016-08-01

Microbial oxidation of methane (CH4) plays a central role in carbon cycling in Arctic lakes, reducing potential CH4 emissions associated with warming. Isotopic signatures of CH4 (δ13C and δ2H) are indicators of microbial oxidation, wherein the process strongly enriches 13C and 2H in residual CH4. We present δ13C and δ2H measurements obtained from sampling the water column and sediment for dissolved CH4 from three, small Arctic lakes in western Greenland under both open-water and ice-covered conditions from 2013 to 2014. Despite substantial variations in aquatic chemistry among the lakes, δ13C and δ2H of CH4 suggested that CH4 was produced predominantly by acetoclastic methanogenesis in the littoral sediments and hydrogenotrophic methanogenesis in the profundal sediments in all of the lakes. Surprisingly large variations for both δ13C and δ2H of CH4 were observed, with δ13C extending from -72‰ to +7.4‰ and δ2H from -390‰ to +250‰. The CH4 isotopic values reported here were significantly more enriched (p < 0.0001) in both 13C and 2H than values reported from other Arctic freshwater environments. As is characteristic of methanotrophy, the enrichment in 13C and 2H was associated with low CH4 concentrations. We suggest that the CH4 most enriched in 13C and 2H may reflect unusually efficient methanotrophic communities in Arctic ice-margin lakes. This study provides the first measurement of δ2H for CH4 in an Arctic freshwater environment at concentrations <10 μM. The extreme enrichment of 13C and 2H of CH4 from Arctic methanotrophy has significant implications for interpreting sources and sinks of CH4. Without knowledge of local geology, stable isotope values of CH4 higher than -30‰ for δ13C and -150‰ for δ2H could be misinterpreted as thermogenic, geothermal, or abiogenic origins. Given crystalline bedrock and the strong positive correlation between δ13C and δ2H throughout the water columns in three Arctic lakes confirms that CH4 heavily enriched in 13C and 2H is the result of methanotrophy.

Investigating Uranium Concentrations in Groundwaters in the State of Idaho Using Kinetic Phosphorescence Analysis and Inductively Coupled Plasma Mass Spectrometry.

PubMed

Tkavadze, Levan; Dunker, Roy E; Brey, Richard R; Dudgeon, John

2016-11-01

The determination of uranium concentrations in natural water samples is of great interest due to the environmental consequences of this radionuclide. In this study, 380 groundwater samples from various locations within the state of Idaho were analyzed using two different techniques. The first method was Kinetic Phosphorescence Analysis (KPA), which gives the total uranium concentrations in water samples. The second analysis method was inductively coupled plasma mass spectrometry (ICP- MS). This method determines the total uranium concentration as well as the separate isotope concentrations of uranium. The U/U isotopic ratio was also measured for each sample to confirm that there was no depleted or enriched uranium present. The results were compared and mapped separately from each other. The study also found that in some areas of the state, natural uranium concentrations are relatively high.

Stable carbon and hydrogen isotope fractionation of dissolved organic groundwater pollutants by equilibrium sorption.

PubMed

Höhener, Patrick; Yu, Xianjing

2012-03-15

Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by "heavy divided by light", carbon enrichment factors for equilibrium sorption were derived which ranged from -0.13±0.04‰ (benzene) to -0.52±0.19‰ (trichloroethene at 5-15 °C). Hydrogen enrichment factors for sorption of 14 different compounds were between -2.4 and -9.2‰. For perdeuterated hydrocarbons the predicted enrichment factors ranged from -19±5.4‰ (benzene) to -64±30‰ (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for (13)C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants. Copyright © 2011 Elsevier B.V. All rights reserved.

Fungal functioning in a pine forest: evidence from a 15N-labeled global change experiment

Treesearch

Erik A. Hobbie; Linda T.A. van Diepen; Erik A. Lilleskov; Andrew P. Oiumette; Adrien C. Finzi; Kirsten S. Hofmockel

2014-01-01

We used natural and tracer nitrogen (N) isotopes in a Pinus taeda free air CO2 enrichment (FACE) experiment to investigate functioning of ectomycorrhizal and saprotrophic fungi in N cycling. Fungal sporocarps were sampled in 2004 (natural abundance and 15N tracer) and 2010 (tracer) and δ15...

A Multi-Proxy Paradigm in the Pursuit of Ocean Paleoredox

NASA Astrophysics Data System (ADS)

Anbar, A. D.; Duan, Y.; Kendall, B.; Reinhard, C.; Severmann, S.; Lyons, T. W.

2011-12-01

The geologic record provides abundant evidence for variations in ocean oxygenation throughout Earth history. Expansion of ocean anoxic zones is expected in the future as a consequence of global climate change, with attendant effects on global nutrient inventories, carbon cycling and fluxes of trace greenhouse gases to the atmosphere. Therefore, studying ancient ocean redox variations not only teaches us about the history of the Earth system, but also provides insights into how the system may respond to analogous human perturbations. However, the extent, duration, causes, and consequences of most past variations are poorly understood. This problem motivates the development of paleoredox proxies, including novel stable isotope systems such as Mo, Fe, U and Tl. Experience with these emerging isotope systems demonstrates great promise but also many challenges. The Mo isotope system is illustrative. To first order, the geochemical cycling and isotope systematics of this element are straightforward, making it a useful proxy. However, critical unresolved issues include: (a) uncertainties in the ocean inputs through time; (b) ambiguities about fractionation mechanisms; (c) inadequate understanding of how modern analogs map to ancient systems. Similar challenges confront all the novel isotope systems. The way forward requires integration of multiple isotopic proxies, as well as information gleaned from careful analyses of element concentrations. For example, an episode of Mo enrichment in the 2.5 Ga Mt. McRae Shale is generally interpreted as resulting from buildup of Mo in seawater due to oxidative weathering. This enrichment is therefore thought to indicate a "whiff" of O2 in the environment prior to the Great Oxidation Event that began at 2.4 Ga. Molybdenum isotopes are consistent with this interpretation. However, Mo enrichment due to enhanced input from low-T hydrothermal sources in an anoxic regime cannot be completely excluded given the current state of knowledge of Mo isotope systematics from such sources. By considering sedimentary Fe enrichments together with Fe isotopes, we find that the Mo enrichment correlates with the telltale signature of a shelf-to-basin Fe redox "shuttle". Uranium isotopes also exhibit variations indicative of redox transformations. This multi-proxy dataset therefore paints a robust picture of trace metal redox cycling consistent with the "whiff" interpretation.

Specific pathways for the incorporation of dissolved barium and molybdenum into the bivalve shell: an isotopic tracer approach in the juvenile Great Scallop (Pecten maximus).

PubMed

Tabouret, Hélène; Pomerleau, Sébastien; Jolivet, Aurélie; Pécheyran, Christophe; Riso, Ricardo; Thébault, Julien; Chauvaud, Laurent; Amouroux, David

2012-07-01

Dissolved barium and molybdenum incorporation in the calcite shell was investigated in the Great Scallop Pecten maximus. Sixty six individuals were exposed for 16 days to two successive dissolved Ba and Mo concentrations accurately differentiated by two different isotopic enrichments (⁹⁷Mo, ⁹⁵Mo; ¹³⁵Ba, ¹³⁷Ba). Soft tissue and shell isotopic composition were determined respectively by quantitative ICP-MS (Inductively Coupled Plasma Mass Spectrometer) and laser ablation--ICP-MS. Results from Ba enrichment indicate the direct incorporation of dissolved Ba into the shell in proportion to the levels in the water in which they grew with a 6-8 day delay. The low spike contributions and the low partition coefficient (D(Mo) = 0.0049 ± 0.0013), show that neither the soft tissue nor the shell were significantly sensitive to Mo enrichment. These results eliminate direct Mo shell enrichment by the dissolved phase, and favour a trophic uptake that will be investigated using the successive isotopic enrichment approach developed in this study. Copyright © 2012 Elsevier Ltd. All rights reserved.

Process for preparing a chemical compound enriched in isotope content. [nitrogen 15-enriched nitric acid

DOEpatents

Michaels, E.D.

1981-02-25

A process to prepare a chemical enriched in isotope content includes: a chemical exchange reaction between a first and second compound which yields an isotopically enriched first compound and an isotopically depleted second compound; the removal of a portion of the first compound as product and the removal of a portion of the second compound as spent material; the conversion of the remainder of the first compound to the second compound for reflux at the product end of the chemical exchange reaction region; the conversion of the remainder of the second compound to the first compound for reflux at the spent material end of the chemical exchange region; and the cycling of the additional chemicals produced by one conversion reaction to the other conversion reaction, for consumption therein. One of the conversion reactions is an oxidation reaction, and the energy that it yields is used to drive the other conversion reaction, a reduction. The reduction reaction is carried out in a solid polymer electrolyte electrolytic reactor. The overall process is energy efficient and yields no waste by-products. A particular embodiment of the process in the production of nitrogen-15-enriched nitric acid.

Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits, Cantabria, Spain

NASA Astrophysics Data System (ADS)

Pašava, Jan; Tornos, Fernando; Chrastný, Vladislav

2014-10-01

We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ66Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from -0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ34S = +6.6 and stage 2 has δ34S = -0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light 66Zn-depleted signatures with δ66Zn values from -0.80 to -0.01 per mil (mostly between -0.80 and -0.24 per mil) and δ34S values from +10.7 to +15.7 per mil without any relationship between the δ66Zn and δ34S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250-320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH2S > mZn2+ as a result of change in pH, T, and Zn predominant species. The light δ66Zn accompanied by heavy δ34S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ66Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.

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

NASA Astrophysics Data System (ADS)

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

2005-04-01

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

Two-Dimensional Stable Isotope Fractionation During Aerobic and Anaerobic Alkane Biodegradation and Implications for the Field

NASA Astrophysics Data System (ADS)

El Morris, Brandon; Suflita, Joseph M.; Richnow, Hans-Hermann

2010-05-01

Quantitatively, n-alkanes comprise a major portion of most crude oils. In petroliferous formations, it may be possible to relate the loss of these compounds to the levels of biodegradation occurring in situ [1]. Moreover, it is important to develop indicators of alkane degradation that may be used to monitor bioremediation of hydrocarbon-impacted environments. Desulfoglaeba alkanexedens and Pseudomonas putida GPo1 were used to determine if carbon and hydrogen stable isotope fractionation could differentiate between n-alkane degradation under anaerobic and aerobic conditions, respectively in the context of the Rayleigh equation model [2]. Bacterial cultures were sacrificed by acidification and headspace samples were analyzed for stable isotope composition using gas chromatography-isotope ratio mass spectrometry. Carbon enrichment factors (bulk) for anaerobic and aerobic biodegradation of hexane were -5.52 ± 0.2‰ and -4.34 ± 0.3‰, respectively. Hydrogen enrichment during hexane degradation was -43.14 ± 6.32‰ under sulfate-reducing conditions, and was too low for quantification during aerobiosis. Collectively, this indicates that the correlation between carbon and hydrogen stable isotope fractionation (may be used to help elucidate in situ microbial processes in oil reservoirs, and during intrinsic as well as engineered remediation efforts. References 1. Asif, M.; Grice, K.; Fazeelat, T., Assessment of petroleum biodegradation using stable hydrogen isotopes of individual saturated hydrocarbon and polycyclic aromatic hydrocarbon distributions in oils from the Upper Indus Basin, Pakistan. Organic Geochemistry 2009, 40, (3), 301-311. 2. Fischer, A.; Herklotz, I.; Herrmann, S.; Thullner, M.; Weelink, S. A. B.; Stams, A., J. M.; Schloemann, M.; Richnow, H.-H.; Vogt, C., Combined carbon and hydrogen isotope fractionation investigations for elucidating benzene biodegradation pathways. Environ. Sci. Technol. 2008, 42, 4356-4363.

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

NASA Astrophysics Data System (ADS)

Boutt, D. F.

2017-12-01

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

Chemical Imaging and Stable Isotope Analysis of Atmospheric Particles by NanoSIMS (Invited)

NASA Astrophysics Data System (ADS)

Sinha, B.; Harris, E. J.; Pöhlker, C.; Wiedemann, K. T.; van Pinxteren, D.; Tilgner, A.; Fomba, K. W.; Schneider, J.; Roth, A.; Gnauk, T.; Fahlbusch, B.; Mertes, S.; Lee, T.; Collett, J. L.; Shiraiwa, M.; Gunthe, S. S.; Smith, M.; Artaxo, P. P.; Gilles, M.; Kilcoyne, A. L.; Moffet, R.; Weigand, M.; Martin, S. T.; Poeschl, U.; Andreae, M. O.; Hoppe, P.; Herrmann, H.; Borrmann, S.

2013-12-01

Chemical imaging analysis of the internal distribution of chemical compounds by a combination of SEM-EDX, and NanoSIMS allows investigating the physico-chemical properties and isotopic composition of individual aerosol particles. Stable sulphur isotope analysis provides insight into the sources, sinks and oxidation pathways of SO2 in the environment. Oxidation by OH radicals, O3 and H2O2 enriches the heavier isotope in the product sulphate, whereas oxidation by transition metal ions (TMI), hypohalites and hypohalous acids depletes the heavier isotope in the product sulphate. The isotope fractionation during SO2 oxidation by stabilized Criegee Intermediate radicals is unknown. We studied the relationship between aerosol chemical composition and predominant sulphate formation pathways in continental clouds in Central Europe and during the wet season in the Amazon rain forest. Sulphate formation in continental clouds in Central Europe was studied during HCCT-2010, a lagrangian-type field experiment, during which an orographic cloud was used as a natural flow-through reactor to study in-cloud aerosol processing (Harris et al. 2013). Sulphur isotopic compositions in SO2 and H2SO4 gas and particulate sulphate were measured and changes in the sulphur isotope composition of SO2 between the upwind and downwind measurement sites were used to determine the dominant SO2 chemical removal process occurring in the cloud. Changes in the isotopic composition of particulate sulphate revealed that transition metal catalysis pathway was the dominant SO2 oxidation pathway. This reaction occurred primarily on coarse mineral dust particles. Thus, sulphate produced due to in-cloud SO2 oxidation is removed relatively quickly from the atmosphere and has a minor climatic effect. The aerosol samples from the Amazonian rainforest, a pristine tropical environment, were collected during the rainy season. The samples were found to be dominated by SOA particles in the fine mode and primary biological aerosol particles in the coarse mode (Pöhlker et al. 2012). We applied STXM-NEXAFS analysis, SEM-EDX analysis and NanoSIMS analysis to investigate the morphology, chemical composition and isotopic composition of aerosol samples. Biogenic salt particles emitted from active biota in the rainforest were found to be enriched in the heavier sulphur isotope, whereas particles with a high organic mass fraction modified by condensation of VOC oxidation products and/or cloud processing were significantly depleted in the heavier sulphur isotope compared to the seed particles. This indicates either a depleted gas phase source of sulphur dioxide contributed to the sulphate formation via the H2O2, O3 or OH oxidation pathway or an unaccounted reaction pathway which depletes the heavier isotope in the product sulphate contributes to the secondary sulphate formation in the pristine Amazon rainforest. Harris, E., et al., Science 340, 727-730, 2013 Pöhlker, C., Science 337, 1075-1078, 2012

Re-Os isotopic evidence for an enriched-mantle source for the Noril'sk-type, ore-bearing intrusions, Siberia

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.; Horan, M.F.; Czamanske, G.K.; Krogstad, E.J.; Fedorenko, V.A.; Kunilov, V.E.

1994-01-01

Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Noril'sk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Noril'sk I intrusion have ??Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have ??Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have ??Os values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Noril'sk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also have relatively uniform ??{lunate}Nd values that range only from -0.8 to + 1.1. This limited variation in neodymium isotopic composition may reflect the characteristics of the mantle sources of the rocks, or it may indicate that somehow similar proportions of crust contaminated the parental melts. The osmium, lead, and neodymium isotopic data for these rocks most closely resemble the mantle sources of certain ocean island basalts (OIB), such as some Hawaiian basalts. Hence, these data are consistent with derivation of primary melts from a mantle source similar to that of some types of hotspot activity. The long-term Re/Os enrichment of this and similar mantle sources, relative to chondritic upper mantle, may reflect 1. (1) incorporation of recycled oceanic crust into the source more than 1 Ga ago, 2. (2) derivation from a mantle plume that originated at the outer core-lower mantle interface, or 3. (3) persistence of primordial stratification of rhenium and osmium in the mantle. ?? 1994.

Oxygen isotope exchange between refractory inclusion in Allende and solar nebula gas.

PubMed

Yurimoto, H; Ito, M; Nagasawa, H

1998-12-04

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope composition (approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

PubMed

Yurimoto; Ito; Nagasawa

1998-12-04

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

Device and method for separating oxygen isotopes

DOEpatents

Rockwood, Stephen D.; Sander, Robert K.

1984-01-01

A device and method for separating oxygen isotopes with an ArF laser which produces coherent radiation at approximately 193 nm. The output of the ArF laser is filtered in natural air and applied to an irradiation cell where it preferentially photodissociates molecules of oxygen gas containing .sup.17 O or .sup.18 O oxygen nuclides. A scavenger such as O.sub.2, CO or ethylene is used to collect the preferentially dissociated oxygen atoms and recycled to produce isotopically enriched molecular oxygen gas. Other embodiments utilize an ArF laser which is narrowly tuned with a prism or diffraction grating to preferentially photodissociate desired isotopes. Similarly, desired mixtures of isotopic gas can be used as a filter to photodissociate enriched preselected isotopes of oxygen.

δ 18O(PO 43-) and δ 18O(CO 32-) from belemnite guards from Eastern Europe: implications for palaeoceanographic reconstructions and for the preservation of pristine isotopic values

NASA Astrophysics Data System (ADS)

Longinelli, Antonio; Wierzbowski, Hubert; Di Matteo, Antonella

2003-04-01

The oxygen isotopic composition of coexisting carbonate and phosphate from belemnite rostra was measured according to well established techniques in 42 samples of Early and Middle Jurassic age and in five samples of oyster shells. Most of the samples come from various locations in the Western Carpathians of Slovakia and Ukraine, and from central Poland. Three samples come from the Isle of Skye. The phosphate content of belemnite rostra, though variable, is systematically very low: consistently lower than about 0.3%. However, this phosphate concentration is close to that found in shells of modern marine organisms including pelecypods, gastropods and Sepia cuttlebones which, in some way, could be considered the modern belemnite counterpart. The measured oxygen isotopic composition of carbonate is within the normal range of values obtained from these fossils ranging from about -1.3 to about +0.6‰ (PDB-1) with the exception of three samples; the δ 13C values range from about -0.8 to about +2.8‰ (PDB-1). With the single exception of one sample from the Isle of Skye, the oxygen isotopic composition of phosphate from belemnite rostra ranges from +19.8 to +24.9‰ (V-SMOW), 22 of the samples measured showing δ 18O values equal to or heavier than +23.0‰. In contrast, the oyster values are considerably lighter, in the case of both carbonate and phosphate. 18O-enriched values can hardly be related to diagenetic processes that normally cause an oxygen isotope shift towards light values. If deposition temperatures are calculated from the heavily enriched values by means of the equation of Longinelli and Nuti [Earth Planet. Sci. Lett. 19 (1973) 373-376] and assuming the δ 18O of Jurassic ocean water to be equal to -1‰ taking into account the lack of ice caps during the Jurassic, the obtained temperatures range from about 8°C to about zero. These temperatures are obviously unreliable when Mesozoic palaeoceanographic conditions and palaeoclimate are taken into account. Two different hypotheses are suggested to explain these results, other hypotheses being rejected as unreliable. (1) Phosphate derived from the decaying organic matter of belemnites might have been introduced into belemnite rostra by early diagenetic fluids. If the phosphate of belemnite organic matter was isotopically heavy as happens nowadays in the flesh of molluscs, the inflow of this phosphate into the rostra could be responsible for the very positive δ 18O values shown by many belemnite rostra (this hypothesis is suggested by H.W.); (2) previous oxygen isotope measurements on Upper Cretaceous belemnites yielded δ 18O values very close to the most positive values obtained from Lower Tertiary pelecypods and fish teeth which are known to precipitate their phosphate under isotopic equilibrium conditions with seawater. These data suggest the possibility that the phosphate in belemnite rostra is primary phosphate so that the very positive data reported here can be considered the result of good preservation of the pristine isotopic composition of primary phosphate. Consequently, the only way to explain the very positive δ 18O values is to consider the oxygen isotopic composition of Jurassic ocean water to be more positive than nowadays by at least 3‰. This hypothesis is suggested by A.L. and A.D.M.

Mid-IR enhanced laser ablation molecular isotopic spectrometry

NASA Astrophysics Data System (ADS)

Brown, Staci; Ford, Alan; Akpovo, Codjo A.; Johnson, Lewis

2016-08-01

A double-pulsed laser-induced breakdown spectroscopy (DP-LIBS) technique utilizing wavelengths in the mid-infrared (MIR) for the second pulse, referred to as double-pulse LAMIS (DP-LAMIS), was examined for its effect on detection limits compared to single-pulse laser ablation molecular isotopic spectrometry (LAMIS). A MIR carbon dioxide (CO2) laser pulse at 10.6 μm was employed to enhance spectral emissions from nanosecond-laser-induced plasma via mid-IR reheating and in turn, improve the determination of the relative abundance of isotopes in a sample. This technique was demonstrated on a collection of 10BO and 11BO molecular spectra created from enriched boric acid (H3BO3) isotopologues in varying concentrations. Effects on the overall ability of both LAMIS and DP-LAMIS to detect the relative abundance of boron isotopes in a starting sample were considered. Least-squares fitting to theoretical models was used to deduce plasma parameters and understand reproducibility of results. Furthermore, some optimization for conditions of the enhanced emission was achieved, along with a comparison of the overall emission intensity, plasma density, and plasma temperature generated by the two techniques.

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

NASA Astrophysics Data System (ADS)

Anufriev, G. S.

2012-11-01

The fluxes of hydrogen and helium isotopes in the solar wind are reconstructed over a long time scale since the present time up to 600 million years back. Abundances of helium isotopes, obtained in the helium isotopic analysis made for 8 lunar soil samples, were used as initial data in the reconstruction procedure. Samples were taken off from various levels of the 1.6-m core of lunar soil delivered by the automatic Luna-24 station in 1976. The data on modern hydrogen and helium fluxes were used as well. The developed reconstruction procedure allowed one to select various solar wind components in a "gross" composition. Proton flux variations over the interval of 600 million years do not exceed a value of 40 %. Helium flux variations reach a value of 1.5-2 relative to the average value. Most likely, this circumstance is caused by considerable variations of a number of coronal mass ejections ( CME) enriched by helium. The arguments in favor of solar activity polycyclicity on a long time scale are discussed.

Detection of Human Sewage in Urban Stormwater Using DNA Based Methods and Stable Isotope Analysis

NASA Astrophysics Data System (ADS)

McLellan, S. L.; Malet, N.; Sauer, E.; Mueller-Spitz, S.; Borchardt, M.

2008-12-01

Urban stormwater is a major source of fecal indicator bacteria in the Milwaukee River Basin, a major watershed draining to Lake Michigan. Much of the watershed is in highly urbanized areas and Escherichia coli (E. coli) levels have been found to be 20,000 CFU per 100 ml in the estuary leading to Lake Michigan. Aging infrastructure and illicit cross connections may allow sewage to infiltrate the stormwater system and could contribute both fecal indicator bacteria and human pathogens to these waters. We conducted extensive sampling of stormwater outfalls in the lower reaches of three major tributaries. Three outfalls along the heavily urbanized Kinnickinnick (KK) were found to have geometric mean E. coli and enterococci levels of 16,200 and 28,700 CFU/100 ml, respectively. Four outfalls along the Menomonee River, draining both suburban and urban areas, had geometric mean E. coli and enterococci levels of 14,700 and 12,800 CFU/100 ml, respectively. These seven outfalls had more than 60% of the samples positive for human specific Bacteroides genetic marker (n=46), suggesting the presence of human sources. In addition, two outfalls on Lincoln Creek, a smaller tributary of the Milwaukee River, had geometric mean E. coli and enterococci levels of 16,700 and 14,900 CFU per 100 ml, respectively. The human specific Bacteroides marker was positive in nearly 90% of the samples (n=24). Subsequent virus testing at one of these outfalls confirmed human pathogens were present with adenovirus detected at 1.3 x 10E3 genomic equivalents (ge)/L, enterovirus at 1.9 x 10E4 ge/L and G1 norovirus at 1.5 x 10E3 ge/L; these values are similar to concentrations found in sewage. Stable isotope studies were conducted in the three tributaries to investigate the relationship between delta C and delta N isotopic composition and microbiological quality of this urban freshwater system. This work is based on the premise that the organic matter of the stormwater will have a stable isotopic signature related to the mixed organic matter sources in polluted stormwater runoff, and that this signal will distinct from untreated sanitary sewage. Stable isotope signatures of stormwater and untreated sewage were determined and compared with the rivers. Isotopic values of stormwater was delta 15N = 1.1 ± 2 %; delta 13C = -25.5 ± 3 % and sewage was delta 15N = -1.9 ± 0.2 %; delta 13C = -23.6 ± 0.3. Suspended particular organic matter (SPOM) of Milwaukee River showed depleted delta 13C (-28.6 ± 1.6 %) and enriched delta 15N (7.7 ± 1.9 %) values. SPOM of the KK River exhibited the most depleted delta 15N (0.2 ± 1.6 %) and enriched delta 13C (-24.8 ± 1.8 %) isotopic values. Menomonee River SPOM showed intermediate isotopic values. The delta 13C values of each river and the estuary enriched significantly throughout the summer storm periods. The isotope signals in the KK and Menomonee were indicative of stormwater runoff and sewage contamination. These results suggest that unrecognized sewage inputs are chronically present and may be delivered through urban stormwater systems. DNA based methods combined with isotope analysis may provide a useful tool for urban watershed assessments and to identify sewage inputs. Delineating the relative contribution of stormwater and sewage to overall degraded water quality might give the first indication of the impact of these sources on the Michigan Lake waters.

The 1998-2001 submarine lava balloon eruption at the Serreta ridge (Azores archipelago): Constraints from volcanic facies architecture, isotope geochemistry and magnetic data

NASA Astrophysics Data System (ADS)

Madureira, Pedro; Rosa, Carlos; Marques, Ana Filipa; Silva, Pedro; Moreira, Manuel; Hamelin, Cédric; Relvas, Jorge; Lourenço, Nuno; Conceição, Patrícia; Pinto de Abreu, Manuel; Barriga, Fernando J. A. S.

2017-01-01

The most recent submarine eruption observed offshore the Azores archipelago occurred between 1998 and 2001 along the submarine Serreta ridge (SSR), 4-5 nautical miles WNW of Terceira Island. This submarine eruption delivered abundant basaltic lava balloons floating at the sea surface and significantly changed the bathymetry around the eruption area. Our work combines bathymetry, volcanic facies cartography, petrography, rock magnetism and geochemistry in order to (1) track the possible vent source at seabed, (2) better constrain the Azores magma source(s) sampled through the Serreta submarine volcanic event, and (3) interpret the data within the small-scale mantle source heterogeneity framework that has been demonstrated for the Azores archipelago. Lava balloons sampled at sea surface display a radiogenic signature, which is also correlated with relatively primitive (low) 4He/3He isotopic ratios. Conversely, SSR lavas are characterized by significantly lower radiogenic 87Sr/86Sr, 206Pb/204Pb and 208Pb/204Pb ratios than the lava balloons and the onshore lavas from the Terceira Island. SSR lavas are primitive, but incompatible trace-enriched. Apparent decoupling between the enriched incompatible trace element abundances and depleted radiogenic isotope ratios is best explained by binary mixing of a depleted MORB source and a HIMU­type component into magma batches that evolved by similar shallower processes in their travel to the surface. The collected data suggest that the freshest samples collected in the SSR may correspond to volcanic products of an unnoticed and more recent eruption than the 1998-2001 episode.

Isotope dilution inductively coupled plasma quadrupole mass spectrometry in connection with a chromatographic separation for ultra trace determinations of platinum group elements (Pt, Pd, Ru, Ir) in environmental samples.

PubMed

Müller, M; Heumann, K G

2000-09-01

An isotope dilution inductively coupled plasma quadrupole mass spectrometric (ID-ICP-QMS) method was developed for the simultaneous determination of the platinum group elements Pt, Pd, Ru, and Ir in environmental samples. Spike solutions, enriched with the isotopes 194Pt, 108Pd, 99Ru, and 191Ir, were used for the isotope dilution step. Interfering elements were eliminated by chromatographic separation using an anion-exchange resin. Samples were dissolved with aqua regia in a high pressure asher. Additional dissolution of possible silicate portions by hydrofluoric acid was usually not necessary. Detection limits of 0.15 ng x g(-1), 0.075 ng x g(-1), and 0.015 ng x g(-1) were achieved for Pt, Pd, Ru, and Ir, respectively, using sample weights of only 0.2 g. The reliability of the ID-ICP-QMS method was demonstrated by analyzing a Canadian geological reference material and by participating in an interlaboratory study for the determination of platinum and palladium in a homogenized road dust sample. Surface soil, sampled at different distances from a highway, showed concentrations in the range of 0.1-87 ng x g(-1). An exponential decrease of the platinum and palladium concentration with increasing distance and a small anthropogenic contribution to the natural background concentration of ruthenium and iridium was found in these samples.

Heterogeneity and O-16-Enrichments in Oxygen Isotope Ratios of Olivine from Chondrules in the Mokoia CV3 Chondrite

NASA Technical Reports Server (NTRS)

Jones, R. H.; Leshin, L. A.; Guan, Y.

2002-01-01

Two chondrules from Mokoia contain olivine in which oxygen isotopes are extremely heterogeneous, with some grains highly enriched in O-16. These data provide an important link between CAIs and chondrules. Additional information is contained in the original extended abstract.

Compound-specific isotope analysis as a tool to characterize biodegradation of ethylbenzene.

PubMed

Dorer, Conrad; Vogt, Carsten; Kleinsteuber, Sabine; Stams, Alfons J M; Richnow, Hans-Hermann

2014-08-19

This study applied one- and two-dimensional compound-specific isotope analysis (CSIA) for the elements carbon and hydrogen to assess different means of microbial ethylbenzene activation. Cultures incubated under nitrate-reducing conditions showed significant carbon and highly pronounced hydrogen isotope fractionation of comparable magnitudes, leading to nearly identical slopes in dual-isotope plots. The results imply that Georgfuchsia toluolica G5G6 and an enrichment culture dominated by an Azoarcus species activate ethylbenzene by anaerobic hydroxylation catalyzed by ethylbenzene dehydrogenase, similar to Aromatoleum aromaticum EbN1. The isotope enrichment pattern in dual plots from two strictly anaerobic enrichment cultures differed considerably from those for benzylic hydroxylation, indicating an alternative anaerobic activation step, most likely fumarate addition. Large hydrogen fractionation was quantified using a recently developed Rayleigh-based approach considering hydrogen atoms at reactive sites. Data from nine investigated microbial cultures clearly suggest that two-dimensional CSIA in combination with the magnitude of hydrogen isotope fractionation is a valuable tool to distinguish ethylbenzene degradation and may be of practical use for monitoring natural or technological remediation processes at field sites.

Determination of phenylalanine isotope ratio enrichment by liquid chromatography/time- of-flight mass spectrometry.

PubMed

Wu, Zhanpin; Zhang, Xiao-Jun; Cody, Robert B; Wolfe, Robert R

2004-01-01

The application of time-of-flight mass spectrometry to isotope ratio measurements has been limited by the relatively low dynamic range of the time-to-digital converter detectors available on commercial LC/ToF-MS systems. Here we report the measurement of phenylalanine isotope ratio enrichment by using a new LC/ToF-MS system with wide dynamic range. Underivatized phenylalanine was injected onto a C18 column directly with 0.1% formic acid/acetonitrile as the mobile phase. The optimal instrument parameters for the time-of-flight mass spectrometer were determined by tuning the instrument with a phenylalanine standard. The accuracy of the isotope enrichment measurement was determined by the injection of standard solutions with known isotope ratios ranging from 0.02% to 9.2%. A plot of the results against the theoretical values gave a linear curve with R2 of 0.9999. The coefficient of variation for the isotope ratio measurement was below 2%. The method is simple, rapid, and accurate and presents an attractive alternative to traditional GC/MS applications.

Compound-Specific Isotopic Analysis of Meteoritic Amino Acids as a Tool for Evaluating Potential Formation Pathways

NASA Technical Reports Server (NTRS)

Elsila, Jamie E.; Burton, Aaron S.; Callahan, Michael C.; Charnley, Steven B.; Glavin, Daniel P.; Dworkin, Jason P.

2012-01-01

Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.

Polychlorinated biphenyls in aquatic invertebrates and fish and observations about nitrogen and carbon isotope composition in relation to trophic structure and bioaccumulation patterns, Lake Worth and Meandering Road Creek, Fort Worth, Texas, 2007-08

USGS Publications Warehouse

Moring, J. Bruce

2010-01-01

During 2007-08 the U.S. Geological Survey, in cooperation with the U.S. Air Force, evaluated the concentration of polychlorinated biphenyls (PCBs) in aquatic invertebrates and fish from one site in the main body of Lake Worth, two sites in a small inlet in Lake Worth (upper and lower Woods Inlet), and one site in Meandering Road Creek in Fort Worth, Texas. The four sites sampled during 2007-08 were located at or near sites where surficial bed-sediment samples had been collected and analyzed for PCBs during previous U.S. Geological Survey studies so that PCB concentrations in aquatic invertebrates and fish and PCB concentrations in surficial bed-sediment samples could be compared. Stable nitrogen and carbon isotopes were used to help assess differences in the amount of these isotopes by species and sampling location. The sum of 15 PCB-congener concentrations was highest for aquatic invertebrates and fish from the upper Woods Inlet site and lowest for the same aquatic invertebrates and fish from Lake Worth site, where PCBs historically had not been detected in lake bed sediment. An increase in the ratio of the heavier nitrogen-15 (15N) isotope to the lighter nitrogen-14 (14N) isotope, referred to as enrichment of 15N, was highest in largemouth bass (representing the highest trophic level sampled) at all sites and lowest for true midge larvae inhabiting surficial bed sediment in the lake (representing the lowest trophic level sampled). Enrichment of 15N was less variable in largemouth bass and other fish from the highest trophic level compared with shorter lived, primary consumer invertebrates from lower trophic levels, such as true midge larvae, mayfly nymphs, and zooplankton. The delta carbon-13 (delta13C) values measured in true midge larvae collected at the Lake Worth and upper and lower Woods Inlet sites were more negative compared with the delta13C values measured for all other taxa, indicating true midge larvae were more depleted of carbon-13 (13C) compared with all other aquatic invertebrate and fish. The relative depletion of 13C might indicate the carbon sources consumed by true midge larvae are different from the carbon sources consumed by all other taxon that were sampled. Ratios of stable nitrogen isotopes nitrogen-15 to nitrogen-14 (delta15N) were similar between taxa from the Lake Worth site and Woods Inlet sites. The sum of 15 PCB-congener concentrations, however, was an order of magnitude higher in largemouth bass from the upper Woods Inlet site, indicating that PCB-congener concentrations in lake bed sediment likely controls biomagnification within the lake because of the similarities in trophic structure of the resident aquatic community. The biota at the Lake Worth reference site, where PCBs were not detected in the surficial sediment during previous studies, were less contaminated than the biota at sites where PCBs had been detected in the surficial sediment. The highest trophic-level consumers (as evidenced by the most 15N-enriched delta15N values) showed the maximum bioaccumulation.

Isotopic homogeneity of iron in the early solar nebula.

PubMed

Zhu, X K; Guo, Y; O'Nions, R K; Young, E D; Ash, R D

2001-07-19

The chemical and isotopic homogeneity of the early solar nebula, and the processes producing fractionation during its evolution, are central issues of cosmochemistry. Studies of the relative abundance variations of three or more isotopes of an element can in principle determine if the initial reservoir of material was a homogeneous mixture or if it contained several distinct sources of precursor material. For example, widespread anomalies observed in the oxygen isotopes of meteorites have been interpreted as resulting from the mixing of a solid phase that was enriched in 16O with a gas phase in which 16O was depleted, or as an isotopic 'memory' of Galactic evolution. In either case, these anomalies are regarded as strong evidence that the early solar nebula was not initially homogeneous. Here we present measurements of the relative abundances of three iron isotopes in meteoritic and terrestrial samples. We show that significant variations of iron isotopes exist in both terrestrial and extraterrestrial materials. But when plotted in a three-isotope diagram, all of the data for these Solar System materials fall on a single mass-fractionation line, showing that homogenization of iron isotopes occurred in the solar nebula before both planetesimal accretion and chondrule formation.

On-line hydrogen-isotope measurements of organic samples using elemental chromium: An extension for high temperature elemental-analyzer techniques

USGS Publications Warehouse

Gehre, Matthias; Renpenning, Julian; Gilevska, Tetyana; Qi, Haiping; Coplen, Tyler B.; Meijer, Harro A.J.; Brand, Willi A.; Schimmelmann, Arndt

2015-01-01

The high temperature conversion (HTC) technique using an elemental analyzer with a glassy carbon tube and filling (temperature conversion/elemental analysis, TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ2H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1‰) from the true value for some materials. We show that a single-oven, chromium-filled elemental analyzer coupled to an IRMS substantially improves the measurement quality and reliability for hydrogen isotopic compositions of organic substances (Cr-EA method). Hot chromium maximizes the yield of molecular hydrogen in a helium carrier gas by irreversibly and quantitatively scavenging all reactive elements except hydrogen. In contrast, under TC/EA conditions, heteroelements like nitrogen or chlorine (and other halogens) can form hydrogen cyanide (HCN) or hydrogen chloride (HCl) and this can cause isotopic fractionation. The Cr-EA technique thus expands the analytical possibilities for on-line hydrogen-isotope measurements of organic samples significantly. This method yielded reproducibility values (1-sigma) for δ2H measurements on water and caffeine samples of better than 1.0 and 0.5 mUr, respectively. To overcome handling problems with water as the principal calibration anchor for hydrogen isotopic measurements, we have employed an effective and simple strategy using reference waters or other liquids sealed in silver-tube segments. These crimped silver tubes can be employed in both the Cr-EA and TC/EA techniques. They simplify considerably the normalization of hydrogen-isotope measurement data to the VSMOW-SLAP (Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation) scale, and their use improves accuracy of the data by eliminating evaporative loss and associated isotopic fractionation while handling water as a bulk sample. The calibration of organic samples, commonly having high δ2H values, will benefit from the availability of suitably 2H-enriched reference waters, extending the VSMOW-SLAP scale above zero.

Rubidium Isotope Composition of the Earth and the Moon: Evidence for the Origin of Volatile Loss During Planetary Accretion

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.

2016-12-01

The Earth-Moon system has a variety of chemical and isotopic characteristics that provide clues to understanding the mechanism of lunar formation. One important observation is the depletion in moderately volatile elements in the Moon compared to the Earth. This volatile element depletion may be a signature of volatile loss during the Moon-forming Giant Impact. Stable isotopes are powerful tracers of such a process, since volatile loss via evaporation enriches the residue in heavy isotopes. However, early studies searching for the fingerprint of volatile loss failed to find any resolvable variations [1]. Recent work has now revealed heavy isotope enrichments in the Moon relative to the Earth for the moderately volatile elements Zn [2,3] and K [4]. The purely lithophile nature of Rb (in contrast to the chalcophile/lithophile nature of Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to study the origin of lunar volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. The Rb isotope compositions of terrestrial rocks define a narrow range, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). There is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. In particular, eucrites are significantly enriched in 87Rb (up to several per mil) relative to chondrites. Similarly, lunar basalts are enriched in 87Rb compared to terrestrial basalts, by 200 ppm for 87Rb/85Rb. These data are the first measurements of a resolvable difference in Rb isotope composition between the Earth and the Moon. The variations in Rb isotope composition between the Earth and the Moon are consistent with Rb isotope fractionation due to evaporation. References: [1] Humayun & Clayton GCA 1995. [2] Paniello et al. Nature 2012. [3] Kato et al. Nat. Comm. 2015. [4] Wang and Jacobsen Nature in press.

Enrichment of 18O in the mantle sources of the Antarctic portion of the Karoo large igneous province

NASA Astrophysics Data System (ADS)

Heinonen, Jussi S.; Luttinen, Arto V.; Whitehouse, Martin J.

2018-03-01

Karoo continental flood basalt (CFB) province is known for its highly variable trace element and isotopic composition, often attributed to the involvement of continental lithospheric sources. Here, we report oxygen isotopic compositions measured with secondary ion mass spectrometry for hand-picked olivine phenocrysts from 190 to 180 Ma CFBs and intrusive rocks from Vestfjella, western Dronning Maud Land, that form an Antarctic extension of the Karoo province. The Vestfjella lavas exhibit heterogeneous trace element and radiogenic isotope compositions (e.g., ɛ Nd from - 16 to + 2 at 180 Ma) and the involvement of continental lithospheric mantle and/or crust in their petrogenesis has previously been suggested. Importantly, our sample set also includes rare primitive dikes that have been derived from depleted asthenospheric mantle sources ( ɛ Nd up to + 8 at 180 Ma). The majority of the oxygen isotopic compositions of the olivines from these dike rocks (δ18O = 4.4-5.2‰; Fo = 78-92 mol%) are also compatible with such sources. The olivine phenocrysts in the lavas, however, are characterized by notably higher δ18O (6.2-7.5‰; Fo = 70-88 mol%); and one of the dike samples gives intermediate compositions (5.2‒6.1‰, Fo = 83-87 mol%) between the other dikes and the CFBs. The oxygen isotopic compositions do not correlate with radiogenic isotope compositions susceptible to crustal assimilation (Sr, Nd, and Pb) or with geochemical indicators of pyroxene-rich mantle sources. Instead, δ18O correlates positively with enrichments in large-ion lithophile elements (especially K) and 187Os. We suggest that the oxygen isotopic compositions of the Vestfjella CFB olivines primarily record large-scale subduction-related metasomatism of the sub-Gondwanan mantle (base of the lithosphere or deeper) prior to Karoo magmatism. The overall influence of such sources to Karoo magmatism is not known, but, in addition to continental lithosphere, they may be responsible for some of the geochemical heterogeneity observed in the CFBs.

Moss stable isotopes (carbon-13, oxygen-18) and testate amoebae reflect environmental inputs and microclimate along a latitudinal gradient on the Antarctic Peninsula.

PubMed

Royles, Jessica; Amesbury, Matthew J; Roland, Thomas P; Jones, Glyn D; Convey, Peter; Griffiths, Howard; Hodgson, Dominic A; Charman, Dan J

2016-07-01

The stable isotope compositions of moss tissue water (δ(2)H and δ(18)O) and cellulose (δ(13)C and δ(18)O), and testate amoebae populations were sampled from 61 contemporary surface samples along a 600-km latitudinal gradient of the Antarctic Peninsula (AP) to provide a spatial record of environmental change. The isotopic composition of moss tissue water represented an annually integrated precipitation signal with the expected isotopic depletion with increasing latitude. There was a weak, but significant, relationship between cellulose δ(18)O and latitude, with predicted source water inputs isotopically enriched compared to measured precipitation. Cellulose δ(13)C values were dependent on moss species and water content, and may reflect site exposure to strong winds. Testate amoebae assemblages were characterised by low concentrations and taxonomic diversity, with Corythion dubium and Microcorycia radiata types the most cosmopolitan taxa. The similarity between the intra- and inter-site ranges measured in all proxies suggests that microclimate and micro-topographical conditions around the moss surface were important determinants of proxy values. Isotope and testate amoebae analyses have proven value as palaeoclimatic, temporal proxies of climate change, whereas this study demonstrates that variations in isotopic and amoeboid proxies between microsites can be beyond the bounds of the current spatial variability in AP climate.

Geochemical gradients in soil O-horizon samples from southern Norway: Natural or anthropogenic?

USGS Publications Warehouse

Reimann, C.; Englmaier, P.; Flem, B.; Gough, L.; Lamothe, P.; Nordgulen, O.; Smith, D.

2009-01-01

Forty soil O- and C-horizon samples were collected along a south-to-north transect extending inland for approximately 200 km from the southern tip of Norway. The elements As, Au, Bi, Cd, Cu, Ga, Ge, Hf, Hg, In, Mg, Mn, Mo, Na, Ni, Pb, Sb, Se, V, W, Zn and Zr all show a distinct decrease in concentration in soil O-horizons with increasing distance from the coast. The elements showing the strongest coastal enrichment, some by more than an order of magnitude compared to inland samples, are Au, Bi, As, Pb, Sb and Sn. Furthermore, the elements Cd (median O-/median C-horizon = 31), C, Sb, Ag, K, S, Ge (10), Hg, Pb, As, Bi, Sr (5), Se, Au, Ba, Na, Zn, P, Cu and Sn (2) are all strongly enriched in the O-horizon when compared to the underlying C-horizon. Lead isotope ratios, however, do not show any gradient with distance from the coast (declining Pb concentration). Along a 50 km topographically steep east-west transect in the centre of the survey area, far from the coast but crossing several vegetation zones, similar element enrichment patterns and concentration gradients can be observed in the O-horizon. Lead isotope ratios in the O-horizon correlate along both transects with pH and the C/N-ratio, both proxies for the quality of the organic material. Natural conditions in southern Norway, related to climate and vegetation, rather than long range atmospheric transport of air pollutants (LRT), cause the observed features. ?? 2008 Elsevier Ltd.

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, R.J.; Cecchi, J.L.

1991-08-20

Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen. 4 figures.

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1991-01-01

Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen.

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1990-01-01

Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen.

Transgenerational marking of freshwater fishes with enriched stable isotopes: a tool for fisheries management and research.

PubMed

Munro, A R; Gillanders, B M; Thurstan, S; Crook, D A; Sanger, A C

2009-08-01

A promising new method of marking larval freshwater fishes with enriched stable isotopes by means of injecting the maternal parent with the marking agent was investigated. The (138)Ba:(137)Ba ratios in the otoliths of larval golden perch Macquaria ambigua were compared to determine the effect of injecting female broodstock with different dosages of enriched (137)Ba at various times before spawning. There was 100% mark success in the progeny of fish injected with 20 microg g(-1) of enriched (137)Ba 24 h before inducing spawning with hormones and 40 microg g(-1) administered at the same time as inducement of spawning. Injection of 40 microg g(-1) enriched (137)Ba 21 days before spawning resulted in only 81% mark success and suggests rapid elimination of barium in M. ambigua. Injection with enriched (137)Ba did not significantly affect the fertilization rate, number of fertilized eggs or hatching rate compared with long-term hatchery records. These results suggest that transgenerational marking is an effective and affordable means of mass-marking larval fishes. Thousands of larval fishes can be permanently marked with a unique artificial isotopic mark via a single injection into the maternal parent, thus avoiding the handling of individual fishes or having to deal with chemical baths. Because no single mark or tagging method is suitable for all situations, transgenerational marking with enriched stable isotopes provides another method for researchers and managers to discriminate both hatchery-reared and wild fishes.

A status of progress for the Laser Isotope Separation (LIS) process

NASA Technical Reports Server (NTRS)

Delionback, L. M.

1976-01-01

An overview of the Laser Isotope Separation (LIS) methodology is given together with illustrations showing a simplified version of the LIS technique, an example of the two-photon photoionization category, and a diagram depicting how the energy levels of various isotope influence the LIS process. Applications were proposed for the LIS system which, in addition to enriching uranium, could in themselves develop into programs of tremendous scope and breadth. These include the treatment of radioactive wastes from light-water nuclear reactors, enriching the deuterium isotope to make heavy-water, and enriching the light isotopes of such elements as titanium for aerospace weight-reducing programs. Economic comparisons of the LIS methodology with the current method of gaseous diffusion indicate an overwhelming advantage; the laser process promises to be 1000 times more efficient. The technique could also be utilized in chemical reactions with the tuned laser serving as a universal catalyst to determine the speed and direction of a chemical reaction.

Physics overview of AVLIS

NASA Astrophysics Data System (ADS)

Solarz, R. W.

1985-02-01

Atomic vapor laster isotope separation (AVLIS) represents the largest-scale potential application of tunable lasers that has received serious attention. The underlying physical principles were identified and optimized, the major technology components were developed, and the integrated enrichment performance of the process was tested. The central physical processes are outlined, progress to date on the technology elements is reviewed, and scaling laws are fomulated. Two primary applications are the production of light-water reactor fuel and the conversion of fuel-grade plutonium to weapons-grade material. A variety of applications exist that all potentially use a common base of AVLIS technology. These include missions such as the enrichment of mercury isotopes to improve fluorescent lamp efficiency, the enrichment of iodine isotopes for medical isotope use, and the cleanup of strontium from defense waste for recovering strontium isotopes for radiothermal mechanical generators. The ability to radidly assess the economic and technical feasibility of each mission is derived from the general applicability of AVLIS physics and AVLIS technology.

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.

Trivalent chromium solubility and its influence on quantification of hexavalent chromium in ambient particulate matter using EPA method 6800.

PubMed

Huang, Lihui; Yu, Chang Ho; Hopke, Philip K; Shin, Jin Young; Fan, Zhihua

2014-12-01

Measurement of carcinogenic Cr(VI) in ambient PM is challenging due to potential errors associated with conversion between Cr (VI) (a carcinogen) and Cr(III) (an essential nutrient). Cr(III) conversion is a particular concern due to its > 80% atomic abundance in total Cr. US. Environmental Protection Agency (EPA) method 6800 that uses water-soluble isotope spikes can be used to correct the interconversion. However, whether the enriched Cr(III) isotope spikes can adequately mimic the Cr(III) species originally in ambient PM is unknown. This study examined the water solubility of Cr(III) in ambient PM and discussed its influence on Cr(VI) measurement. Ambient PM10 samples were collected on Teflon filters at four sites in New Jersey that may have different Cr emission sources. The samples were ultrasonically extracted with 5 mL DI-H2O (pH 5.7) at room temperature for 40 min, and then analyzed by ion chromatography-inductively coupled plasma mass spectrometry (IC-ICPMS). Cr(III) was below detection limit (0.06 ng/m3) for all samples, suggesting water-soluble Cr(III) species, such as CrCl3, Cr(NO3)3, and amorphous Cr(OH)3, in the ambient PM were negligible. Therefore, the enriched 50Cr(III) isotope spike (in the form of Cr(NO3)3) could not mimic the original ambient Cr(III). Only the conversion of 53Cr(VI) (in the form of K2CrO4) was taken into account when correcting the interconversion. We then used NaHCO3-pretreated MCE filters (prespiked with enriched isotope species) to measure Cr(VI) in the ambient PM10. The samples were ultrasonically extracted at 60 C pH 9 solutions for 40 min followed by IC-ICPMS analysis. Due to the correction of Cr(VI) reduction, the Cr(VI) concentrations determined by EPA method 6800, 0.26 ± 0.16 (summer) and 0.16 ± 0.11(winter) ng/m3 (n = 64), were significantly greater than those by the external standard curve, 0.21 ± 0.17 (summer) and 0.10 ± 0.07 (winter) ng/m3 (n = 56) (p < 0.01, Student's t-test). Our study revealed that appropriate application of EPA method 6800 is important because it only applies to soluble fraction of Cr species in ambient PM. Implications: Accurate measurement of carcinogenic Cr(VI) in ambient PM is challenging due to conversion between Cr(VI) (a human carcinogen) and Cr(III) (a human essential nutrient). The conversion of CR(III) is of particular concern due to its dominant presence in total Cr (>80%). This study examined the water solubility of Cr(III) in ambient PM that was collected at four locations in New Jersey. Then we discussed the influence of Cr(III) solubility on the application of EPA method 6800, which utilizes enriched isotope spikes to correct the interconversion. Our results suggested that appropriate application of EPA method 6800 is important because it only applies to soluble fraction of Cr species.

Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, L-Valines, Polyethylenes, and Oils.

PubMed

Schimmelmann, Arndt; Qi, Haiping; Coplen, Tyler B; Brand, Willi A; Fong, Jon; Meier-Augenstein, Wolfram; Kemp, Helen F; Toman, Blaza; Ackermann, Annika; Assonov, Sergey; Aerts-Bijma, Anita T; Brejcha, Ramona; Chikaraishi, Yoshito; Darwish, Tamim; Elsner, Martin; Gehre, Matthias; Geilmann, Heike; Gröning, Manfred; Hélie, Jean-François; Herrero-Martín, Sara; Meijer, Harro A J; Sauer, Peter E; Sessions, Alex L; Werner, Roland A

2016-04-19

An international project developed, quality-tested, and determined isotope-δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope-δ scales. The RMs span a range of δ(2)H(VSMOW-SLAP) values from -210.8 to +397.0 mUr or ‰, for δ(13)C(VPDB-LSVEC) from -40.81 to +0.49 mUr and for δ(15)N(Air) from -5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C16 n-alkanes, n-C20-fatty acid methyl esters (FAMEs), glycines, and l-valines, together with polyethylene powder and string, one n-C17-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a (2)H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ(2)H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain (13)C and carbon-bound organic (2)H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies.

S- and Sr-isotopic compositions in barite-silica chimney from the Franklin Seamount, Woodlark Basin, Papua New Guinea: constraints on genesis and temporal variability of hydrothermal fluid

NASA Astrophysics Data System (ADS)

Ray, Durbar; Banerjee, Ranadip; Balakrishnan, S.; Paropkari, Anil L.; Mukhopadhyay, Subir

2017-07-01

Isotopic ratios of strontium and sulfur in six layers across a horizontal section of a hydrothermal barite-silica chimney from Franklin Seamount of western Woodlark Basin have been investigated. Sr-isotopic ratios in barite samples (87Sr/86Sr = 0.70478-0.70493) are less radiogenic than seawater (87Sr/86Sr = 0.70917) indicating that substantial leaching of sub-seafloor magma was involved in the genesis of hydrothermal fluid. The SO2 of magma likely contributed a considerable amount of lighter S-isotope in fluid and responsible for the formation of barite, which is isotopically lighter (δ34S = 19.4-20.5 ‰) than modern seawater (δ34S 21 ‰). The systematic changes in isotopic compositions across the chimney wall suggest temporal changes in the mode of mineral formation during the growth of the chimney. Enrichment of heavy S- and Sr-isotopes (δ34S = 20.58 ‰; 87Sr/86Sr = 0.70493) in the outermost periphery of the chimney indicates that, at the initial stage of chimney development, there was a significant contribution of seawater sulfate during barite mineralization. Thereafter, thickening of chimney wall occurred due to precipitation of fluid carrying more magmatic components relative to seawater. This led to a gradual enrichment of lighter isotopes (δ34S = 20.42-19.48 ‰; 87Sr/86Sr = 0.70491-0.704787) toward the inner portion of the chimney wall. In contrast, the innermost layer surrounding the fluid conduit is characterized by heavier and more radiogenic isotopes (δ34S = 20.3 ‰; 87Sr/86Sr = 0.7049). This suggests there was increasing influence of percolating seawater on the mineral paragenesis at the waning phase of the chimney development.

Labile pools of Pb in vegetable-growing soils investigated by an isotope dilution method and its influence on soil pH.

PubMed

Xie, Hong; Huang, Zhi-Yong; Cao, Ying-Lan; Cai, Chao; Zeng, Xiang-Cheng; Li, Jian

2012-08-01

Pollution of Pb in the surface of agricultural soils is of increasing concern due to its serious impact on the plant growth and the human health through the food chain. However, the mobility, activity and bioavailability of Pb rely mainly on its various chemical species in soils. In the present study, E and L values, the labile pools of isotopically exchangeable Pb, were estimated using the method of isotope dilution in three vegetable-growing soils. The experiments involved adding a stable enriched isotope ((206)Pb > 96%) to a soil suspension and to soils in which plants are subsequently grown, the labile pools of Pb were then estimated by measuring the isotopic composition of Pb in soil solutions and in the plant tissues, respectively. In addition, the correlation of E values and soil pH was investigated at the ranges of pH 4.5-7.0. The amount of labile Pb in soils was also estimated using different single chemical extractants and a modified BCR approach. The results showed that after spiking the enriched isotopes of (206)Pb (>96%) for 24 hours an equilibration of isotopic exchanges in soil suspensions was achieved, and the isotope ratios of (208)Pb/(206)Pb measured at that time was used for calculating the E(24 h) values. The labile pools of Pb by %E(24 h) values, ranging from 53.2% to 61.7% with an average 57%, were found to be significantly higher (p < 0.05) than the values estimated with L values, single chemical extractants and the Σ(BCR) values obtained with the BCR approach, respectively. A strong negative correlation (R(2) = 0.984) between E(24 h) values and soil pH was found in the tested soil sample. The results indicate that the %E(24 h) value can more rapidly and easily predict the labile pools of Pb in soils compared with L values, but it might be readily overestimated because of the artificial soil acidity derived from the spiked isotopic tracer and the excess of spiked enriched isotopes. The results also suggest that the amounts of Pb extracted with EDTA and the Σ(BCR) values extracted with the modified BCR approach are helpful to detect the labile pools of Pb in soils. In addition, the negative correlation between soil pH and the labile pools of Pb in soils may be useful for further remediation to reduce the bioavailability of Pb in contaminated soils.

Mixed fluid sources involved in diamond growth constrained by Sr-Nd-Pb-C-N isotopes and trace elements

NASA Astrophysics Data System (ADS)

Klein-BenDavid, Ofra; Pearson, D. Graham; Nowell, Geoff M.; Ottley, Chris; McNeill, John C. R.; Cartigny, Pierre

2010-01-01

Sub-micrometer inclusions in diamonds carry high-density fluids (HDF) from which the host diamonds have precipitated. The chemistry of these fluids is our best opportunity of characterizing the diamond-forming environment. The trace element patterns of diamond fluids vary within a limited range and are similar to those of carbonatitic/kimberlitic melts that originate from beneath the lithospheric mantle. A convecting mantle origin for the fluid is also implied by C isotopic compositions and by a preliminary Sr isotopic study (Akagi, T., Masuda, A., 1988. Isotopic and elemental evidence for a relationship between kimberlite and Zaire cubic diamonds. Nature 336, 665-667.). Nevertheless, the major element chemistry of HDFs is very different from that of kimberlites and carbonatites, varying widely and being characterized by extreme K enrichment (up to ˜ 39 wt.% on a water and carbonate free basis) and high volatile contents. The broad spectrum of major element compositions in diamond-forming fluids has been related to fluid-rock interaction and to immiscibility processes. Elemental signatures can be easily modified by a variety of mantle processes whereas radiogenic isotopes give a clear fingerprint of the time-integrated evolution of the fluid source region. Here we present the results of the first multi radiogenic-isotope (Sr, Nd, Pb) and trace element study on fluid-rich diamonds, implemented using a newly developed off-line laser sampling technique. The data are combined with N and C isotope analysis of the diamond matrix to better understand the possible sources of fluid involved in the formation of these diamonds. Sr isotope ratios vary significantly within single diamonds. The highly varied but unsupported Sr isotope ratios cannot be explained by immiscibility processes or fluid-mineral elemental fractionations occurring at the time of diamond growth. Our results demonstrate the clear involvement of a mixed fluid, with one component originating from ancient incompatible element-enriched parts of the lithospheric mantle while the trigger for releasing this fluid source was probably carbonatitic/kimberlitic melts derived from greater depths. We suggest that phlogopite mica was an integral part of the enriched lithospheric fluid source and that breakdown of this mica releases K and radiogenic Sr into a fluid phase. The resulting fluids operate as a major metasomatic agent in the sub-continental lithospheric mantle as reflected by the isotopic composition and trace element patterns of G10 garnets.

Recent Developments in MC-ICP-MS for Uranium Isotopic Determination from Small Samples.

NASA Astrophysics Data System (ADS)

Field, P.; Lloyd, N. S.

2016-12-01

V002: Advances in approaches and instruments for isotope studies Session ID#: 12653 Recent Developments in MC-ICP-MS for Uranium Isotopic Determination from small samples.M. Paul Field 1 & Nicholas S. Lloyd. 1 Elemental Scientific Inc., Omaha, Nebraska, USA. field@icpms.com 2 Thermo Fisher Scientific, Hanna-Kunath-Str. 11, 28199 Bremen, Germany. nicholas.lloyd@thermofisher.com Uranium isotope ratio determination for nuclear, nuclear safeguards and for environmental applications can be challenging due to, 1) the large isotopic differences between samples and 2) low abundance of 234U and 236U. For some applications the total uranium quantities can be limited, or it is desirable to run at lower concentrations for radiological protection. Recent developments in inlet systems and detector technologies allow small samples to be analyzed at higher precisions using MC-ICP-MS. Here we evaluate the combination of Elemental Scientific apex omega desolvation system and microFAST-MC dual loop-loading flow-injection system with the Thermo Scientific NEPTUNE Plus MC-ICP-MS. The inlet systems allow for the automated syringe loading and injecting handling of small sample volumes with efficient desolvation to minimize the hydride interference on 236U. The highest ICP ion sampling efficiency is realized using the Thermo Scientific Jet Interface. Thermo Scientific 1013 ohm amplifier technology allows small ion beams to be measured at higher precision, offering the highest signal/noise ratio with a linear and stable response that covers a wide dynamic range (ca. 1 kcps - 30 Mcps). For nanogram quantities of low enriched and depleted uranium standards the 235U was measured with 1013 ohm amplifier technology. The minor isotopes (234U and 236U) were measured by SEM ion counters with RPQ lens filters, which offer the lowest detection limits. For sample amounts ca. 20 ng the minor isotopes can be moved onto 1013 ohm amplifiers and the 235U onto standard 1011 ohm amplifier. To illustrate the application a set of solutions from environmental particles [1] were analyzed, the use of precise three isotope ratio plots allows for source attribution with increased confidence. [1] Lloyd et al. 2009, J. Anal. At. Spectrom., 24(6), 752-758.

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

NASA Technical Reports Server (NTRS)

Hollander, D. J.; Sinninghe Damste, J. S.; Hayes, J. M.; de Leeuw, J. W.; Huc, A. Y.

1993-01-01

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.

Cl/Br ratios and chlorine isotope evidences for groundwater salinization and its impact on groundwater arsenic, fluoride and iodine enrichment in the Datong basin, China.

PubMed

Li, Junxia; Wang, Yanxin; Xie, Xianjun

2016-02-15

In order to identify the salinization processes and its impact on arsenic, fluoride and iodine enrichment in groundwater, hydrogeochemical and environmental isotope studies have been conducted on groundwater from the Datong basin, China. The total dissolved solid (TDS) concentrations in groundwater ranged from 451 to 8250 mg/L, and 41% of all samples were identified as moderately saline groundwater with TDS of 3000-10,000 mg/L. The results of groundwater Cl concentrations, Cl/Br molar ratio and Cl isotope composition suggest that three processes including water-rock interaction, surface saline soil flushing, and evapotranspiration result in the groundwater salinization in the study area. The relatively higher Cl/Br molar ratio in groundwater from multiple screening wells indicates the contribution of halite dissolution from saline soil flushed by vertical infiltration to the groundwater salinization. However, the results of groundwater Cl/Br molar ratio model indicate that the effect of saline soil flushing practice is limited to account for the observed salinity variation in groundwater. The plots of groundwater Cl vs. Cl/Br molar ratio, and Cl vs δ(37)Cl perform the dominant effects of evapotranspiration on groundwater salinization. Inverse geochemical modeling results show that evapotranspiration may cause approximately 66% loss of shallow groundwater to account for the observed hydrochemical pattern. Due to the redox condition fluctuation induced by irrigation activities and evapotranspiration, groundwater salinization processes have negative effects on groundwater arsenic enrichment. For groundwater iodine and fluoride enrichment, evapotranspiration partly accounts for their elevation in slightly saline water. However, too strong evapotranspiration would restrict groundwater fluoride concentration due to the limitation of fluorite solubility. Copyright © 2015. Published by Elsevier B.V.

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.

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.

Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

USGS Publications Warehouse

Schimmelmann, A.; Mastalerz, Maria; Gao, L.; Sauer, P.E.; Topalov, K.

2009-01-01

Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2H/1H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., {single bond}OH, {single bond}COOH, {single bond}NH2). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ???2.5 to ???3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong ??13Ckerogen vs. ??15Nkerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back-reactions between mobile pyrolysis products from the hot zone as they encounter less hot kerogen. Vein and cell filling carbonate is most abundant in highest rank coals where carbonate ??13CVPDB and ??18OVSMOW values are consistent with thermal generation of 13C-depleted and 18O-enriched CO2 from decarboxylation and pyrolysis of organic matter. Lower background concentrations of 13C-enriched carbonate in thermally unaffected coal may be linked to 13C-enrichment in residual CO2 in the process of CO2 reduction via microbial methanogenesis. Our compilation and comparison of available organic H, C, N isotopic findings on magmatic intrusions result in re-assessments of majors factors influencing isotopic shifts in kerogen during magmatic heating. (i) Thermally induced shifts in organic ??D values of kerogen are primarily driven by the availability of water or steam. Hydrologic isolation (e.g., near Illinois dikes) results in organic D-depletion in kerogen, whereas more common hydrologic connectivity results in organic D-enrichment. (ii) Shifts in kerogen (or coal) ??13C and ??15N values are typically small and may follow sinusoidal patterns over short distances from magmatic contacts. Laterally limited sampling strategies may thus result in misleading and non-representative data. (iii) Fluid transport of chemically active, mobile carbon and nitrogen species and recombination reactions with kerogen result in isotopic changes in kerogen that are unrelated to the original, autochthonous part of kerogen. ?? 2009 Elsevier Ltd. All rights reserved.

Application of Nitrogen and Carbon Stable Isotopes (δ15N and δ13C) to Quantify Food Chain Length and Trophic Structure

PubMed Central

Perkins, Matthew J.; McDonald, Robbie A.; van Veen, F. J. Frank; Kelly, Simon D.; Rees, Gareth; Bearhop, Stuart

2014-01-01

Increasingly, stable isotope ratios of nitrogen (δ15N) and carbon (δ13C) are used to quantify trophic structure, though relatively few studies have tested accuracy of isotopic structural measures. For laboratory-raised and wild-collected plant-invertebrate food chains spanning four trophic levels we estimated nitrogen range (NR) using δ15N, and carbon range (CR) using δ13C, which are used to quantify food chain length and breadth of trophic resources respectively. Across a range of known food chain lengths we examined how NR and CR changed within and between food chains. Our isotopic estimates of structure are robust because they were calculated using resampling procedures that propagate variance in sample means through to quantified uncertainty in final estimates. To identify origins of uncertainty in estimates of NR and CR, we additionally examined variation in discrimination (which is change in δ15N or δ13C from source to consumer) between trophic levels and among food chains. δ15N discrimination showed significant enrichment, while variation in enrichment was species and system specific, ranged broadly (1.4‰ to 3.3‰), and importantly, propagated variation to subsequent estimates of NR. However, NR proved robust to such variation and distinguished food chain length well, though some overlap between longer food chains infers a need for awareness of such limitations. δ13C discrimination was inconsistent; generally no change or small significant enrichment was observed. Consequently, estimates of CR changed little with increasing food chain length, showing the potential utility of δ13C as a tracer of energy pathways. This study serves as a robust test of isotopic quantification of food chain structure, and given global estimates of aquatic food chains approximate four trophic levels while many food chains include invertebrates, our use of four trophic level plant-invertebrate food chains makes our findings relevant for a majority of ecological systems. PMID:24676331

Stable Isotope (δ13C, δ15N, δ34S) Analysis and Satellite Telemetry Depict the Complexity of Gray Wolf (Canis lupus) Diets in Southwest Alaska

NASA Astrophysics Data System (ADS)

Stanek, A.; Watts, D. E.; Cohn, B. R.; Spencer, P.; Mangipane, B.; Welker, J. M.

2010-12-01

Throughout Alaska, gray wolves (Canis lupus) are a top predator of large ungulates. While they primarily rely on ungulates such as moose (Alces alces) and caribou (Rangifer tarandus) as food, they are opportunistic and use alternative resources. The variation and supplemental protein sources in wolf diet has not been studied extensively on live animals currently using the landscape. With large seasonal influxes of Pacific salmon (Oncorhynchus sp.) into Alaska, terrestrial carnivore use of marine species is of particular interest. Using stable isotope (δ13C, δ15N, δ34S) analysis of wolf guard hair and blood, this study aims to determine the proportion of marine derived nutrients (MDN) in the diet of wolf packs within and surrounding Lake Clark National Park and Preserve and Alaska Peninsula and Becharof National Wildlife Refuges in Southwest Alaska. Satellite telemetry from the animals sampled facilitates quantification of landscape use patterns in correspondence with isotopic traits. Wolf pack territories within and surrounding the Lake Clark region appear to vary in spatial extent and in availability of MDN, such as salmon. Initial analysis shows that two packs with smaller home ranges, centrally located around areas with greater salmon availability, have enriched δ15N values compared to packs that have larger home ranges not centralized around salmon spawning waters. This pattern of isotopic enrichment is found in red blood cells, blood serum and hair, representing diets over different time scales. The enrichment in both blood and hair indicates a sustained use of MDN over the previous six to nine months. In the Lake Clark region, simple mixing model estimates suggest that up to 30% of wolf pack diets may be from marine sources. In contrast, packs with larger home ranges and less access to salmon have stable isotope values representative of a terrestrial diet.

Target-fueled nuclear reactor for medical isotope production

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

Coats, Richard L.; Parma, Edward J.

A small, low-enriched, passively safe, low-power nuclear reactor comprises a core of target and fuel pins that can be processed to produce the medical isotope .sup.99Mo and other fission product isotopes. The fuel for the reactor and the targets for the .sup.99Mo production are the same. The fuel can be low enriched uranium oxide, enriched to less than 20% .sup.235U. The reactor power level can be 1 to 2 MW. The reactor is passively safe and maintains negative reactivity coefficients. The total radionuclide inventory in the reactor core is minimized since the fuel/target pins are removed and processed after 7more » to 21 days.« less

Isotopic Discrimination During Leaf Litter Decomposition

NASA Astrophysics Data System (ADS)

Ngao, J.; Rubino, M.

2006-12-01

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

Identification of triclosan-degrading bacteria using stable isotope probing, fluorescence in situ hybridization and microautoradiography.

PubMed

Lolas, Ihab Bishara; Chen, Xijuan; Bester, Kai; Nielsen, Jeppe Lund

2012-11-01

Triclosan is considered a ubiquitous pollutant and can be detected in a wide range of environmental samples. Triclosan removal by wastewater treatment plants has been largely attributed to biodegradation processes; however, very little is known about the micro-organisms involved. In this study, DNA-based stable isotope probing (DNA-SIP) combined with microautoradiography-fluorescence in situ hybridization (MAR-FISH) was applied to identify active triclosan degraders in an enrichment culture inoculated with activated sludge. Clone library sequences of 16S rRNA genes derived from the heavy DNA fractions of enrichment culture incubated with (13)C-labelled triclosan showed a predominant enrichment of a single bacterial clade most closely related to the betaproteobacterial genus Methylobacillus. To verify that members of the genus Methylobacillus were actively utilizing triclosan, a specific probe targeting the Methylobacillus group was designed and applied to the enrichment culture incubated with (14)C-labelled triclosan for MAR-FISH. The MAR-FISH results confirmed a positive uptake of carbon from (14)C-labelled triclosan by the Methylobacillus. The high representation of Methylobacillus in the (13)C-labelled DNA clone library and its observed utilization of (14)C-labelled triclosan by MAR-FISH reveal that these micro-organisms are the primary consumers of triclosan in the enrichment culture. The results from this study show that the combination of SIP and MAR-FISH can shed light on the networks of uncultured micro-organisms involved in degradation of organic micro-pollutants.

Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird

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

Pearson, Scott, F.; Levey, Douglas, J.; Greenberg, Catheryn, H.

2003-02-28

Pearson, S.F., D.J. Levey, C.H. Greenberg, and C.M. del Rio. 2003. Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird. Oecologia. 135:516-523. The use of stable isotopes to infer diet requires quantifying the relationship between diet and tissues and, in particular, knowing of how quickly isotopes turnover in different tissues and how isotopic concentrations of different food components change (discriminate) when incorporated into consumer tissues. We used feeding trials with wild-caught yellow-rumped warblers (Dendroica coronata) to determine d15N and d13C turnover rates for blood, d15N and d13C diet-tissue discrimination factors, andmore » diet-tissue relationships for blood and feathers. After 3 weeks on a common diet, 36 warblers were assigned to one of four diets differing in the relative proportion of fruit and insects. Plasma half-life estimates ranged from 0.4 to 0.7 days for d13C and from 0.5 to 1.7 days for d15N. Half-life did not differ among diets. Whole blood half-life for d13C ranged from 3.9 to 6.1 days. Yellow-rumped warbler tissues were enriched relative to diet by 1.7.3.6% for nitrogen isotopes and by 1.2 to 4.3% for carbon isotopes, depending on tissue and diet. Consistent with previous studies, feathers were the most enriched and whole blood and plasma were the least enriched or, in the case of carbon, slightly depleted relative to diet. In general, tissues were more enriched relative to diet for birds with high percentages of insects. For all tissues, carbon and nitrogen isotope discrimination factors increased with carbon and nitrogen concentrations of diets. The isotopic signature of plasma increased linearly with the sum of the isotopic signature of the diet and the discrimination factor. Because the isotopic signature of tissues depends on both elemental concentration and isotopic signature of the diet, attempts to reconstruct diet from stable isotope signatures require mixing models that incorporate elemental concentration.« less

Noble gases in submarine pillow basalt glasses from Loihi and Kilauea, Hawaii: A solar component in the Earth

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

Honda, M.; McDougall, I.; Patterson, D.B.

1993-02-01

Noble gas elemental and isotopic abundances have been analysed in twenty-two samples of basaltic glass dredged from the submarine flanks of two currently active Hawaiian volcanoes, Loihi Seamount and Kilauea. Neon isotopic ratios are enriched in [sup 20]Ne and [sup 21]Ne by as much as 16% with respect to atmospheric ratios. All the Hawaiian basalt glass samples show relatively high [sup 3]He/[sup 4]He ratios. The high [sup 20]Ne/[sup 22]Ne values in some of the Hawaiian samples, together with correlations between neon and helium systematics, suggest the presence of a solar component in the source regions of the Hawaiian mantle plume.more » The solar hypothesis for the Earth's primordial noble gas composition can account for helium and neon isotopic ratios observed in basaltic glasses from both plume and spreading systems, in fluids in continental hydrothermal systems, in CO[sub 2] well gases, and in ancient diamonds. These results provide new insights into the origin and evolution of the Earth's atmosphere.« less

Cold-seep carbonates of the middle and lower continental slope, northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Roberts, Harry H.; Feng, Dong; Joye, Samantha B.

2010-11-01

Authigenic carbonates from cold seeps on the middle and lower continental slope of the northern Gulf of Mexico (GOM) exhibit a wide range of mineralogical and stable isotopic compositions. These carbonates consist of concretions and nodules in surface sediments, hardgrounds of crusts and isolated slabs, and mounded buildups of blocks and slabs of up to over 10 meters in relief above the surrounding seafloor. Mineralogically, the carbonates are dominated by high-Mg calcite (HMC) and aragonite. However, low levels (<5 wt%) of dolomite are present in most samples. Petrographically, Mg-calcite peloidal matrix and acicular to botryoidal aragonitic void-filling cements are the most frequent associations. The carbon isotopic compositions of the carbonates range from -60.8 to 14.0‰ PDB, indicating complex carbon sources that include 13C-depleted biogenic and thermogenic methane, biodegraded crude oil, seawater CO2, and 13C-enriched residual CO2 from methanogenesis. A similarly large variability in δ18O values (2.5 to 6.7‰ PDB) demonstrates the geochemical complexity of the slope, with some samples pointing toward an 18O-enriched oxygen source that is possibly related to advection of 18O-enriched formation water and/or to the decomposition of gas hydrate. A considerable range of mineralogical and isotopic variations in cold-seep carbonate composition was noted even within individual study sites. However, common trends occur across multiple geographic areas. This situation suggests that local controls on fluid and gas flux, types of seep hydrocarbons, the presence or absence of gas hydrate in the near-surface sediment, and chemosynthetic communities, as well as the temporal evolution of the local hydrocarbon reservoir, all may play a part in determining carbonate mineralogy and isotope geochemistry. The carbon isotope data clearly indicate that between-site variation is greater than within-site variation. Seep carbonates formed on the middle and lower continental slope of the GOM do not appear to be substantially different from those found on the upper slope (<1000-m water depth). The highly variable fluids and gases that leave their geochemical imprints on seep carbonate of the middle and lower continental slope are similar to their outer shelf and upper slope counterparts.

Stable mercury isotope ratios as tracers for Hg cycling at the inoperative New Idria Hg mine, California

NASA Astrophysics Data System (ADS)

Wiederhold, J. G.; Jew, A. D.; Brown, G. E.; Bourdon, B.; Kretzschmar, R.

2010-12-01

The seven stable isotopes of Hg are fractionated in the environment as a result of mass-dependent (MDF) and mass-independent (MIF) fractionation processes that can be studied in parallel by analyzing the ratios of even and odd mass Hg isotopes. MDF and MIF Hg isotope signatures of natural samples may provide a new tool to trace sources and transformations in environmental Hg cycling. However, the mechanisms controlling the extent of kinetic and equilibrium Hg isotope fractionations are still only partially understood. Thus, development of this promising tracer requires experimental calibration of relevant fractionation factors as well as assessment of natural variations of Hg isotope ratios under different environmental conditions. The inoperative Hg mine in New Idria (California, USA) represents an ideal case study to explore Hg isotope fractionation during Hg transformation and transport processes. More than a century of Hg mining and on-site thermal refining to obtain elemental Hg until 1972 produced large volumes of contaminated mine wastes which now represent sources of Hg pollution for the surrounding ecosystems. Here, we present Hg isotope data from various materials collected at New Idria using Cold-Vapor-MC-ICPMS with a long-term δ202Hg reproducibility of ±0.1‰ (2SD). Uncalcined mine waste samples were isotopically similar to NIST-3133 and did not exhibit any MIF signatures. In contrast, calcine samples, which represent the residue of the thermal ore processing at 700°C, had significantly heavier δ202Hg values of up to +1.5‰. In addition, we observed small negative MIF anomalies of the odd-mass Hg isotopes in the calcine samples, which could be caused either by nuclear volume fractionation or a magnetic isotope effect during or after the roasting process. The mass-dependent enrichment of heavy Hg isotopes in the calcine materials indicates that light Hg isotopes were preferentially removed during the roasting process, in agreement with a previous study by Stetson et al. (ES&T, 2009, 43:7331-7336). In order to further elucidate the Hg isotope signatures of the New Idria samples, we performed a three-step sequential extraction procedure to separate different Hg pools. The calcine samples exhibited a higher proportion of leachable Hg phases compared with the unrefined ore waste samples. The most soluble Hg pool (HAc/HCl, pH 2) had a significantly heavier MDF and more negative MIF signature than the bulk calcine samples, suggesting that the dissolution of more soluble Hg phases from calcine materials results in an enhanced flux of leached Hg which is isotopically distinct from the original ore. Moreover, this finding demonstrates that the Hg isotope fractionation during the ore roasting cannot be solely explained by a kinetic Rayleigh-type process which removes light Hg isotopes, but must additionally involve the formation of isotopically heavy secondary Hg phases in the calcine. The analysis of additional samples will enable us to test this hypothesis and to gain further insights into the applicability of stable Hg isotope ratios as source and process tracers in Hg-contaminated environments.

Gold and isotopically enriched platinium targets for the production of radioactive beams of francium

NASA Astrophysics Data System (ADS)

Lipski, A. R.; Orozco, L. A.; Pearson, M. R.; Simsarian, J. E.; Sprouse, G. D.; Zhao, W. Z.

1999-12-01

Au and isotopically enriched Pt targets are discussed for the production of radioactive Fr beams. Target foils, serving also as ionizers, have to be heated in order to enhance the diffusion of atoms to the surface for further extraction and injection into the electrostatic transport system.

DUPAL anomaly in the Sea of Japan: Pb, Nd, and Sr isotopic variations at the eastern Eurasian continental margin

USGS Publications Warehouse

Tatsumoto, M.; Nakamura, Y.

1991-01-01

Volcanic rocks from the eastern Eurasian plate margin (southwestern Japan, the Sea of Japan, and northeastern China) show enriched (EMI) component signatures. Volcanic rocks from the Ulreung and Dog Islands in the Sea of Japan show typical DUPAL anomaly characteristics with extremely high ??208/204 Pb (up to 143) and enriched Nd and Sr isotopic compositions (??{lunate}Nd = -3 to -5, 87Sr 86Sr = ~0.705). The ??208/204 Pb values are similar to those associated with the DUPAL anomaly (up to 140) in the southern hemisphere. Because the EMI characteristics of basalts from the Sea of Japan are more extreme than those of southwestern Japan and inland China basalts, we propose that old mantle lithosphere was metasomatized early (prior to the Proterozoic) with subduction-related fluids (not present subduction system) so that it has been slightly enriched in incompatible elements and has had a high Th/U for a long time. The results of this study support the idea that the old subcontinental mantle lithosphere is the source for EMI of oceanic basalts, and that EMI does not need to be stored at the core/ mantle boundary layer for a long time. Dredged samples from seamounts and knolls from the Yamato Basin Ridge in the Sea of Japan show similar isotopic characteristics to basalts from the Mariana arc, supporting the idea that the Yamato Basin Ridge is a spreading center causing separation of the northeast Japan Arc from Eurasia. ?? 1991.

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.

Asthenospheric and lithospheric sources for Mesozoic dolerites from Liberia (Africa): trace element and isotopic evidence

NASA Astrophysics Data System (ADS)

Dupuy, C.; Marsh, J.; Dostal, J.; Michard, A.; Testa, S.

1988-01-01

Combined elemental, and Sr and Nd isotopic data are presented for Mesozoic dolerite dikes of Liberia (Africa) which are related to the initial stage of opening of the Atlantic Ocean. The large scatter of both trace element and isotopic data allows the identification of five groups of dolerites which cannot be related to each other by simple processes of mineral fractionation from a common source. On the contrary, the observed chemical and isotopic variation within some dolerites (Groups I and II) may result either from variable degrees of melting of an isotopically heterogeneous source or mixing between enriched and depleted oceanic type mantle. For the other dolerites (Groups III-V) mixing with a third mantle source with more radiogenic Sr and with element ratios characteristic of subduction environments is suggested. This third source is probably the subcontinental lithospheric mantle. Finally, no significant modification by interaction with continental crust is apparent in most of the analyzed samples.

Thermal Neutron Capture onto the Stable Tungsten Isotopes

NASA Astrophysics Data System (ADS)

Hurst, A. M.; Firestone, R. B.; Sleaford, B. W.; Summers, N. C.; Revay, Zs.; Szentmiklósi, L.; Belgya, T.; Basunia, M. S.; Capote, R.; Choi, H.; Dashdorj, D.; Escher, J.; Krticka, M.; Nichols, A.

2012-02-01

Thermal neutron-capture measurements of the stable tungsten isotopes have been carried out using the guided thermal-neutron beam at the Budapest Reactor. Prompt singles spectra were collected and analyzed using the HYPERMET γ-ray analysis software package for the compound tungsten systems 183W, 184W, and 187W, prepared from isotopically-enriched samples of 182W, 183W, and 186W, respectively. These new data provide both confirmation and new insights into the decay schemes and structure of the tungsten isotopes reported in the Evaluated Gamma-ray Activation File based upon previous elemental analysis. The experimental data have also been compared to Monte Carlo simulations of γ-ray emission following the thermal neutron-capture process using the statistical-decay code DICEBOX. Together, the experimental cross sections and modeledfeeding contribution from the quasi continuum, have been used to determine the total radiative thermal neutron-capture cross sections for the tungsten isotopes and provide improved decay-scheme information for the structural- and neutron-data libraries.

Extreme 13Ccarb enrichment in ca. 2.0 Ga magnesite-stromatolite-dolomite-`red beds' association in a global context: a case for the world-wide signal enhanced by a local environment

NASA Astrophysics Data System (ADS)

Melezhik, Victor A.; Fallick, Anthony E.; Medvedev, Pavel V.; Makarikhin, Vladimir V.

1999-12-01

The Palaeoproterozoic positive excursion of δ 13Ccarb is now considered as three positive shifts of δ 13Ccarb separated by returns to 0‰, which all occurred between 2.40 and 2.06 Ma. This isotopic event is unique in terms of both duration (>300 Ma) and 13C enrichment (up to +18‰). The mechanism responsible for one of the most significant carbon isotopic shifts in Earth history remains highly debatable. To date, δ 13C of +10‰ to +15‰ cannot be balanced by organic carbon burial ( forg) as there is no geological evidence for an enhanced C org accumulation prior to or synchronous with the excursion. Instead, termination of these excursions is followed by formation of a vast reservoir of 13C-depleted organic material (-45‰ at Shunga) and by one of the earliest known oil-generation episodes at 2.0 Ga. None of the three positive excursions of δ 13Ccarb is followed by a negative isotopic shift significantly below 0‰, as has always been observed in younger isotopic events, reflecting an overturn of a major marine carbon reservoirs. This may indicate that forg was constant: implying that the mechanism involved in the production of C org was different. Onset of intensive methane cycling resulting in Δc change is another possibility. The majority of sampled 13Ccarb-rich localities represents shallow-water stromatolitic dolostones, `red beds' and evaporites formed in restricted intracratonic basins, and may not reflect global δ 13Ccarb values. Closely spaced drill core samples ( n=73) of stromatolitic dolostones from the >1980±27 Ma Tulomozerskaya Formation in the Onega palaeobasin, Russian Karelia, have been analysed for δ 13Ccarb and δ 18Ocarb in order to demonstrate that different processes were involved in the formation of 13Ccarb-rich carbonates. The 800 m-thick magnesite-stromatolite-dolomite-`red beds' succession formed in a complex combination of environments on the Karelian craton: peritidal shallow marine, low-energy protected bights, barred basins, evaporative ephemeral ponds, coastal sabkhas and playa lakes. The carbonate rocks exhibit extreme 13C enrichment with δ 13C values ranging from +5.7 to +17.2‰ vs. V-PDB (mean+9.9±2.3‰) and δ 18O from 18.6 to 26.0‰ vs. V-SMOW (mean 22.0±1.6‰). The Tulomozerskaya isotopic excursion is characteristic of the global 2.4-2.06 Ga positive shifts of carbonate 13C/ 12C, although it reveals the greatest enrichment in 13C known from this interval. An external basin(s) is considered to have provided an enhanced C org burial and global seawater enrichment in 13C: the global background value for the isotopic shift at Tulomozero time (ca. 2.0 Ga) is roughly estimated at around +5‰. An explosion of stromatolite-forming microbial communities in shallow-water basins, evaporative and partly restricted environments, high bioproductivity, enhanced uptake of 12C, and pene-contemporaneous recycling of organic material in cyanobacterial mats with the production and consequent loss of CO 2 (and CH 4?) are believed to be additional local factors which may have enhanced δ 13C from +5‰ up to +17‰. Such factors should be taken into account when interpreting carbon isotopic data and attempting to discriminate between the local enrichment in 13C and globally enhanced δ 13C values. We propose that many previously reported δ 13C values from other localities, where environmental interpretations are not available or have not been taken into account may not represent the global δ 13C values.

Isotopic tracing of the outflow during artificial rain-on-snow event

NASA Astrophysics Data System (ADS)

Juras, Roman; Pavlásek, Jirka; Vitvar, Tomáš; Šanda, Martin; Holub, Jirka; Jankovec, Jakub; Linda, Miloslav

2016-10-01

The frequency of rain-on-snow (ROS) occurrence is increasing and this natural phenomenon is beginning to play an important role in temperate climate regions. Present knowledge of outflow generation mechanisms and rainwater dynamics during ROS is still insufficient. The study introduces a combined method of artificial ROS, isotopic tracing and energy balance to partition the event rainwater and the pre-event non-rainwater in the outflow. A rainfall simulator and water enriched with deuterium were used for identifying event rainwater and pre-event non-rainwater during an ROS event. The ROS experiment was conducted in the Krkonoše Mountains in the Czech Republic. An experimental snow block consisting of ripe and isothermal snow was sprayed with deuterium enriched water. The outflow from the snowpack was continuously monitored to gain quantitative and qualitative information about outflow water. The isotopic deuterium content was further analysed from the samples by means of laser spectroscopy in order to separate the hydrograph components. The deuterium content was also analysed from the snow samples gathered before and after the experiment to identify the retention of event rainwater in the snowpack. Isotopic hydrograph separation revealed that although high rain intensity was applied, the event rainwater represented one half (52.7%) of the total outflow volume. The ripe snowpack retained about one third of the rainwater input (33.6%). Significant changes in the outflowing water quality can therefore be expected during ROS events. This experiment also shows that rainwater during ROS firstly pushes-out the non-rainwater and then contributes to the outflow. These results show that the presented technique allows us to gain sufficient information about rainwater dynamics during ROS.

A new feature in the internal heavy isotope distribution in ozone.

PubMed

Bhattacharya, S K; Savarino, Joel; Michalski, G; Liang, Mao-Chang

2014-10-07

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition ((18)O/(16)O and (17)O/(16)O ratio) which does not follow normal mass fractionation rule: δ(17)O ∼ 0.52(*)δ(18)O, expressed as an anomaly Δ(17)O = δ(17)O - 0.52(*)δ(18)O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ(18)O (s) or δ(18)O (as) (and similarly for δ(17)O) as well as position dependent isotope anomaly Δ(17)O (s) and Δ(17)O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ(17)O (s) is zero. Consequently, Δ(17)O (as) = 1.5 (*) Δ(17)O (bulk) (named here simply as the "1.5 rule") which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.

A new feature in the internal heavy isotope distribution in ozone

NASA Astrophysics Data System (ADS)

Bhattacharya, S. K.; Savarino, Joel; Michalski, G.; Liang, Mao-Chang

2014-10-01

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition (18O/16O and 17O/16O ratio) which does not follow normal mass fractionation rule: δ17O ˜ 0.52*δ18O, expressed as an anomaly Δ17O = δ17O - 0.52*δ18O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ18O (s) or δ18O (as) (and similarly for δ17O) as well as position dependent isotope anomaly Δ17O (s) and Δ17O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ17O (s) is zero. Consequently, Δ17O (as) = 1.5 * Δ17O (bulk) (named here simply as the "1.5 rule") which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.

Isotopic effects on phonon anharmonicity in layered van der Waals crystals: Isotopically pure hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Cuscó, Ramon; Artús, Luis; Edgar, James H.; Liu, Song; Cassabois, Guillaume; Gil, Bernard

2018-04-01

Hexagonal boron nitride (h -BN) is a layered crystal that is attracting a great deal of attention as a promising material for nanophotonic applications. The strong optical anisotropy of this crystal is key to exploit polaritonic modes for manipulating light-matter interactions in 2D materials. h -BN has also great potential for solid-state neutron detection and neutron imaging devices, given the exceptionally high thermal neutron capture cross section of the boron-10 isotope. A good knowledge of phonons in layered crystals is essential for harnessing long-lived phonon-polariton modes for nanophotonic applications and may prove valuable for developing solid-state 10BN neutron detectors with improved device architectures and higher detection efficiencies. Although phonons in graphene and isoelectronic materials with a similar hexagonal layer structure have been studied, the effect of isotopic substitution on the phonons of such lamellar compounds has not been addressed yet. Here we present a Raman scattering study of the in-plane high-energy Raman active mode on isotopically enriched single-crystal h -BN. Phonon frequency and lifetime are measured in the 80-600-K temperature range for 10B-enriched, 11B-enriched, and natural composition high quality crystals. Their temperature dependence is explained in the light of perturbation theory calculations of the phonon self-energy. The effects of crystal anisotropy, isotopic disorder, and anharmonic phonon-decay channels are investigated in detail. The isotopic-induced changes in the phonon density of states are shown to enhance three-phonon anharmonic decay channels in 10B-enriched crystals, opening the possibility of isotope tuning of the anharmonic phonon decay processes.

Enrichment of 57Fe isotope in neutron flux of nuclear reactors observed by Mössbauer spectroscopy.

PubMed

Sawicki, Jerzy A

2018-02-01

The abundance of 57 Fe isotope in nuclear reactor core materials can be considerably enriched by neutron-capture 56 Fe(n,γ) reactions. This is demonstrated using the sections of Zr-2.5 wt.%Nb pressure tubes removed from two CANDU* reactors. The tubes contained 0.11 and 0.04wt% Fe and were irradiated for about 10 effective full power years (EFPY) up to ~10 26 n/m 2 fast neutron (E > 1MeV) fluencies. The Mössbauer spectra of 57 Fe in irradiated samples indicated up to 10 times larger areas than unirradiated off-cuts from the same pressure tubes. The observed effect is in accord with the values calculated for known thermal neutron-capture cross-sections and resonance capture integrals, neutron flux profiles and spectra, and times of irradiation. The build-up of 57 Fe facilitated recording Mössbauer absorption spectra of alloys with minor amount of Fe down to ~ 400ppm, despite intense background radiation emitted by samples. These findings can open new possibilities in post-irradiation studies of alloys used in nuclear reactors and in other objects subjected to large neutron fluencies. Copyright © 2017 Elsevier Ltd. All rights reserved.

Oxygen isotope values of tree ring α-cellulose as a proxy of hydroclimate variability in arid regions

NASA Astrophysics Data System (ADS)

Dodd, J. P.; Freimuth, E. J.; Olson, E. J.; Diefendorf, A. F.

2015-12-01

One of the main goals of tree ring isotope studies is to reconstruct climate-driven variations in the source water and antecedent precipitation; however, evaporation in the soil and leaves can significantly modify the isotope values of the source water. This is particularly the case in arid environments where evaporative effects are perhaps the most significant unknown variable when attempting to reconstruct regional-scale hydroclimate variations from tree ring isotope proxies. To quantify the effects of extreme aridity on α-cellulose δ18O values, we measured the oxygen isotope values of groundwater, xylem water, leaf water, and tree ring α-cellulose in an endemic species of drought-resistant trees (Prosopis tamarugo) from different microenvironments throughout the Atacama Desert of Northern Chile. Average annual precipitation is <5 mm/yr, and groundwater is the primary water source for P. tamarugo trees in the region. Groundwater δ18O values at the sample locations range from -6.7 to -9.7‰, and xylem water δ18O values record a systematic increase (ave. Δ18Ox-gw =+1.3‰; 2σ =1.0‰). Leaf waters are significantly affected by evaporative enrichment with a range of δ18O values from 7 to 23‰. This range most likely reflects a number of physiological and environmental conditions including tree size, canopy development, and sample time (i.e. morning vs. evening). However, despite the large variation in leaf water δ18O values, the average difference between the α-cellulose and groundwater is very consistent (Δ18Oc-gw = +39.7‰; 2σ =1.3‰). P. tamarugo samples were collected in austral spring, when tree growth was at its maximum; therefore, any seasonal variations in plant physiology not captured with this dataset will have a limited impact on cellulose production. These data demonstrate that despite the variable evaporative enrichment of 18O in the leaf water, the α-cellulose δ18O values provide a remarkably consistent record of variations in groundwater δ18O values in this extremely arid environment.

Image fusion of Secondary Ion Mass Spectrometry and Energy-dispersive X-Ray Spectroscopy data for the characterization of uranium-molybdenum fuel foils

NASA Astrophysics Data System (ADS)

Willingham, David; Naes, Benjamin E.; Tarolli, Jay G.; Schemer-Kohrn, Alan; Rhodes, Mark; Dahl, Michael; Guzman, Anthony; Burkes, Douglas E.

2018-01-01

Uranium-molybdenum (U-Mo) monolithic fuels represent one option for converting civilian research and test reactors operating with high enriched uranium (HEU) to low enriched uranium (LEU), effectively reducing the threat of nuclear proliferation world-wide. However, processes associated with fabrication of U-Mo monolithic fuels result in regions of elemental heterogeneity, observed as bands traversing the cross-section of representative samples. Isotopic variations (e.g., 235U and 238U) could also be introduced because of associated processing steps, particularly since HEU feedstock is melted with natural or depleted uranium diluent to produce LEU. This study demonstrates the utility of correlative analysis of Energy-Dispersive X-ray Spectroscopy (EDS) and Secondary Ion Mass Spectrometry (SIMS) with their image data streams using image fusion, resulting in a comprehensive microanalytical characterization toolbox. Elemental and isotopic measurements were made on a sample from the Advanced Test Reactor (ATR) Full-sized plate In-center flux trap Position (AFIP)-7 experiment and compared to previous optical and electron microscopy results. The image fusion results are characteristic of SIMS isotopic maps, but with the spatial resolution of EDS images and, therefore, can be used to increase the effective spatial resolution of the SIMS imaging results to better understand homogeneity or heterogeneity that persists because of processing selections. Visual inspection using the image fusion methodology indicated slight variations in the 235U/238U ratio and quantitative analysis using the image intensities across several FoVs revealed an average 235U atom percent value of 17.9 ± 2.4%, which was indicative of a non-uniform U isotopic distribution in the area sampled. Further development of this capability is useful for understanding the connections between the properties of LEU fuel alternatives and the ability to predict performance under irradiation.

Fractionation of 238U/235U by reduction during low temperature uranium mineralisation processes

NASA Astrophysics Data System (ADS)

Murphy, Melissa J.; Stirling, Claudine H.; Kaltenbach, Angela; Turner, Simon P.; Schaefer, Bruce F.

2014-02-01

Investigations of ‘stable’ uranium isotope fractionation during low temperature, redox transformations may provide new insights into the usefulness of the 238U/235U isotope system as a tracer of palaeoredox processes. Sandstone-hosted uranium deposits accumulate at an oxidation/reduction interface within an aquifer from the low temperature reduction of soluble U(VI) complexes in groundwaters, forming insoluble U(IV) minerals. This setting provides an ideal environment in which to investigate the effects of redox transformations on 238U/235U fractionation. Here we present the first coupled measurements of 238U/235U isotopic compositions and U concentrations for groundwaters and mineralised sediment samples from the same redox system in the vicinity of the high-grade Pepegoona sandstone-hosted uranium deposit, Australia. The mineralised sediment samples display extremely variable 238U/235U ratios (herein expressed as δUCRM145238, the per-mil deviation from the international NBL standard CRM145). The majority of mineralised sediment samples have δUCRM145238 values between -1.30±0.05 and 0.55±0.12‰, spanning a ca. 2‰ range. However, one sample has an unusually light isotopic composition of -4.13±0.05‰, which suggests a total range of U isotopic variability of up to ca. 5‰, the largest variation found thus far in a single natural redox system. The 238U/235U isotopic signature of the mineralised sediments becomes progressively heavier (enriched in 238U) along the groundwater flow path. The groundwaters show a greater than 2‰ variation in their 238U/235U ratios, ranging from δUCRM145238 values of -2.39±0.07 to -0.71±0.05‰. The majority of the groundwater data exhibit a clear systematic relationship between 238U/235U isotopic composition and U concentration; samples with the lowest U concentrations have the lowest 238U/235U ratios. The preferential incorporation of 238U during reduction of U(VI) to U(IV) and precipitation of uranium minerals leaves the groundwaters enriched in 235U, resulting in a progressive shift in 238U/235U towards lighter values in the aqueous phase as U is removed. These data can be modelled by a closed system Rayleigh fractionation model, with a fractionation factor (α, representing the 238U/235U composition of the groundwater relative to the solid uranium minerals) ranging from ∼0.9996 to 1.0000, with the majority of datapoints ranging from α values of 0.9998 to 0.9999. The sense and magnitude of the results of this study imply that 238U/235U fractionation is likely to be controlled by volume-dependent nuclear field shift effects during the reduction of U(VI) to U(IV) during mineralisation processes. These findings support the use of the 238U/235U isotopic system as a tracer to constrain the nature and timing of palaeoredox conditions.

Gallium isotopic evidence for the fate of moderately volatile elements in planetary bodies and refractory inclusions

NASA Astrophysics Data System (ADS)

Kato, Chizu; Moynier, Frédéric

2017-12-01

The abundance of moderately volatile elements, such as Zn and Ga, show variable depletion relative to CI between the Earth and primitive meteorite (chondrites) parent bodies. Furthermore, the first solar system solids, the calcium-aluminum-rich inclusions (CAIs), are surprisingly rich in volatile element considering that they formed under high temperatures. Here, we report the Ga elemental and isotopic composition of a wide variety of chondrites along with five individual CAIs to understand the origin of the volatile elements and to further characterize the enrichment of the volatile elements in high temperature condensates. The δ71Ga (permil deviation of the 71Ga/69Ga ratio from the Ga IPGP standard) of carbonaceous chondrites decreases in the order of CI >CM >CO >CV and is inversely correlated with the Al/Ga ratio. This implies that the Ga budget of the carbonaceous chondrites parent bodies were inherited from a two component mixing of a volatile rich reservoir enriched in heavy isotope of Ga and a volatile poor reservoir enriched in light isotope of Ga. Calcium-aluminum-rich inclusions are enriched in Ga and Zn compared to the bulk meteorite and are both highly isotopically fractionated with δ71Ga down to -3.56‰ and δ66Zn down to -0.74‰. The large enrichment in the light isotopes of Ga and Zn in the CAIs implies that the moderately volatile elements were introduced in the CAIs during condensation in the solar nebula as opposed to secondary processing in the meteorite parent body and supports a change in gas composition in which CAIs were formed.

Leaf water enrichment of stable water isotopes (δ18O and δD) in a mature oil palm plantation in Jambi province, Indonesia.

NASA Astrophysics Data System (ADS)

Bonazza, Mattia; Tjoa, Aiyen; Knohl, Alexander

2017-04-01

During the last few decades, Indonesia experienced rapid and large scale land-use change towards intensively managed crops, one of them is oil palm. This transition results in warmer and dryer conditions in microclimate. The impacts on the hydrological cycle and on water-use by plants are, however, not yet completely clear. Water stable isotopes are useful tracers of the hydrological processes and can provide means to partition evapotranspiration into evaporation and transpiration. A key parameter, however, is the enrichment of water stable isotope in plant tissue such as leaves that can provide estimates on the isotopic composition of transpiration. Here we present the results of a field campaign conducted in a mature oil palm plantation in Jambi province, Indonesia. We combined continuous measurements of water vapor isotopic composition and mixing ratio with isotopic analysis of water stored in different pools like oil palm leaves, epiphytes, trunk organic matter and soil collected over a three days period. Leaf enrichment varied from -2 ‰ to 10 ‰ relative to source (ground) water. The temporal variability followed Craig and Gordon model predictions for leaf water enrichment. An improved agreement was reached after considering the Péclet effect with an appropriate value of the characteristic length (L). Measured stomatal conductance (gs) on two different sets of leaves (top and bottom canopy) was mainly controlled by radiation (photosynthetically active radiation) and vapor pressure deficit. We assume that this control could be explained in conditions where soil water content is not representing a limiting factor. Understanding leaf water enrichment provides one step towards partitioning ET.

99 Tc NMR determination of the oxygen isotope content in 18 O-enriched water.

PubMed

Tarasov, Valerii P; Kirakosyan, Gayana А; German, Konstantin E

2018-03-01

99 Tc NMR has been suggested as an original method of evaluating the content of oxygen isotopes in oxygen-18-enriched water, a precursor for the production of radioisotope fluorine-18 used in positron emission tomography. To this end, solutions of NH 4 TcO 4 or NaTcO 4 (up to 0.28 mol/L) with natural abundance of oxygen isotopes in virgin or recycled 18 O-enriched water have been studied by 99 Tc NMR. The method is based on 16 O/ 17 O/ 18 O intrinsic isotope effects in the 99 Tc NMR chemical shifts, and the statistical distribution of oxygen isotopes in the coordination sphere of TcO 4 - and makes it possible to quantify the composition of enriched water by measuring the relative intensities of the 99 Tc NMR signals of the Tc 16 O 4-n 18 O n - isotopologues. Because the oxygen exchange between TcO 4 - and enriched water in neutral and alkaline solutions is characterized by slow kinetics, gaseous HCl was bubbled through a solution for a few seconds to achieve the equilibrium distribution of oxygen isotopes in the Tc coordination sphere without distortion of the oxygen composition of the water. Pertechnetate ion was selected as a probe due to its high stability in solutions and the significant 99 Tc NMR shift induced by a single 16 O→ 18 O substitution (-0.43 ± 0.01 ppm) in TcO 4 - and spin coupling constant 1 J( 99 Tc- 17 O) (131.46 Hz) favourable for the observation of individual signals of Tc 16 O 4-n 18 O n - isotopologues. Copyright © 2017 John Wiley & Sons, Ltd.

Nitrogen control of 13C enrichment in heterotrophic organs relative to leaves in a landscape-building desert plant species

DOE PAGES

Zhang, J.; Gu, L.; Bao, F.; ...

2014-09-10

A longstanding puzzle in isotope studies of C 3 plant species is that heterotrophic plant organs (e.g., stems, roots, seeds, and fruits) tend to be enriched in 13C compared to the autotrophic organ (leaves) that provides them with photosynthate. Our inability to explain this puzzle suggests key deficiencies in understanding post-photosynthetic metabolic processes. It also limits the effectiveness of applications of stable carbon isotope analyses in a variety of scientific disciplines ranging from plant physiology to global carbon cycle studies. To gain insight into this puzzle, we excavated whole plant architectures of Nitraria tangutorum Bobrov, a C 3 species thatmore » has an exceptional capability of fixing sands and building sand dunes, in two deserts in northwestern China. We systematically and simultaneously measured carbon isotope ratios and nitrogen and phosphorous contents of different parts of the excavated plants. We also determined the seasonal variations in leaf carbon isotope ratios on nearby intact plants of N. tangutorum. We found, for the first time, that higher nitrogen contents in heterotrophic organs were significantly correlated with increased heterotrophic 13C enrichment compared to leaves. However, phosphorous contents had no effect on the enrichment. In addition, new leaves had carbon isotope ratios similar to roots but were progressively depleted in 13C as they matured. We concluded that a nitrogen-mediated process, probably the refixation of respiratory CO 2 by phosphoenolpyruvate (PEP) carboxylase, was responsible for the differences in 13C enrichment among different heterotrophic organs while processes within leaves or during phloem loading may contribute to the overall autotrophic – heterotrophic difference in carbon isotope compositions.« less

Covariance of oxygen and hydrogen isotopic composition in plant water: Species effects

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

Cooper, L.W.; DeNiro, M.J.

1989-12-01

Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species-specific factors on leaf water enrichment of D and {sup 18}O have not been studied for different plants growing together. To learn whether leaf water enrichment patterns and processes for D and {sup 18}O are different for individual species growing under the same environmental conditions the authors tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show high sloped (m in the leafmore » water equation {delta}D = m {delta}{sup 18}O + b) than in C{sub 3} plants. They determined the relationships between the stable hydrogen ({delta}D) and oxygen ({delta}{sup 18}O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes.« less

Dispersal of adult culex mosquitoes in an urban west nile virus hotspot: a mark-capture study incorporating stable isotope enrichment of natural larval habitats.

PubMed

Hamer, Gabriel L; Anderson, Tavis K; Donovan, Danielle J; Brawn, Jeffrey D; Krebs, Bethany L; Gardner, Allison M; Ruiz, Marilyn O; Brown, William M; Kitron, Uriel D; Newman, Christina M; Goldberg, Tony L; Walker, Edward D

2014-03-01

Dispersal is a critical life history behavior for mosquitoes and is important for the spread of mosquito-borne disease. We implemented the first stable isotope mark-capture study to measure mosquito dispersal, focusing on Culex pipiens in southwest suburban Chicago, Illinois, a hotspot of West Nile virus (WNV) transmission. We enriched nine catch basins in 2010 and 2011 with 15N-potassium nitrate and detected dispersal of enriched adult females emerging from these catch basins using CDC light and gravid traps to distances as far as 3 km. We detected 12 isotopically enriched pools of mosquitoes out of 2,442 tested during the two years and calculated a mean dispersal distance of 1.15 km and maximum flight range of 2.48 km. According to a logistic distribution function, 90% of the female Culex mosquitoes stayed within 3 km of their larval habitat, which corresponds with the distance-limited genetic variation of WNV observed in this study region. This study provides new insights on the dispersal of the most important vector of WNV in the eastern United States and demonstrates the utility of stable isotope enrichment for studying the biology of mosquitoes in other disease systems.

Collisionless dissociation and isotopic enrichment of SF6 using high-powered CO2 laser radiation

NASA Technical Reports Server (NTRS)

Gower, M. C.; Billman, K. W.

1977-01-01

Dissociation of S-32F6 and the resultant isotopic enrichment of S-34F6 using high-powered CO2 laser radiation has been studied with higher experimental sensitivity than previously reported. Enrichment factors have been measured as a function of laser pulse number, wavelength, energy and time duration. A geometry independent dissociation cross section is introduced and measured values are presented. Threshold energy densities, below which no dissociation was observed, were also determined.

Energy expenditure in space flight (doubly labelled water method) (8-IML-1)

NASA Technical Reports Server (NTRS)

Parsons, Howard G.

1992-01-01

The objective of the Energy Expenditure in Space Flight (ESS) experiment is to demonstrate and evaluate the doubly labeled water method of measuring the energy expended by crew members during approximately 7 days in microgravity. The doubly labeled water technique determines carbon dioxide production which is then used to calculate energy expenditure. The method relies on the equilibrium between oxygen in respiratory carbon dioxide and oxygen in body water. Because of this equilibrium, the kinetic of water turnover and respiration are interdependent. Under normal conditions, man contains small but significant amounts of deuterium and oxygen 18. Deuterium is eliminated from the body as water while oxygen 18 is eliminated as water and carbon dioxide. The difference in the turnover rates in the two isotopes is proportional to the carbon dioxide production. Deliberately enriching the total body water with both of these isotopes allows the isotope turnovers to be accurately measured in urine, plasma, or saliva samples. The samples are taken to the laboratory for analysis using an ion-ratio spectrometer.

The peculiar geochemical signatures of São Miguel (Azores) lavas: Metasomatised or recycled mantle sources?

NASA Astrophysics Data System (ADS)

Beier, Christoph; Stracke, Andreas; Haase, Karsten M.

2007-07-01

The island of São Miguel, Azores consists of four large volcanic systems that exhibit a large systematic intra-island Sr-Nd-Pb-Hf isotope and trace element variability. The westernmost Sete Cidades volcano has moderately enriched Sr-Nd-Pb-Hf isotope ratios. In contrast, lavas from the easternmost Nordeste volcano have unusually high Sr and Pb and low Nd and Hf isotope ratios suggesting a long-term evolution with high Rb/Sr, U/Pb, Th/Pb, Th/U and low Sm/Nd and Lu/Hf parent-daughter ratios. They have trace element concentrations similar to those of the HIMU islands, with the exception of notably higher alkali element (Cs, Rb, K, Ba) and Th concentrations. The time-integrated parent-daughter element evolution of both the Sete Cidades and Nordeste source matches the incompatibility sequence commonly observed during mantle melting and consequently suggests that the mantle source enrichment is caused by a basaltic melt, either as a metasomatic agent or as recycled oceanic crust. Our calculations show that a metasomatic model involving a small degree basaltic melt is able to explain the isotopic enrichment but, invariably, produces far too enriched trace element signatures. We therefore favour a simple recycling model. The trace element and isotopic signatures of the Sete Cidades lavas are consistent with the presence of ancient recycled oceanic crust that has experienced some Pb loss during sub-arc alteration. The coherent correlation of the parent-daughter ratios (e.g. Rb/Sr, Th/U, U/Pb) and incompatible element ratios (e.g. Nb/Zr, Ba/Rb, La/Nb) with the isotope ratios in lavas from the entire island suggest that the Sete Cidades and Nordeste source share a similar genetic origin. The more enriched trace element and isotopic variations of Nordeste can be reproduced by recycled oceanic crust in the Nordeste source that contains small amounts of evolved lavas (˜ 1-2%), possibly from a subducted seamount. The rare occurrence of enriched source signatures comparable to Nordeste may be taken as circumstantial evidence that stirring processes in the Earth's mantle are not able to homogenise material within the size of seamounts over timescales of mantle recycling.

Isotope effects accompanying evaporation of water from leaky containers.

PubMed

Rozanski, Kazimierz; Chmura, Lukasz

2008-03-01

Laboratory experiments aimed at quantifying isotope effects associated with partial evaporation of water from leaky containers have been performed under three different settings: (i) evaporation into dry atmosphere, performed in a dynamic mode, (ii) evaporation into dry atmosphere, performed in a static mode, and (iii) evaporation into free laboratory atmosphere. The results demonstrate that evaporative enrichment of water stored in leaky containers can be properly described in the framework of the Craig-Gordon evaporation model. The key parameter controlling the degree of isotope enrichment is the remaining fraction of water in the leaking containers. Other factors such as temperature, relative humidity, or extent of kinetic fractionation play only minor roles. Satisfactory agreement between observed and predicted isotope enrichments for both (18)O and (2)H in experiments for the case of evaporation into dry atmosphere could be obtained only when molecular diffusivity ratios of isotope water molecules as suggested recently by Cappa et al. [J. Geophys. Res., 108, 4525-4535, (2003).] were adopted. However, the observed and modelled isotope enrichments for (2)H and (18)O could be reconciled also for the ratios of molecular diffusivities obtained by Merlivat [J. Chem. Phys., 69, 2864-2871 (1978).], if non-negligible transport resistance in the viscous liquid sub-layer adjacent to the evaporating surface is considered. The evaporation experiments revealed that the loss of mass of water stored in leaky containers in the order of 1%, will lead to an increase of the heavy isotope content in this water by ca. 0.35 and 1.1 per thousand, for delta (18)O and delta (2)H, respectively.

Preliminary evaluation of thermal and nonthermal waters at selected sites in Panama, Central America. Evaluacion preliminar de aguas termales y no termales de sitios seleccionados en Panama, Centroamerica

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

Shevenell, L.

1989-11-01

Thirty-one thermal and nonthermal water samples were collected in Panama by the Instituto de Recursos Hidraulicos y Electrificacion and analyzed by the Earth and Space Sciences Division at Los Alamos National Laboratory to evaluate the geothermal potential of four different areas. Chemical and isotopic analyses were performed on each sample. Because samples from several areas were submitted, the chemistry of the samples is varied, with total dissolved solids of thermal fluids ranging from 900 to nearly 10,000 mg/{ell}. All water samples studied are meteoric in origin, and none of the thermal waters exhibit an {sup 18}O enrichment, which is characteristicmore » of high-temperature isotopic, exchange between water and rock. At all four areas, calculated geothermometer temperatures within a reservoir of less than 160{degrees}C. 4 refs., 4 figs., 6 tabs.« less

Laser ablation inductively coupled plasma mass spectrometry for direct isotope ratio measurements on solid samples

NASA Astrophysics Data System (ADS)

Pickhardt, Carola; Dietze, Hans-Joachim; Becker, J. Sabine

2005-04-01

Isotope ratio measurements have been increasingly used in quite different application fields, e.g., for the investigation of isotope variation in nature, in geoscience (geochemistry and geochronology), in cosmochemistry and planetary science, in environmental science, e.g., in environmental monitoring, or by the application of the isotope dilution technique for quantification purposes using stable or radioactive high-enriched isotope tracers. Due to its high sensitivity, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is today a challenging mass spectrometric technique for the direct determination of precise and accurate isotope ratios in solid samples. In comparison to laser ablation quadrupole ICP-MS (LA-ICP-QMS), laser ablation coupled to a double-focusing sector field ICP-MS (LA-ICP-SFMS) with single ion detection offers a significant improvement of sensitivity at low mass resolution, whereby isotope ratios can be measured with a precision to 0.1% relative standard deviation (R.S.D.). In LA-ICP-SFMS, many disturbing isobaric interferences of analyte and molecular ions can be separated at the required mass resolution (e.g., 40Ar16O+ and 56Fe+ for iron isotope ratio measurements). The precision on isotope ratio measurements was improved by one order of magnitude via the simultaneous detection of mass-separated ion currents of isotopes using multiple ion collectors in LA-ICP-MS (LA-MC-ICP-MS). The paper discusses the state of the art, the challenges and limits in isotope ratio measurements by LA-ICP-MS using different instrumentations at the trace and ultratrace level in different fields of application as in environmental and biological research, geochemistry and geochronology with respect to their precision and accuracy.

Geochemical analysis of atlantic rim water, carbon county, wyoming: New applications for characterizing coalbed natural gas reservoirs

USGS Publications Warehouse

McLaughlin, J.F.; Frost, C.D.; Sharma, Shruti

2011-01-01

Coalbed natural gas (CBNG) production typically requires the extraction of large volumes of water from target formations, thereby influencing any associated reservoir systems. We describe isotopic tracers that provide immediate data on the presence or absence of biogenic natural gas and the identify methane-containing reservoirs are hydrologically confined. Isotopes of dissolved inorganic carbon and strontium, along with water quality data, were used to characterize the CBNG reservoirs and hydrogeologic systems of Wyoming's Atlantic Rim. Water was analyzed from a stream, springs, and CBNG wells. Strontium isotopic composition and major ion geochemistry identify two groups of surface water samples. Muddy Creek and Mesaverde Group spring samples are Ca-Mg-S04-type water with higher 87Sr/86Sr, reflecting relatively young groundwater recharged from precipitation in the Sierra Madre. Groundwaters emitted from the Lewis Shale springs are Na-HCO3-type waters with lower 87Sr/86Sr, reflecting sulfate reduction and more extensive water-rock interaction. To distinguish coalbed waters, methanogenically enriched ??13CDIC wasused from other natural waters. Enriched ??13CDIC, between -3.6 and +13.3???, identified spring water that likely originates from Mesaverde coalbed reservoirs. Strongly positive ??13CDIC, between +12.6 and +22.8???, identified those coalbed reservoirs that are confined, whereas lower ??13CDIC, between +0.0 and +9.9???, identified wells within unconfined reservoir systems. Copyright ?? 2011. The American Association of Petroleum Geologists. All rights reserved.

Pb-Sr-Nd-O isotopic characterization of Mesozoic rocks throughout the northern end of the Peninsular Ranges batholith: Isotopic evidence for the magmatic evolution of oceanic arc–continental margin accretion during the Late Cretaceous of southern California

USGS Publications Warehouse

Kistler, Ronald W.; Wooden, Joseph L.; Premo, Wayne R.; Morton, Douglas M.

2014-01-01

Within the duration of the U.S. Geological Survey (USGS)–based Southern California Areal Mapping Project (SCAMP), many samples from the northern Peninsular Ranges batholith were studied for their whole-rock radioisotopic systematics (rubidium-strontium [Rb-Sr], uranium-thorium-lead [U-Th-Pb], and samarium-neodymium [Sm-Nd]), as well as oxygen (O), a stable isotope. The results of three main studies are presented separately, but here we combine them (>400 analyses) to produce a very complete Pb-Sr-Nd-O isotopic profile of an arc-continent collisional zone—perhaps the most complete in the world. In addition, because many of these samples have U-Pb zircon as well as argon mineral age determinations, we have good control of the timing for Pb-Sr-Nd-O isotopic variations.The ages and isotopic variations help to delineate at least four zones across the batholith from west to east—an older western zone (126–108 Ma), a transitional zone (111–93 Ma), an eastern zone (94–91 Ma), and a much younger allochthonous thrust sheet (ca. 84 Ma), which is the upper plate of the Eastern Peninsular Ranges mylonite zone. Average initial 87Sr/86 Sr (Sri), initial 206Pb/204Pb (206 Pbi), initial 208Pb/204Pb (average 208Pbi), initial epsilon Nd (average εNdi), and δ18O signatures range from 0.704, 18.787, 38.445, +3.1, and 4.0‰–9.0‰, respectively, in the westernmost zone, to 0.7071, 19.199, 38.777, −5, and 9‰–12‰, respectively, in the easternmost zone. The older western zone is therefore the more chemically and isotopically juvenile, characterized mostly by values that are slightly displaced from a mantle array at ca. 115 Ma, and similar to some modern island-arc signatures. In contrast, the isotopic signatures in the eastern zones indicate significant amounts of crustal involvement in the magmatic plumbing of those plutons. These isotopic signatures confirm previously published results that interpreted the Peninsular Ranges batholith as a progressively contaminated magmatic arc. The Peninsular Ranges batholith magmatic arc was initially an oceanic arc built on Panthalassan lithosphere that eventually evolved into a continental margin magmatic arc collision zone, eventually overriding North American cratonic lithosphere. Our Pb-Sr-Nd data further suggest that the western arc rocks represent a nearshore or inboard oceanic arc, as they exhibit isotopic signatures that are more enriched than typical mid-ocean-ridge basalt (MORB). Isotopic signatures from the central zone are transitional and indicate that enriched crustal magma sources were becoming involved in the northern Peninsular Ranges batholith magmatic plumbing. As the oceanic arc–continental margin collision progressed, a mixture of oceanic mantle and continental magmatic sources transpired. Magmatic production in the northern Peninsular Ranges batholith moved eastward and continued to tap enriched crustal magmatic sources. Similar modeling has been previously proposed for two other western margin magmatic arcs, the Sierra Nevada batholith of central California and the Idaho batholith.Calculated initial Nd signatures at ca. 100 Ma for Permian–Jurassic and Proterozoic basement rocks from the nearby San Gabriel Mountains and possible source areas along the southwestern Laurentian margin of southern California, southwestern Arizona, and northern Sonora strongly suggest their involvement with deep crustal magma mixing beneath the eastern zones of the Peninsular Ranges batholith, as well as farther east in continental lithospheric zones.Last, several samples from the allochthonous, easternmost upper-plate zone, which are considerably younger (ca. 84 Ma) than any of the rocks from the northern Peninsular Ranges batholith proper, have even more enriched average Sri, 206Pbi, 208Pbi, and εNdisignatures of 0.7079, 19.344, 38.881, and −6.6, respectively, indicative of the most-evolved magma sources in the northern Peninsular Ranges batholith and similar to radioisotopic values for rocks from the nearby Transverse Ranges, suggesting a genetic connection between the two.

Application of multiple-isotope and groundwater-age data to identify factors affecting the extent of denitrification in a shallow aquifer near a river in South Korea

NASA Astrophysics Data System (ADS)

Kaown, Dugin; Koh, Eun-Hee; Mayer, Bernhard; Kim, Heejung; Park, Dong Kyu; Park, Byeong-Hak; Lee, Kang-Kun

2018-01-01

The extent of denitrification in a small agricultural area near a river in Yangpyeong, South Korea, was determined using multiple isotopes, groundwater age, and physicochemical data for groundwater. The shallow groundwater at one monitoring site had high concentrations of NO3-N (74-83 mg L-1). The δ15N-NO3 values for groundwater in the study area ranged between +9.1 and +24.6‰ in June 2014 and +12.2 to +21.6‰ in October 2014. High δ15N-NO3 values (+10.7 to +12.5‰) in both sampling periods indicated that the high concentrations of nitrate in the groundwater originated from application of organic fertilizers and manure. In the northern part of the study area, some groundwater samples showed elevated δ15N-NO3 and δ18O-NO3 values, which suggest that nitrate was removed from the groundwater via denitrification, with N isotope enrichment factors ranging between -4.8 and -7.9‰ and O isotope enrichment factors varying between -3.8 and -4.9‰. Similar δD and δ18O values of the surface water and groundwater in the south appear to indicate that groundwater in that area was affected by surface-water infiltration. The mean residence times (MRTs) of groundwater showed younger ages in the south (10-20 years) than in the north (20-30 years). Hence, it was concluded that denitrification processes under anaerobic conditions with longer groundwater MRT in the northern part of the study area removed considerable amounts of nitrate. This study demonstrates that multi-isotope data combined with physicochemical data and age-dating information can be effectively applied to characterize nitrate contaminant sources and attenuation processes.

Formation waters from Mississippian-Pennsylvanian reservoirs, Illinois basin, USA: Chemical and isotopic constraints on evolution and migration

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

Stueber, A.M.; Walter, L.M.; Huston, T.J.

1993-02-01

We have analyzed a suite of seventy-four formation-water samples from Mississippian and Pennsylvanian carbonate and siliciclastic strata in the Illinois basin for major, minor, and trace element concentrations and for strontium isotopic composition. A subset of these samples was also analyzed for boron isotopic composition. Data are used to interpret origin of salinity and chemical and Sr isotopic evolution of the brines and in comparison with a similar data set from an earlier study of basin formation waters from Silurian-Devonian reservoirs. Systematics of Cl-Br-Na show that present Mississippian-Pennsylvanian brine salinity can be explained by a combination of subaerial seawater evaporationmore » short of halite saturation and subsurface dissolution of halite from an evaporite zone in the middle Mississippian St. Louis Limestone, along with extensive dilution by mixing with meteoric waters. Additional diagenetic modifications in the subsurface interpreted from cation/Br ratios include K depletion through interaction with clay minerals, Ca enrichment, and Mg depletion by dolomitization, and Sr enrichment through CaCO[sub 3] recrystallization and dolomitization. Ste. Genevieve Limestone (middle Mississippian) formation waters show [sup 87]Sr/[sup 86]Sr ratios in the range 0.70782-0.70900, whereas waters from the siliciclastic reservoirs are in the rante 0.70900-0.71052. Inverse correlations between [sup 87]Sr/[sup 86]Sr and B,Li, and Mg concentrations suggest that the brines acquired radiogenic [sup 87]Sr through interaction with siliciclastic minerals. Completely unsystematic relations between [sup 87]Fr/[sup 86]Sr and 1/Sr are observed; Sr concentrations in Ste. Genevieve and Aux Vases (middle Mississippian) waters appear to be buffered by equilibrium with respect to SrSo[sub 4]. These formation waters are distinguished from Silurian-Devonian brines in the basin by elevated Cl/Br and Na/Br ratios and by unsystematic Sr isotope relationships.« less

Analysis of the site-specific carbon isotope composition of propane by gas source isotope ratio mass spectrometer

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Neto, E. V. Santos; Eiler, John M.

2016-09-01

Site-specific isotope ratio measurements potentially provide valuable information about the formation and degradation of complex molecules-information that is lost in conventional bulk isotopic measurements. Here we discuss the background and possible applications of such measurements, and present a technique for studying the site-specific carbon isotope composition of propane at natural abundance based on mass spectrometric analysis of the intact propane molecule and its fragment ions. We demonstrate the feasibility of this approach through measurements of mixtures of natural propane and propane synthesized with site-specific 13C enrichment, and we document the limits of precision of our technique. We show that mass balance calculations of the bulk δ13C of propane based on our site-specific measurements is generally consistent with independent constraints on bulk δ13C. We further demonstrate the accuracy of the technique, and illustrate one of its simpler applications by documenting the site-specific carbon isotope signature associated with gas phase diffusion of propane, confirming that our measurements conform to the predictions of the kinetic theory of gases. This method can be applied to propane samples of moderate size (tens of micromoles) isolated from natural gases. Thus, it provides a means of studying the site-specific stable isotope systematics of propane at natural isotope abundances on sample sizes that are readily recovered from many natural environments. This method may also serve as a model for future techniques that apply high-resolution mass spectrometry to study the site-specific isotopic distributions of larger organic molecules, with potential applications to biosynthesis, forensics and other geochemical subjects.

Evaluation of soil water stable isotope analysis by H2O(liquid)-H2O(vapor) equilibration method

NASA Astrophysics Data System (ADS)

Gralher, Benjamin; Stumpp, Christine

2014-05-01

Environmental tracers like stable isotopes of water (δ18O, δ2H) have proven to be valuable tools to study water flow and transport processes in soils. Recently, a new technique for soil water isotope analysis has been developed that employs a vapor phase being in isothermal equilibrium with the liquid phase of interest. This has increased the potential application of water stable isotopes in unsaturated zone studies as it supersedes laborious extraction of soil water. However, uncertainties of analysis and influencing factors need to be considered. Therefore, the objective of this study was to evaluate different methodologies of analysing stable isotopes in soil water in order to reduce measurement uncertainty. The methodologies included different preparation procedures of soil cores for equilibration of vapor and soil water as well as raw data correction. Two different inflatable sample containers (freezer bags, bags containing a metal layer) and equilibration atmospheres (N2, dry air) were tested. The results showed that uncertainties for δ18O were higher compared to δ2H that cannot be attributed to any specific detail of the processing routine. Particularly, soil samples with high contents of organic matter showed an apparent isotope enrichment which is indicative for fractionation due to evaporation. However, comparison of water samples obtained from suction cups with the local meteoric water line indicated negligible fractionation processes in the investigated soils. Therefore, a method was developed to correct the raw data reducing the uncertainties of the analysis.. We conclude that the evaluated method is advantageous over traditional methods regarding simplicity, resource requirements and sample throughput but careful consideration needs to be made regarding sample handling and data processing. Thus, stable isotopes of water are still a good tool to determine water flow and transport processes in the unsaturated zone.

Probing soil nitrogen transformations using triple nitrate isotopes

NASA Astrophysics Data System (ADS)

Yu, Z.; Elliott, E. M.

2017-12-01

Models of soil nitrogen (N) transformations are essential for understanding biogeochemical N cycling and its environmental implications. While natural abundance stable N isotopes (δ15N) of the soil N pool are widely used to infer soil N dynamics, its quantitative use is limited by uncertainties in the relevant isotopic fractionations. Oxygen-17 isotope anomalies in nitrate (Δ17O-NO3-), originating from mass-independent fractionation during photochemical NO3- formation, are a conservative tracer of atmospherically deposited NO3- in terrestrial ecosystems. Therefore, measurement of soil Δ17O-NO3- may provide additional tracing power for δ15N-based process models, in that Δ17O-NO3- is not altered by mass-dependent isotopic fractionations. In this study, we conducted both laboratory and field experiments to assess the effectiveness of using triple NO3- isotopes (Δ17O, δ15N, δ18O) for modeling soil N transformations. Surface soil (0-7 cm) was sampled from an urban riparian area and temperate, upland forests in rural and urban settings for batch incubations and amendments with Δ17O-enriched NO3-. After amendment, the soils were extracted on six occasions over a 4-day period to measure concentrations and isotopic composition of NO3- and ammonium. A Δ17O-based numerical model was developed and used to derive gross N fluxes. In situ field soil and lysimeter sampling was also conducted at the rural forest site on five consecutive days immediately following snowmelt input of Δ17O-enriched NO3-. The results show that the temporal dynamics of Δ17O-NO3- can provide quantitative information on soil N turnover. In the laboratory incubations, modeled gross nitrification and denitrification rates were significantly higher for the urban forest and riparian soils, consistent with results from inhibitor-based potential measurements. Non-zero Δ17O-NO3- values, up to 4.3‰, were measured in the rural forest soil following the snowmelt event. A numerical model of the progressive decrease of soil Δ17O-NO3- indicates high NO3- production and consumption rates, revealing active post-snowmelt N cycling in soils. These preliminary results suggest that the triple NO3- isotopes are a powerful tracer for probing soil N transformations and future applications are expected to help disentangle soil N cycling complexity.

Heavy atom labeled nucleotides for measurement of kinetic isotope effects.

PubMed

Weissman, Benjamin P; Li, Nan-Sheng; York, Darrin; Harris, Michael; Piccirilli, Joseph A

2015-11-01

Experimental analysis of kinetic isotope effects represents an extremely powerful approach for gaining information about the transition state structure of complex reactions not available through other methodologies. The implementation of this approach to the study of nucleic acid chemistry requires the synthesis of nucleobases and nucleotides enriched for heavy isotopes at specific positions. In this review, we highlight current approaches to the synthesis of nucleic acids enriched site specifically for heavy oxygen and nitrogen and their application in heavy atom isotope effect studies. This article is part of a special issue titled: Enzyme Transition States from Theory and Experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Oxygen stable isotope ratios from British oak tree-rings provide a strong and consistent record of past changes in summer rainfall

NASA Astrophysics Data System (ADS)

Young, Giles H. F.; Loader, Neil J.; McCarroll, Danny; Bale, Roderick J.; Demmler, Joanne C.; Miles, Daniel; Nayling, Nigel T.; Rinne, Katja T.; Robertson, Iain; Watts, Camilla; Whitney, Matthew

2015-12-01

United Kingdom (UK) summers dominated by anti-cyclonic circulation patterns are characterised by clear skies, warm temperatures, low precipitation totals, low air humidity and more enriched oxygen isotope ratios (δ18O) in precipitation. Such conditions usually result in relatively more positive (enriched) oxygen isotope ratios in tree leaf sugars and ultimately in the tree-ring cellulose formed in that year, the converse being true in cooler, wet summers dominated by westerly air flow and cyclonic conditions. There should therefore be a strong link between tree-ring δ18O and the amount of summer precipitation. Stable oxygen isotope ratios from the latewood cellulose of 40 oak trees sampled at eight locations across Great Britain produce a mean δ18O chronology that correlates strongly and significantly with summer indices of total shear vorticity, surface air pressure, and the amount of summer precipitation across the England and Wales region of the United Kingdom. The isotope-based rainfall signal is stronger and much more stable over time than reconstructions based upon oak ring widths. Using recently developed methods that are precise, efficient and highly cost-effective it is possible to measure both carbon (δ13C) and oxygen (δ18O) isotope ratios simultaneously from the same tree-ring cellulose. In our study region, these two measurements from multiple trees can be used to reconstruct summer temperature (δ13C) and summer precipitation (δ18O) with sufficient independence to allow the evolution of these climate parameters to be reconstructed with high levels of confidence. The existence of long, well-replicated oak tree-ring chronologies across the British Isles mean that it should now be possible to reconstruct both summer temperature and precipitation over many centuries and potentially millennia.

75 FR 42466 - Notice of Availability of Draft Environmental Impact Statement and Public Meeting for the AREVA...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-21

... electrical transmission line required to power the proposed EREF. On March 17, 2010, the NRC granted an... facility. Specifically, AES proposes to use gas centrifuge technology to enrich the uranium-235 isotope... centrifuge-based technology to enrich the uranium- 235 isotope found in natural uranium to concentrations up...

Influence of uncertainties of isotopic composition of the reprocessed uranium on effectiveness of its enrichment in gas centrifuge cascades

NASA Astrophysics Data System (ADS)

Smirnov, A. Yu; Mustafin, A. R.; Nevinitsa, V. A.; Sulaberidze, G. A.; Dudnikov, A. A.; Gusev, V. E.

2017-01-01

The effect of the uncertainties of the isotopic composition of the reprocessed uranium on its enrichment process in gas centrifuge cascades while diluting it by adding low-enriched uranium (LEU) and waste uranium. It is shown that changing the content of 232U and 236U isotopes in the initial reprocessed uranium within 15% (rel.) can significantly change natural uranium consumption and separative work (up to 2-3%). However, even in case of increase of these parameters is possible to find the ratio of diluents, where the cascade with three feed flows (depleted uranium, LEU and reprocessed uranium) will be more effective than ordinary separation cascade with one feed point for producing LEU from natural uranium.

The enrichment of natural radionuclides in oil shale-fired power plants in Estonia--the impact of new circulating fluidized bed technology.

PubMed

Vaasma, Taavi; Kiisk, Madis; Meriste, Tõnis; Tkaczyk, Alan Henry

2014-03-01

Burning oil shale to produce electricity has a dominant position in Estonia's energy sector. Around 90% of the overall electric energy production originates from the Narva Power Plants. The technology in use has been significantly renovated - two older types of pulverized fuel burning (PF) energy production units were replaced with new circulating fluidized bed (CFB) technology. Additional filter systems have been added to PF boilers to reduce emissions. Oil shale contains various amounts of natural radionuclides. These radionuclides concentrate and become enriched in different boiler ash fractions. More volatile isotopes will be partially emitted to the atmosphere via flue gases and fly ash. To our knowledge, there has been no previous study for CFB boiler systems on natural radionuclide enrichment and their atmospheric emissions. Ash samples were collected from Eesti Power Plant's CFB boiler. These samples were processed and analyzed with gamma spectrometry. Activity concentrations (Bq/kg) and enrichment factors were calculated for the (238)U ((238)U, (226)Ra, (210)Pb) and (232)Th ((232)Th, (228)Ra) family radionuclides and for (40)K in different CFB boiler ash fractions. Results from the CFB boiler ash sample analysis showed an increase in the activity concentrations and enrichment factors (up to 4.5) from the furnace toward the electrostatic precipitator block. The volatile radionuclide ((210)Pb and (40)K) activity concentrations in CFB boilers were evenly distributed in finer ash fractions. Activity balance calculations showed discrepancies between input (via oil shale) and output (via ash fractions) activities for some radionuclides ((238)U, (226)Ra, (210)Pb). This refers to a situation where the missing part of the activity (around 20% for these radionuclides) is emitted to the atmosphere. Also different behavior patterns were detected for the two Ra isotopes, (226)Ra and (228)Ra. A part of (226)Ra input activity, unlike (228)Ra, was undetectable in the solid ash fractions of the boiler. Most probably it is released to the surrounding environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

A dual stable-isotope approach to analyse the linkages between tree water fluxes and soil water pools in a Mediterranean mountain catchment

NASA Astrophysics Data System (ADS)

Llorens, Pilar; Cayuela, Carles; Sánchez-Costa, Elisenda; Gallart, Francesc; Latron, Jérôme

2017-04-01

This work uses a dual isotope-based approach (18O, 2H) to examine the mixing of water in the soil and the linkages between tree water fluxes and soil water pools in a Mediterranean mountain catchment (Vallcebre Research Catchments, NE Spain, 42° 12'N, 1° 49'E). Since May 2015, water-isotopes have been monitored in rainfall, throughfall and stemflow below a Scots pine stand and in stream water at the Can Vila (0.56 km2) catchment outlet. Moreover, fortnightly (From May to December 2015) soil samples (10, 20, 30, 50 and 100 cm), xylem samples (3 Scots pines) and mobile soil water samples in low-suction lysimeters (20, 50 and 100 cm) and in a piezometer (150-300 cm deep) were collected at the same stand. Water from soil and xylem samples was extracted by cryogenic vacuum distillation and isotope analyses were obtained by infrared spectroscopy. All this information has been combined with continuous measurement of meteorological, soil moisture and water potential, piezometric levels and hydrological variables at the stand and catchment scales. Stable isotopes ratios of bound soil water fell below the local meteoric water line (LMWL), with more evaporative enrichment in the shallow horizons. On the contrary, mobile soil water (low suction lysimeters) and groundwater fell along the LMWL, well mixed with stream water. The differences observed between these two water pools remained similar during the whole study period. Stable isotopes ratios indicate that Scots pine trees use shallow bound soil water during the whole study period. No marked changes in depth of water uptake were observed, presumably due to the availability of water in the shallow horizons, even during the summer months.

Method and apparatus for noble gas atom detection with isotopic selectivity

DOEpatents

Hurst, G. Samuel; Payne, Marvin G.; Chen, Chung-Hsuan; Parks, James E.

1984-01-01

Apparatus and methods of operation are described for determining, with isotopic selectivity, the number of noble gas atoms in a sample. The analysis is conducted within an evacuated chamber which can be isolated by a valve from a vacuum pumping system capable of producing a pressure of 10.sup.-8 Torr. Provision is made to pass pulses of laser beams through the chamber, these pulses having wavelengths appropriate for the resonance ionization of atoms of the noble gas under analysis. A mass filter within the chamber selects ions of a specific isotope of the noble gas, and means are provided to accelerate these selected ions sufficiently for implantation into a target. Specific types of targets are discussed. An electron measuring device produces a signal relatable to the number of ions implanted into the target and thus to the number of atoms of the selected isotope of the noble gas removed from the gas sample. The measurement can be continued until a substantial fraction, or all, of the atoms in the sample have been counted. Furthermore, additional embodiments of the apparatus are described for bunching the atoms of a noble gas for more rapid analysis, and for changing the target for repetitive cycling of the gas in the chamber. The number of repetitions of the cyclic steps depend upon the concentration of the isotope of interest, the separative efficiency of the mass filter, etc. The cycles are continued until a desired selectivity is achieved. Also described are components and a method of operation for a pre-enrichment operation for use when an introduction of a total sample would elevate the pressure within the chamber to levels in excess of those for operation of the mass filter, specifically a quadrupole mass filter. Specific examples of three noble gas isotope analyses are described.

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. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. 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 (BSM). 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 in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

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.

Specific enrichment of a targeted nitrotyrosine-containing peptide from complex matrices and relative quantification for liquid chromatography-mass spectrometry analysis.

PubMed

Yang, Yun

2017-02-17

Protein tyrosine nitration is considered an important non-enzymatic post-translational modification. In the tyrosine nitration process, 3-nitrotyrosine is formed and recognized as a biomarker of nitrosative/nitrative stress implicated in inflammatory responses and age-related disorders. In view of the complexity of biological samples and the ultra-low abundance of protein-incorporated nitrotyrosine, selective enrichment of nitrotyrosine-containing peptides prior to chromatographic separation is crucial. Herein, I report a simple yet highly specific and efficient enrichment method for nitrotyrosine-containing peptides. After blocking all primary amines in the sample by acetylation with acetic anhydride, I then further converted all nitrotyrosine residues into aminotyrosine residues by reduction with dithiothreitol and hemin. Therefore, I eliminated the side-product with 80Da adduct, since inevitable considerable amount of which was generated in the widely used reduction mediated by sodium dithionite. Both acetylation and reduction yields were close to 100%, and my one-pot sample derivatization applied no solid phase extraction steps or sample transference to avoid sample loss. To capture and release aminotyrosine-containing peptides, I synthesized an N-hydroxysuccinimide-ester-functionalized stationary phase which had very high affinity towards amino groups and possessed a base-cleavable ester linker to retrieve targeted peptides by hydrolysis. I validated this strategy by highly efficient enrichment of the targeted peptide from complex matrices of trypsin-digested bovine serum albumin (BSA) and human plasma spiked with derivatized nitrotyrosine-containing angiotensin II. My enrichment method successfully removed most untargeted peptides in those samples. By relative quantification with home-made identical and stable-isotope labelled internal standards, I investigated the recoveries of a nitrotyrosine-containing peptide from complex biological matrices during enrichment for the first time. Mean recoveries were 49.8% and 41.1% (n=6) for the enrichment of nitrotyrosine-containing angiotensin II from 1:100 (w/w) BSA digest and from 1:10 000 (w/w) human plasma digest, respectively. My enrichment method demonstrated great potential in future applications to clinical samples and biomarker discovery. Copyright © 2017 Elsevier B.V. All rights reserved.

Estimating wetland connectivity to streams in the Prairie Pothole Region: An isotopic and remote sensing approach

USGS Publications Warehouse

Brooks, J. R.; Mushet, David M.; Vanderhoof, Melanie; Leibowitz, Scott G.; Neff, Brian; Christensen, J. R.; Rosenberry, Donald O.; Rugh, W. D.; Alexander, L.C.

2018-01-01

Understanding hydrologic connectivity between wetlands and perennial streams is critical to understanding the reliance of stream flow on inputs from wetlands. We used the isotopic evaporation signal in water and remote sensing to examine wetland‐stream hydrologic connectivity within the Pipestem Creek watershed, North Dakota, a watershed dominated by prairie‐pothole wetlands. Pipestem Creek exhibited an evaporated‐water signal that had approximately half the isotopic‐enrichment signal found in most evaporatively enriched prairie‐pothole wetlands. Groundwater adjacent to Pipestem Creek had isotopic values that indicated recharge from winter precipitation and had no significant evaporative enrichment, indicating that enriched surface water did not contribute significantly to groundwater discharging into Pipestem Creek. The estimated surface water area necessary to generate the evaporation signal within Pipestem Creek was highly dynamic, varied primarily with the amount of discharge, and was typically greater than the immediate Pipestem Creek surface water area, indicating that surficial flow from wetlands contributed to stream flow throughout the summer. We propose a dynamic range of spilling thresholds for prairie‐pothole wetlands across the watershed allowing for wetland inputs even during low‐flow periods. Combining Landsat estimates with the isotopic approach allowed determination of potential (Landsat) and actual (isotope) contributing areas in wetland‐dominated systems. This combined approach can give insights into the changes in location and magnitude of surface water and groundwater pathways over time. This approach can be used in other areas where evaporation from wetlands results in a sufficient evaporative isotopic signal.

Spatial and Temporal Patterns In Ecohydrological Separation

NASA Astrophysics Data System (ADS)

Jarvis, S. K.; Barnard, H. R.; Singha, K.; Harmon, R. E.; Szutu, D.

2017-12-01

The model of ecohydrological separation suggests that trees source water from a different subsurface pool than what is contributing to stream flow during dry periods, however diel fluctuations in stream flow and transpiration are tightly coupled. To better understand the mechanism of this coupling, this study examines spatiotemporal patterns in water isotopic relationships between tree, soil, and stream water. Preliminary analysis of data collected in 2015 show a trend in δ18O enrichment in xylem water, suggesting an increased reliance on enriched soil water not flowing to the stream as the growing season progresses, while xylem samples from 2016, a particularly wet year, do not have this trend. Variations in these temporal trends are explored with regard to distance from stream, aspect of hillslope, position in the watershed, size of the tree, and soil depth. Additionally, a near-stream site is examined at high resolution using water isotope data, sap flow, and electrical resistivity surveying to examine soil moisture and water use patterns across the riparian-hillslope transition.

Determination of 90Sr / 238U ratio by double isotope dilution inductively coupled plasma mass spectrometer with multiple collection in spent nuclear fuel samples with in situ 90Sr / 90Zr separation in a collision-reaction cell

NASA Astrophysics Data System (ADS)

Isnard, H.; Aubert, M.; Blanchet, P.; Brennetot, R.; Chartier, F.; Geertsen, V.; Manuguerra, F.

2006-02-01

Strontium-90 is one of the most important fission products generated in nuclear industry. In the research field concerning nuclear waste disposal in deep geological environment, it is necessary to quantify accurately and precisely its concentration (or the 90Sr / 238U atomic ratio) in irradiated fuels. To obtain accurate analysis of radioactive 90Sr, mass spectrometry associated with isotope dilution is the most appropriated method. But, in nuclear fuel samples the interference with 90Zr must be previously eliminated. An inductively coupled plasma mass spectrometer with multiple collection, equipped with an hexapole collision cell, has been used to eliminate the 90Sr / 90Zr interference by addition of oxygen in the collision cell as a reactant gas. Zr + ions are converted into ZrO +, whereas Sr + ions are not reactive. A mixed solution, prepared from a solution of enriched 84Sr and a solution of enriched 235U was then used to quantify the 90Sr / 238U ratio in spent fuel sample solutions using the double isotope dilution method. This paper shows the results, the reproducibility and the uncertainties that can be obtained with this method to quantify the 90Sr / 238U atomic ratio in an UOX (uranium oxide) and a MOX (mixed oxide) spent fuel samples using the collision cell of an inductively coupled plasma mass spectrometer with multiple collection to perform the 90Sr / 90Zr separation. A comparison with the results obtained by inductively coupled plasma mass spectrometer with multiple collection after a chemical separation of strontium from zirconium using a Sr spec resin (Eichrom) has been performed. Finally, to validate the analytical procedure developed, measurements of the same samples have been performed by thermal ionization mass spectrometry, used as an independent technique, after chemical separation of Sr.

Recycling of subducted crustal components into carbonatite melts revealed by boron isotopes

NASA Astrophysics Data System (ADS)

Hulett, Samuel R. W.; Simonetti, Antonio; Rasbury, E. Troy; Hemming, N. Gary

2016-12-01

The global boron geochemical cycle is closely linked to recycling of geologic material via subduction processes that have occurred over billions of years of Earth’s history. The origin of carbonatites, unique melts derived from carbon-rich and carbonate-rich regions of the upper mantle, has been linked to a variety of mantle-related processes, including subduction and plume-lithosphere interaction. Here we present boron isotope (δ11B) compositions for carbonatites from locations worldwide that span a wide range of emplacement ages (between ~40 and ~2,600 Ma). Hence, they provide insight into the temporal evolution of their mantle sources for ~2.6 billion years of Earth’s history. Boron isotope values are highly variable and range between -8.6‰ and +5.5‰, with all of the young (<300 Ma) carbonatites characterized by more positive δ11B values (>-4.0‰), whereas most of the older carbonatite samples record lower B isotope values. Given the δ11B value for asthenospheric mantle of -7 +/- 1‰, the B isotope compositions for young carbonatites require the involvement of an enriched (crustal) component. Recycled crustal components may be sampled by carbonatite melts associated with mantle plume activity coincident with major tectonic events, and linked to past episodes of significant subduction associated with supercontinent formation.

Active-Interrogation Measurements of Induced-Fission Neutrons from Low-Enriched Uranium

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

J. L. Dolan; M. J. Marcath; M. Flaska

2012-07-01

Protection and control of nuclear fuels is paramount for nuclear security and safeguards; therefore, it is important to develop fast and robust controlling mechanisms to ensure the safety of nuclear fuels. Through both passive- and active-interrogation methods we can use fast-neutron detection to perform real-time measurements of fission neutrons for process monitoring. Active interrogation allows us to use different ranges of incident neutron energy to probe for different isotopes of uranium. With fast-neutron detectors, such as organic liquid scintillation detectors, we can detect the induced-fission neutrons and photons and work towards quantifying a sample’s mass and enrichment. Using MCNPX-PoliMi, amore » system was designed to measure induced-fission neutrons from U-235 and U-238. Measurements were then performed in the summer of 2010 at the Joint Research Centre in Ispra, Italy. Fissions were induced with an associated particle D-T generator and an isotopic Am-Li source. The fission neutrons, as well as neutrons from (n, 2n) and (n, 3n) reactions, were measured with five 5” by 5” EJ-309 organic liquid scintillators. The D-T neutron generator was available as part of a measurement campaign in place by Padova University. The measurement and data-acquisition systems were developed at the University of Michigan utilizing a CAEN V1720 digitizer and pulse-shape discrimination algorithms to differentiate neutron and photon detections. Low-enriched uranium samples of varying mass and enrichment were interrogated. Acquired time-of-flight curves and cross-correlation curves are currently analyzed to draw relationships between detected neutrons and sample mass and enrichment. In the full paper, the promise of active-interrogation measurements and fast-neutron detection will be assessed through the example of this proof-of-concept measurement campaign. Additionally, MCNPX-PoliMi simulation results will be compared to the measured data to validate the MCNPX-PoliMi code when used for active-interrogation simulations.« less

Identifying Hydrological Controls in the Lower Nelson River Basin utilizing Stable Water Isotopes

NASA Astrophysics Data System (ADS)

Delavau, C. J.; Smith, A. A.; Stadnyk, T.; Koenig, K.

2012-12-01

In 2010 a Stable Water Isotope (SWI) Monitoring Network was established within the lower Nelson River Basin (LNRB) (approximately 90,000 km2) in northern Manitoba, Canada, through a joint collaboration between the University of Manitoba and Manitoba Hydro (MH). The monitoring network encompasses over 60 sites where surface waters are regularly sampled, four sites sampling isotopes in precipitation, two sites utilizing drive point piezometers for the isotopic sampling of baseflow waters, and one site collecting evaporatively enriched water samples from an evaporation pan. In addition, two synoptic surveys have been completed in June 2011 and July 2012 to obtain annual snapshots of the monitoring network at a point in time. Currently, over 700 samples have been collected and analyzed. The LNRB contains approximately 9% of the total Nelson River Basin (NRB) drainage area, which encompasses an area of over 1 million km2. A diversion from the Churchill River through the Rat/Burntwood system routes an additional portion of flow into the northwest portion of the LNRB. The LNRB is significant to MH's network as it represents 75% of their power generation potential through six generating stations, thus resulting in a large portion of the basin being regulated. The watershed is topographically flat, therefore the movement and runoff of water, as well as isotopic composition of streamflow, is suspected to be highly impacted by changes in landscape and hydrography. The LNRB is a coniferous and wetland dominated basin, with almost 35% of the land cover composed of coniferous forest and 40% comprised of wetlands and lakes. Interpretation of the LNRB isotope framework shows that the major water sources (rainfall, snowfall, groundwater and surface waters) and rivers are isotopically distinct from one another. The main stem of the Nelson River shows little spatial or temporal variability, with an average δ18O of -10.6‰ and a standard deviation of 0.5‰ throughout the sampling period. Conversely, the main stem of the Burntwood River system shows increased variability relative to the Nelson River and overall is more depleted (average δ18O of -12.9‰ and a standard deviation of 0.75‰). Many of the headwater tributaries to the Nelson and Burntwood River systems such as Birchtree Brook, and the Minago, Gunisao, Grass, Odei, Footprint and Sapochi Rivers show large temporal and spatial variability due to relatively smaller drainage areas and differences in typology and connectivity. For this reason, further investigation into the correlation of land cover with isotopic composition is assessed for the aforementioned tributaries to better establish the hydrological controls (i.e., sources and sinks) for each sub-basin at the mesoscale. Results signify a strong relationship between percent wetland coverage and the slope of the Local Evaporation Line (SLEL) for headwater sub-basins (R2=0.99), indicating the likelihood of enhanced evaporative enrichment for sub-basins with increased wetland coverage. The collection of SWI's within the LNRB will help to develop a comprehensive understanding of water sources and cycling in this basin with the end goal of improving hydrological forecasting tools to predict, with improved certainty, future water availability for hydroelectric power production.

Neogene volcanism associated with back-arc basin tectonics at the northern Fossa Magna, NE Japan

NASA Astrophysics Data System (ADS)

Okamura, S.; Inaba, M.; Shinjo, R.; Adachi, Y.

2016-12-01

New isotopic and trace element data presented here imply a temporal change in magma sources and thermal conditions beneath the northern Fossa Magna of NE Japan from the Miocene to the Pliocene. Rocks from more sediment melt-rich Early Miocene volcanoes have less radiogenic 176Hf/177Hf and 143Nd/144Nd, high Zr/Hf, and little or no Hf anomaly (Hf/Hf*; ˜1.0). The mantle wedge in the Early Miocene consisted of enriched mantle source. We propose that during the onset of subduction, influx of hot asthenospheric mantle provided sufficient heat to partially melt newly subducting sediment. Geochemical modeling results suggest breakdown of zircon in the slab surface sediments for the Early Miocene lavas in the northern Fossa Magna region. In the Middle Miocene, the injection of hot and depleted asthenospheric material replaced the mantle beneath the northern Fossa Magna region of NE Japan. This caused the isotopic signature of the rocks to change from enriched to depleted. The Middle Miocene lavas characterized by most radiogenic Hf and Nd isotope ratios, have high Zr/Hf, low Lu/Hf, and little or no Hf anomaly. An appropriate working petrogenetic model is that the Middle Miocene lavas were derived from asthenospheric depleted mantle, slightly ( < 1%) contaminated by slab melt accompanied by full dissolution of zircon. All the Late Miocene and Pliocene samples are characterized by distinctly more radiogenic 176Hf/177Hf and 143Nd/144Nd, and more negative Hf anomalies (greater Hf/Hf* variability; ˜0.3). The Pliocene samples are displaced toward lower Hf/Hf* and Zr/Hf, and higher Lu/Hf relative to the Middle Miocene samples, which requires mixing between depleted mantle and a partial melt of subducted metasediment saturated with trace quantity of zircon.

Picrite "Intelligence" from the Middle-Late Triassic Stikine arc: Composition of mantle wedge asthenosphere

NASA Astrophysics Data System (ADS)

Milidragovic, D.; Zagorevski, A.; Weis, D.; Joyce, N.; Chapman, J. B.

2018-05-01

Primitive, near-primary arc magmas occur as a volumetrically minor ≤100 m thick unit in the Canadian Cordillera of northwestern British Columbia, Canada. These primitive magmas formed an olivine-phyric, picritic tuff near the base of the Middle-Late Triassic Stuhini Group of the Stikine Terrane (Stikinia). A new 40Ar/39Ar age on hornblende from a cross-cutting basaltic dyke constrains the tuff to be older than 221 ± 2 Ma. An 87Sr/86Sr isochron of texturally-unmodified tuff samples yields 212 ± 25 Ma age, which is interpreted to represent syn-depositional equilibration with sea-water. Parental trace element magma composition of the picritic tuff is strongly depleted in most incompatible trace elements relative to MORB and implies a highly depleted ambient arc mantle. High-precision trace element and Hf-Nd-Pb isotopic analyses indicate an origin by mixing of a melt of depleted ambient asthenosphere with ≤2% of subducted sediment melt. Metasomatic addition of non-conservative incompatible elements through melting of subducted Panthalassa Ocean floor sediments accounts for the arc signature of the Stuhini Group picritic tuff, enrichment of light rare earth elements (LREE) relative to heavy rare earth elements (HREE) and high field strength elements (HFSE), and anomalous enrichment in Pb. The inferred Panthalassan sediments are similar in composition to the Neogene-Quaternary sediments of the modern northern Cascadia Basin. The initial Hf isotopic composition of the picritic tuff closely approximates that of the ambient Middle-Late Triassic asthenosphere beneath Stikinia and is notably less radiogenic than the age-corrected Hf isotopic composition of the Depleted (MORB) Mantle reservoir (DM or DMM). This suggests that the ambient asthenospheric mantle end-member experienced melt depletion (F ≤ 0.05) a short time before picrite petrogenesis. The mantle end-member in the source of the Stuhini Group picritic tuff is isotopically similar to the mantle source of enriched mid-ocean ridge basalts (E-MORB) erupted today at the southern end of the Explorer Ridge in northeastern Pacific Ocean. The isotopic similarity between the Middle-Late Triassic ambient mantle under Stikinia, and mantle presently tapped at the southern Explorer Ridge suggests that enriched domains in the northeastern Pacific mantle are long-lived (≥222 million years).

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.

Evidence from mantle xenoliths for lithosphere removal beneath the central Rio Grande Rift

NASA Astrophysics Data System (ADS)

Byerly, Benjamin L.; Lassiter, John C.

2012-11-01

Seismic tomography beneath the Central Rio Grande Rift (RGR) at ˜34°N shows a low P and S wave velocity zone in the mantle that extends up the base of the Moho. This low-velocity region has been interpreted by (Gao et al., 2004) to be the result of convective removal of a portion of the once >100 km thick Proterozoic lithosphere. The amount of extension in the central RGR is thought to be low (˜25%) and thus cannot account for the amount of lithosphere thinning suggested by seismic tomography. We measured whole rock and mineral major element, trace element, and isotopic compositions of spinel-peridotite xenoliths erupted along the central axis of the rift (Elephant Butte) and the eastern margin of the Colorado Plateau (Cerro Chato) to determine their depth of origin and mantle provenance and to test the delamination hypothesis. If lithosphere removal has not occurred and the low P and S wave velocities are instead the result of hydration or melt infiltration in the lithosphere, then xenoliths erupted on the rift axis should have geochemical compositions similar to Proterozoic sub-continental lithospheric mantle (SCLM). At Cerro Chato, on the margin of the Colorado Plateau, xenoliths were derived from ˜60 km depth and have geochemical signatures similar to Proterozoic sub-continental lithospheric mantle (e.g. refractory major element compositions, LREE-enrichment, enriched Sr and Nd isotopes, unradiogenic Os isotopes). At Elephant Butte, along the central rift axis, two distinct groups of xenoliths are present. The majority of xenoliths from Elephant Butte are LREE-depleted and have fertile major element compositions. Additionally, these xenoliths have isotopic signatures similar to the range for DMM (e.g. 87Sr/86Sr ranging from 0.7018 to 0.7023, ɛNd ranging from 7 to 21, and 187Os/188Os ranging from 0.122 to 0.130). We interpret this group of xenoliths to be derived from asthenospheric mantle. A less-abundant group of xenoliths at Elephant Butte are LREE enriched, have refractory major element compositions, enriched Sr, Nd, and Pb isotopes, and unradiogenic Os isotopes. These are characteristic of Proterozoic SCLM. Both groups of xenoliths from Elephant Butte are derived from ˜45 km depth. We interpret the suite of xenoliths at Elephant Butte to have sampled what was recently the base of the Proterozoic SCLM. We conclude that a portion of the mantle lithosphere has been removed which allowed modern convecting mantle (DMM) to be emplaced at the base of the pre-existing SCLM.

Ion probe measurements of carbon and nitrogen in iron meteorites

NASA Astrophysics Data System (ADS)

Sugiura, Naoji

1998-05-01

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

Tracing the hydrological cycle by water stable isotopes on the Tibetan plateau

NASA Astrophysics Data System (ADS)

Tian, L.; Yao, T.; Yu, W.

2013-05-01

A network of precipitation, river, lake water, ice core and atmospheric vapor sampling was set up on the Tibetan Plateau to trance the moisture origins supplied to the plateau, the inland hydrological cycle process and land surface evaporation processes. This work shows different moisture from Indian Ocean monsoon and the westerlies dominate the precipitation δ18O in the south and north of the plateau respectively, which can cause a difference in precipitation δ18O of about 5‰ in average. Precipitation δ18O bears "temperature effect" in the northern Tibetan Plateau, whereas the seasonal precipitation δ18O shows precipitation "amount effect" in the south. This relation is also held in the ice core records on the plateau. An instance is the δ18O record from shallow ice cores in Muztagata Glacier, Dunde ice cap and Naimona'Nyi Glacier. The ice core δ18O record from monsoon region in south Tibet, such as Dasuopu glacier in Xixiabangma, shows a precipitation "amount effect" at least in the annual scale. Further isotope enrichment can be found in the land surface evaporation processes. A simple case is in the close lake system in Yamdruk-tso catchment, southern part of Tibetan Plateau. Both observation and simulation work shows the enrichment of heavy isotope in lake water can be over 10‰ for δ18O, which is much linked to the local climatic condition. Simulation work also shows that atmospheric vapor isotope is also very important to capture the lake water δD value. However, vapor isotopes data are usually less available on the plateau.

Investigating the Relationship Between Soil Water Mobility and Stable Isotope Composition with Implications for the Ecohydrologic Separation Hypothesis

NASA Astrophysics Data System (ADS)

Shuler, J.; McNamara, J. P.; Benner, S. G.; Kohn, M. J.; Evans, S.

2017-12-01

The ecohydrologic separation (ES) hypothesis states that streams and plants return different soil water compartments to the atmosphere and that these compartments bear distinct isotopic compositions that can be used to infer soil water mobility. Recent studies have found isotopic evidence for ES in a variety of ecosystems, though interpretations of these data vary. ES investigations frequently suffer from low sampling frequencies as well as incomplete or missing soil moisture and matric potential data to support assumptions of soil water mobility. We sampled bulk soil water every 2-3 weeks in the upper 1 m of a hillslope profile from May 2016 to July 2017 in a semi-arid watershed outside Boise, ID. Twig samples of three plant species were also collected concurrently. Plant and soil water samples extracted via cryogenic vacuum distillation were analyzed for δ2H and δ18O composition. Soil moisture and soil matric potential sensors were installed at five and four depths in the profile, respectively. Shallow bulk soil water was progressively enriched in both isotopes over the growing season and plotted along a soil evaporation line in a plot of δ2H versus δ18O. Plant water during the growing season plotted below both the Local Meteoric Water Line and soil evaporation line. Plant water isotopic composition could not be traced to any source sampled in this study. Additionally, soil moisture and matric potential data revealed that soils were well-drained and that mobile soil water was unavailable throughout most of the growing season at the depths sampled. Soil water isotopic composition alone failed to predict mobility as observed in soil moisture and matric potential data. These results underscore the need for standard hydrologic definitions for the mobile and immobile compartments of soil water in future studies of the ES hypothesis and ecohydrologic processes in general.

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

USGS Publications Warehouse

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

2013-01-01

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

Individual-specific transgenerational marking of fish populations based on a barium dual-isotope procedure.

PubMed

Huelga-Suarez, Gonzalo; Moldovan, Mariella; Garcia-Valiente, America; Garcia-Vazquez, Eva; Alonso, J Ignacio Garcia

2012-01-03

The present study focuses on the development and evaluation of an individual-specific transgenerational marking procedure using two enriched barium isotopes, (135)Ba and (137)Ba, mixed at a given and selectable molar ratio. The method is based on the deconvolution of the isotope patterns found in the sample into four molar contribution factors: natural xenon (Xe nat), natural barium (Ba nat), Ba135, and Ba137. The ratio of molar contributions between Ba137 and Ba135 is constant and independent of the contribution of natural barium in the sample. This procedure was tested in brown trout ( Salmo trutta ) kept in captivity. Trout were injected with three different Ba137/Ba135 isotopic signatures ca. 7 months and 7 days before spawning to compare the efficiency of the marking procedure at long and short term, respectively. The barium isotopic profiles were measured in the offspring by means of inductively coupled plasma mass spectrometry. Each of the three different isotopic signatures was unequivocally identified in the offspring in both whole eggs and larvae. For 9 month old offspring, the characteristic barium isotope signatures could also be detected in the otoliths even in the presence of a high and variable amount of barium of natural isotope abundance. In conclusion, it can be stated that the proposed dual-isotope marking is inheritable and can be detected after both long-term and short-term marking. Furthermore, the dual-isotope marking can be made individual-specific, so that it allows identification of offspring from a single individual or a group of individuals within a given fish group. © 2011 American Chemical Society

Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

NASA Astrophysics Data System (ADS)

Horst, A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

2015-12-01

Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

Speleothem records of changes in the South American Summer Monsoon during MIS stages 5 and 6

NASA Astrophysics Data System (ADS)

Burns, S. J.; Kanner, L.; Cheng, H.; Edwards, R.

2011-12-01

Little information exists about the behavior of the South American Summer Monsoon prior to the Last Glacial Period. Speleothems from the Peruvian Altiplano are one possible archive of SASM intensity because oxygen isotopes of rainfall on the Altiplano are primarily controlled by the intensity of rainfall in upstream moisture source region, the Amazon Basin. Here, we present results from a two speleothems collected from Gruta de Huagapo, a cave in the central Peruvian Altiplano (12°S, 76°W, ~3800m elevation). The samples grew from approximately 115-125 ky BP and from 136-168 ky BP, spanning time periods equivalent to much of MIS stage 5e and the transition into MIS 5d and MIS 6. Chronologies were determined by U-Th dating techniques and the dates are in stratigraphic with analytical errors < 0.4%. 100 preliminary δ18O values were micromilled from each sample along the growth axis. Oxygen isotopic values of the younger sample, stalagmite P10-H1, range from -12.5% to -16.5%. The overall trend in isotopic values generally parallels summer insolation, with more depleted values associated with greater insolation. The most enriched values, between -12.5% and -13.5% occur from 121-125 ky BP, with an abrupt transition to more depleted values at 121 ky BP. The values plateau at about -15% until 117 ky BP, then abruptly decrease again to around -16 % for the rest of the record. The enriched values during the middle and latter parts of MIS 5e suggest a weakened monsoon during that time and coincide with observed low lake levels at Lake Titicaca (Fritz et al, 2007). At present we have isotopic data from only the youngest 10 ky of the older sample. The values are generally more depleted, with most between -16% and -17%, suggesting an intensified SASM during MIS 6 as compared to 5e. A rapid increase in δ18O occurs at ~136 ky BP. Overall the trends in the data parallel major changes in δD from EPICA, but appear to lead the Antarctic time series by ~2 ky.

Evaluating climate controls on isotopic shifts in high-altitude forests during the Last Interglacial

NASA Astrophysics Data System (ADS)

Insel, N.; Berkelhammer, M. B.; Sturm, C.; Karimova, G.

2016-12-01

Forests play a significant role in the global carbon cycle, and influence climate through their effect on albedo and latent heat flux. Predicting the response of these ecosystems to climate change is complicated by competing influences between rising CO2, warming, and shifts in hydrology such as timing, rate, and type of precipitation. A key to detection and prediction of future regional and global changes of modern ecosystems lies in understanding the causes and characteristics of historical variations at the ecosystem level. The Last Interglacial (LIG: 130 to 116 ka) is the most recent period in Earth's history when growing season temperature exceeded those of today. In this study, we are using isotope-enabled regional climate model (REMOiso) simulations under LIG (115ka, 125 ka and 135 ka) and modern forcings to evaluate climate controls on boreal forest in the western US. In particular, we investigate (1) changes in moisture sources and moisture transport, (2) changes in the annual and seasonal extent and duration of precipitation, and (3) temperature variations to explore how ecosystem carbon and water fluxes change under coupled temperature and precipitation variability. Eemian wood samples from the Rocky Mountains in Colorado show a progressive increase in the 18O seasonal cycle that may be related to trees utilizing isotopically enriched monsoonal moisture. However, Eemian climate simulations (125ka) incorporate orbital forcings that result in stronger seasonal changes in temperature, precipitation, and snow cover in comparison to today, while annual anomalies are small. The seasonal shift in climate affects the water availability and the length of growing season for Eemian plants. Model results indicate only a very slight increase in monsoonal moisture transport from the south, resulting in slightly wetter conditions in western Colorado, but slightly drier conditions in the eastern part. Preliminary results suggest that changes in the North American monsoon system were not sufficient to explain the observed isotopic enrichment in Eemian wood samples. Current isotope simulations address changes in the seasonal isotopic cycle in the precipitation during the Eemian and will allow us to distinguish tree's reliance on summer or winter moisture sources more clearly.

Silicon isotopes in angrites and volatile loss in planetesimals

PubMed Central

Moynier, Frédéric; Savage, Paul S.; Badro, James; Barrat, Jean-Alix

2014-01-01

Inner solar system bodies, including the Earth, Moon, and asteroids, are depleted in volatile elements relative to chondrites. Hypotheses for this volatile element depletion include incomplete condensation from the solar nebula and volatile loss during energetic impacts. These processes are expected to each produce characteristic stable isotope signatures. However, processes of planetary differentiation may also modify the isotopic composition of geochemical reservoirs. Angrites are rare meteorites that crystallized only a few million years after calcium–aluminum-rich inclusions and exhibit extreme depletions in volatile elements relative to chondrites, making them ideal samples with which to study volatile element depletion in the early solar system. Here we present high-precision Si isotope data that show angrites are enriched in the heavy isotopes of Si relative to chondritic meteorites by 50–100 ppm/amu. Silicon is sufficiently volatile such that it may be isotopically fractionated during incomplete condensation or evaporative mass loss, but theoretical calculations and experimental results also predict isotope fractionation under specific conditions of metal–silicate differentiation. We show that the Si isotope composition of angrites cannot be explained by any plausible core formation scenario, but rather reflects isotope fractionation during impact-induced evaporation. Our results indicate planetesimals initially formed from volatile-rich material and were subsequently depleted in volatile elements during accretion. PMID:25404309

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

PubMed

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

2008-01-01

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

Assessment of the Interstellar Processes Leading to Deuterium Enrichment in Meteoritic Organics

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Bernstein, Max P.; Dworkin, Jason P.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer has been deuterium (D). We discuss four processes that are expected to lead to D enrichment in interstellar materials and describe how their unique characteristics can be used to assess their relative importance for the organics in meteorites. These enrichment processes are low temperature gas phase ion-molecule reactions, low temperature gas-grain reactions, gas phase unimolecular photodissociation, and ultraviolet photolysis in D-enriched ice mantles. Each of these processes is expected to be associated with distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.), especially in the molecular population of polycyclic aromatic hydrocarbons (PAHs). We describe these differences and discuss how they may be used to delineate the various interstellar processes that may have contributed to meteoritic D enrichments. We also briefly discuss how these processes may affect the isotopic distributions in C, 0, and N in the same compounds.

Midcontinent rift volcanism in the Lake Superior region: Sr, Nd, and Pb isotopic evidence for a mantle plume origin

USGS Publications Warehouse

Nicholson, S.W.; Shirey, S.B.

1990-01-01

Between 1091 and 1098 Ma, most of a 15- to 20-km thickness of dominantly tholeiitic basalt erupted in the Midcontinent Rift System of the Lake Superior region, North America. The Portage Lake Volcanics in Michigan, which are the younget MRS flood basalts, fall into distinctly high- and low-TiO2 types having different liquid lines of descent. Incompatible trace elements in both types of tholeiites are enriched compared to depleted or primitive mantle and both basalt types are isotopically indistinguishable. The isotopic enrichment of the MRS source compared to depleted mantle is striking and must have occurred at least 700 m.y. before 1100 Ma. There are two likely sources for such magmatism: subcontinental lithospheric mantle enriched during the early Proterozoic or enriched mantle derived from an upwelling plume. Decompression melting of an upwelling enriched mantle plume in a region of lithosphere thinned by extension could have successfully generated the enormous volume (850 ?? 103 km3) of relatively homogeneous magma in a restricted time interval. -from Authors

The application of chemical and isotopic tracers to characterize aerosol sources and processing in marine air

NASA Astrophysics Data System (ADS)

Turekian, Vaughan Charles

2000-12-01

Aerosol production, transport, chemical and physical evolution and deposition impact the environment by influencing radiation budgets, altering the composition of the atmosphere, and delivering nutrients to marine and terrestrial ecosystems. The objective of this research was to combine high-resolution chemical measurements with stable isotopic analysis in order to characterize the sources and processing of carbon, nitrogen and sulfur bearing compounds, associated with sized aerosols on Bermuda, during spring. Chemical tracers combined with forward and backward trajectories demonstrated the transport of biomass burning products from North America to Bermuda. The size distributions of NH4+ from 1998 differed from those during spring, 1997, a year without the large-scale burning. These results suggest that transport of biomass burning products altered the pH of the aerosols. Marine and continentally derived carbon was associated with all aerosol size fractions. Supermicron radius sea- salt aerosol was enriched in marine derived carbon by 2 orders of magnitude compared to bulk surface seawater. Enrichments of oxalate relative to methanesulfonic acid (MSA) in supermicron radius aerosol suggested in situ formation of oxalate within the sea-salt solution, or direct injection from the organic rich surface microlayer. Compound specific isotope analysis of oxalic acid, indicated a marine source for all aerosol size fractions, indicating formation from in the gas phase for the submicron radius aerosol. Stable sulfur isotopes indicated that the biogenic non- sea-salt (nss) SO42-/MSA ratio varied with aerosol size indicating that MSA may not be a conservative tracer of biogenic nss SO4 2- in bulk aerosol sampling. The calculated biogenic nss SO 42-/MSA based on stable isotopes and sized aerosol sampling, was 3 times lower than previous estimates for Bermuda. Stable nitrogen isotope values for submicron and supermicron aerosol where significantly different, consistent with their different chemical compositions. Results suggested that HNO3 incorporation into supermicron aerosol was essentially unidirectional whereas submicron aerosol was both a source and a sink for NH3(g). Variable aerosol liquid water content over the relatively longer atmospheric lifetimes of submicron aerosol may lead to multiple NH3 phase changes. This study was the first to combine sized aerosol sampling, high-resolution chemical analysis and multiple stable isotopes to characterize both the sources and the processing of aerosols in marine air. The results of this study, therefore, provide crucial information for source apportionment of environmentally important atmospheric species in continentally impacted, marine air.

Molybdenum isotopic evidence for the origin of chondrules and a distinct genetic heritage of carbonaceous and non-carbonaceous meteorites

NASA Astrophysics Data System (ADS)

Budde, Gerrit; Burkhardt, Christoph; Brennecka, Gregory A.; Fischer-Gödde, Mario; Kruijer, Thomas S.; Kleine, Thorsten

2016-11-01

Nucleosynthetic isotope anomalies are powerful tracers to determine the provenance of meteorites and their components, and to identify genetic links between these materials. Here we show that chondrules and matrix separated from the Allende CV3 chondrite have complementary nucleosynthetic Mo isotope anomalies. These anomalies result from the enrichment of a presolar carrier enriched in s-process Mo into the matrix, and the corresponding depletion of this carrier in the chondrules. This carrier most likely is a metal and so the uneven distribution of presolar material probably results from metal-silicate fractionation during chondrule formation. The Mo isotope anomalies correlate with those reported for W isotopes on the same samples in an earlier study, suggesting that the isotope variations for both Mo and W are caused by the heterogeneous distribution of the same carrier. The isotopic complementary of chondrules and matrix indicates that both components are genetically linked and formed together from one common reservoir of solar nebula dust. As such, the isotopic data require that most chondrules formed in the solar nebula and are not a product of protoplanetary impacts. Allende chondrules and matrix together with bulk carbonaceous chondrites and some iron meteorites (groups IID, IIIF, and IVB) show uniform excesses in 92Mo, 95Mo, and 97Mo that result from the addition of supernova material to the solar nebula region in which these carbonaceous meteorites formed. Non-carbonaceous meteorites (enstatite and ordinary chondrites as well as most iron meteorites) do not contain this material, demonstrating that two distinct Mo isotope reservoirs co-existed in the early solar nebula that remained spatially separated for several million years. This separation was most likely achieved through the formation of the gas giants, which cleared the disk between the inner and outer solar system regions parental to the non-carbonaceous and carbonaceous meteorites. The Mo isotope dichotomy of meteorites provides a new means to determine the provenance of meteoritic and planetary materials, and to assess genetic links between chondrites and differentiated meteorites.

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.

Creating 13C- and 15N-enriched tree leaf litter for decomposition experiments

NASA Astrophysics Data System (ADS)

Szlavecz, K. A.; Pitz, S.; Chang, C.; Bernard, M.

2013-12-01

Labeling plant material with heavy isotopes of carbon and nitrogen can produce a traceable nutrient signal that can be followed into the different trophic levels and decomposer food web. We treated 60 tree saplings with 13C-enriched CO2 gas and 15N-enriched ammonium nitrate over a three-month period to create dually-labeled plant material for future decomposition experiments. The trees included both early (Red maple, Sweetgum, Tulip poplar) and late (American beech, White oak) successional deciduous tree species, and a conifer, White pine. We constructed a 2.4 m × 2.4 m × 2.4 m environmental chamber that was climate-controlled using an air conditioning system. An Arduino microcontroller interfaced with a Vaisala GMP343 CO2 probe maintained a CO2 concentration between 500-520 ppm by controlling a solenoid valve on the CO2 tank regulator. The trees were placed into the chamber in August 2012 and remained until senescence unless they were lost to death or disease. Ammonium nitrate was added twice, in September and October. Leaf samples were collected prior to the start of the experiment and after senescence, whereas root samples were collected only in December. Samples were dried, ground and analyzed using an isotope ratio mass spectrometer. American beech and White oak had 40% mortality, and 34% of tulip poplar trees were removed because of powdery mildew overgrowth or death. Most tulip poplar trees exhibited a second leaf out following senescence in late September. Nearly 1 kg of litter was produced with tulip poplar representing over half of the total mass. Levels of enrichment varied greatly by species. Beech (-14.2‰) and White oak (-4.8‰) had low levels of enrichment in comparison to early successional species such as Sweetgum (41.7‰) and Tulip poplar (30.7‰ [first leaf fall] and 238.0‰ [second leaf fall]). Leaf enrichment with 15N followed a similar pattern, though it was achieved at a higher level with δ15N values varying from 271.6‰ to 1354.2‰ at the end of the experiment. Enrichment of roots was significantly higher than leaves (δ13C range: 111.5-219.2‰; δ15N range: 1516.9-3939.3‰) indicating that nutrients were translocated away from leaves prior to senescence, which is supported by the increase in C:N ratio between the initial (19.0) and final (60.1) leaf sampling. Despite the variable levels of enrichment, leaves from all species were sufficiently labeled for use in future studies aimed at tracking the transformation of carbon and nitrogen during decomposition. The greatest challenges were treating diseases and pests and creating ideal growing conditions for many species within the same chamber. Reducing the number of individuals and better pest management will lead to even higher level enrichment in the future.

Evolution of carbon isotope signatures during reactive transport of hydrocarbons in heterogeneous aquifers.

PubMed

Höyng, Dominik; Prommer, Henning; Blum, Philipp; Grathwohl, Peter; D'Affonseca, Fernando Mazo

2015-03-01

Compound-specific isotope analysis (CSIA) of organic pollutants has become a well-established tool for assessing the occurrence and extent of biodegradation processes in contaminated aquifers. However, the precision of CSIA is influenced by the degree to which assumptions underlying CSIA data interpretation hold under realistic field-scale conditions. For the first time this study demonstrates how aquifer analogs combined with reactive transport models offer an underexplored way to develop generic process understanding, evaluate monitoring and quantification strategies in highly heterogeneous subsurface settings. Data from high-resolution aquifer analogs were used in numerical experiments to track the propagation of a representative oxidizable organic compound (toluene) within a variety of realistic heterogeneous aquifers and to investigate its detailed fate. The simulations were used to analyze (1) the effects of physical aquifer heterogeneities on spatiotemporal patterns of contaminant concentrations and isotope signatures, (2) the performance of the commonly applied Rayleigh equation and (3) the applicability of an extension of the Rayleigh equation for complex hydrogeological conditions. The results indicate that if field-derived enrichment factors are applied without corrections for dilution, the conventional Rayleigh equation is inaccurate and estimates for biodegradation are typically overestimated and unreliable in heterogeneous aquifers. Underestimations can occur due to the partial source zone depletion. In contrast, if dilution can be accurately accounted for, field-derived enrichment factors comprise a suitable alternative to laboratory-derived and redox-specific enrichment factors. The study also examines to what extent variations in monitoring/sampling strategies influence the obtained results. Especially measurements from long-screened wells (>1 m) reveal to be inappropriate for the application of the Rayleigh equation in the investigated aquifer analogs, as low resolution data sampled from the simulated scenarios only enable a qualitative assessment of biodegradation. Measurements from both long- and short-screened wells employing the Rayleigh equation streamline approach are only partly viable for in situ biodegradation measurements in heterogeneous systems. Copyright © 2015 Elsevier B.V. All rights reserved.

Authigenic carbonate formation at hydrocarbon seeps in continental margin sediments: A comparative study

USGS Publications Warehouse

Naehr, T.H.; Eichhubl, P.; Orphan, V.J.; Hovland, M.; Paull, C.K.; Ussler, W.; Lorenson, T.D.; Greene, H. Gary

2007-01-01

Authigenic carbonates from five continental margin locations, the Eel River Basin, Monterey Bay, Santa Barbara Basin, the Sea of Okhotsk, and the North Sea, exhibit a wide range of mineralogical and stable isotopic compositions. These precipitates include aragonite, low- and high-Mg calcite, and dolomite. The carbon isotopic composition of carbonates varies widely, ranging from -60??? to +26???, indicating complex carbon sources that include 13C-depleted microbial and thermogenic methane and residual, 13C-enriched, bicarbonate. A similarly large variability of ??18O values (-5.5??? to +8.9???) demonstrates the geochemical complexity of these sites, with some samples pointing toward an 18O-enriched oxygen source possibly related to advection of 18O-enriched formation water or to the decomposition of gas hydrate. Samples depleted in 18O are consistent with formation deeper in the sediment or mixing of pore fluids with meteoric water during carbonate precipitation. A wide range of isotopic and mineralogical variation in authigenic carbonate composition within individual study areas but common trends across multiple geographic areas suggest that these parameters alone are not indicative for certain tectonic or geochemical settings. Rather, the observed variations probably reflect local controls on the flux of carbon and other reduced ions, such as faults, fluid conduits, the presence or absence of gas hydrate in the sediment, and the temporal evolution of the local carbon reservoir. Areas with seafloor carbonates that indicate formation at greater depth below the sediment-water interface must have undergone uplift and erosion in the past or are still being uplifted. Consequently, the occurrence of carbonate slabs on the seafloor in areas of active hydrocarbon seepage is commonly an indicator of exhumation following carbonate precipitation in the shallow subsurface. Therefore, careful petrographic and geochemical analyses are critical components necessary for the correct interpretation of processes related to hydrocarbon seepage in continental margin environments and elsewhere. ?? 2007 Elsevier Ltd. All rights reserved.

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.

Carbon isotopic fractionation in heterotrophic microbial metabolism

NASA Technical Reports Server (NTRS)

Blair, N.; Leu, A.; Munoz, E.; Olsen, J.; Kwong, E.; Des Marais, D.

1985-01-01

Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4 percent depleted in C-13 relative to the glucose used as the carbon source, whereas the acetate was 12.3 percent enriched in C-13. The acetate C-13 enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6 percent depleted in C-13, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7 percent, respectively. Aspartic and glutamic acids were -1.6 and +2.7 percent, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle.

Isotopic analysis of N and O in nitrite and nitrate by sequential selective bacterial reduction to N2O

USGS Publications Warehouse

Böhlke, J.K.; Smith, R.L.; Hannon, J.E.

2007-01-01

Nitrite is an important intermediate species in the biogeochemical cycling of nitrogen, but its role in natural aquatic systems is poorly understood. Isotopic data can be used to study the sources and transformations of NO2- in the environment, but methods for independent isotopic analyses of NO2- in the presence of other N species are still new and evolving. This study demonstrates that isotopic analyses of N and O in NO2- can be done by treating whole freshwater or saltwater samples with the denitrifying bacterium Stenotrophomonas nitritireducens, which selectively reduces NO2- to N2O for isotope ratio mass spectrometry. When calibrated with solutions containing NO2- with known isotopic compositions determined independently, reproducible δ15N and δ18O values were obtained at both natural-abundance levels (±0.2−0.5‰ for δ15N and ±0.4−1.0‰ for δ18O) and moderately enriched 15N tracer levels (±20−50‰ for δ15N near 5000‰) for 5−20 nmol of NO2- (1−20 μmol/L in 1−5 mL aliquots). This method is highly selective for NO2-and was used for mixed samples containing both NO2- and NO3- with little or no measurable cross-contamination. In addition, mixed samples that were analyzed with S. nitritireducens were treated subsequently with Pseudomonas aureofaciens to reduce the NO3- in the absence of NO2-, providing isotopic analyses of NO2- and NO3- separately in the same aliquot. Sequential bacterial reduction methods like this one should be useful for a variety of isotopic studies aimed at understanding nitrogen cycling in aquatic environments. A test of these methods in an agricultural watershed in Indiana provides isotopic evidence for both nitrification and denitrification as sources of NO2- in a small stream.

Carbon and nitrogen stable isotope analysis of three types of oyster tissue in an impacted estuary

NASA Astrophysics Data System (ADS)

Piola, Richard F.; Moore, Stephanie K.; Suthers, Iain M.

2006-01-01

The stable isotope ratios of carbon ( δ13C) and nitrogen ( δ15N) of the muscle, ctenidia and viscera of the Sydney rock oyster, Saccostrea glomerata, showed the dilution and assimilation of tertiary treated sewage along an estuarine gradient. The enriched 15N values of oyster ctenidia and viscera from within 50 m of the sewage outfall indicated the use of 15N-enriched tertiary treated sewage effluent (16 ± 2.3‰) as a nutrient source. The effect of sewage nitrogen on oyster δ15N was localised, with oysters 5 km upstream and downstream of the outfall not significantly enriched. Viscera δ15N was most sensitive to sewage nutrients and δ13C significantly defined an ocean-to-estuarine gradient. High variance in isotope ratios of viscera compromised its use as an indicator of anthropogenic nutrients, and this also reduced the utility of whole-body stable isotope ratios. Ctenidia was the most useful indicator tissue of sewage discharge at the scale of this study, being consistently and significantly enriched in δ15N close to the sewage outfall and δ13C clearly defined an estuarine gradient with less internal variability than viscera. Muscle δ15N was least sensitive to sewage effluent and showed the least variability, making it more suited to investigations of anthropogenic nutrient enrichment over larger spatio-temporal scales.

Solar helium and neon in the Earth

NASA Technical Reports Server (NTRS)

Honda, M.; Mcdougall, I.; Patterson, D. B.

1994-01-01

Neon isotopic compositions in mantle-derived samples commonly are enriched in (20)Ne and (21)Ne relative to (22)Ne compared with atmospheric neon ((20)Ne/(22)Ne and (21)Ne/(22)Ne ratios in atmospheric neon are 9.8 and 0.029, respectively), together with significant primordial (3)He. Such results have been obtained on MORB's, intraplate plume-related oceanic island basalts, backarc basin basalts, mantle xenoliths, ancient diamonds and CO2 well gases (e.g., 1 - 8). The highest (20)Ne/(22)Ne ratio observed in MORB glasses (= 13.6 plus or minus 1.3 is close to the solar value (= 13.6, as observed in solar wind). In order to explain the enrichment of (20)Ne and (21)Ne relative to atmospheric neon for samples derived from the mantle, it is necessary to postulate the presence of at least two distinct non-atmospheric components. The two most likely candidates are solar and nucleogenic ((20)Ne/(22)Ne solar = 13.6 (21)Ne/(22)Ne solar = 0.032, (20)Ne/(22)Ne nucleogenic = 2.5 and (21)Ne/(22)Ne nucleogenic = 32). This is because solar neon is the only known component with a (20)Ne/(22)Ne ratio greater than both the atmospheric value and that observed in samples derived from the mantle. Nucleogenic neon is well known to elevate (21)Ne/(22)Ne ratios. Neon isotopic signatures observed in mantle-derived samples can be accounted for by mixing of the three neon end members: solar, nucleogenic and atmospheric.

Distribution and Source Identification of Pb Contamination in industrial soil

NASA Astrophysics Data System (ADS)

Ko, M. S.

2017-12-01

INTRODUCTION Lead (Pb) is toxic element that induce neurotoxic effect to human, because competition of Pb and Ca in nerve system. Lead is classified as a chalophile element and galena (PbS) is the major mineral. Although the Pb is not an abundant element in nature, various anthropogenic source has been enhanced Pb enrichment in the environment after the Industrial Revolution. The representative anthropogenic sources are batteries, paint, mining, smelting, and combustion of fossil fuel. Isotope analysis widely used to identify the Pb contamination source. The Pb has four stable isotopes that are 208Pb, 207Pb, 206Pb, and 204Pb in natural. The Pb is stable isotope and the ratios maintain during physical and chemical fractionation. Therefore, variations of Pb isotope abundance and relative ratios could imply the certain Pb contamination source. In this study, distributions and isotope ratios of Pb in industrial soil were used to identify the Pb contamination source and dispersion pathways. MATERIALS AND METHODS Soil samples were collected at depth 0­-6 m from an industrial area in Korea. The collected soil samples were dried and sieved under 2 mm. Soil pH, aqua-regia digestion and TCLP carried out using sieved soil sample. The isotope analysis was carried out to determine the abundance of Pb isotope. RESULTS AND DISCUSSION The study area was developed land for promotion of industrial facilities. The study area was forest in 1980, and the satellite image show the alterations of land use with time. The variations of land use imply the possibilities of bringing in external contaminated soil. The Pb concentrations in core samples revealed higher in lower soil compare with top soil. Especially, 4 m soil sample show highest Pb concentrations that are approximately 1500 mg/kg. This result indicated that certain Pb source existed at 4 m depth. CONCLUSIONS This study investigated the distribution and source identification of Pb in industrial soil. The land use and Pb concentration at depth indicated elusive contamination event or contamination sources. In order to identify the contamination source clearly, isotope and Pb compound/mineralogy analysis are necessary.

Origin of low δ26Mg basalts with EM-I component: Evidence for interaction between enriched lithosphere and carbonated asthenosphere

NASA Astrophysics Data System (ADS)

Tian, H.; Yang, W.; Li, S. G.; Ke, S.; Chu, Z. Y.

2016-12-01

Many studies have focused on the interactions between recycled materials and depleted mantle to explain the origins of EM and HIMU components (e.g., Cohen and O'Nions, 1982; White and Hofmann, 1982). However, little is known about the interactions between recycled materials and enriched mantle and the associated consequences, e.g., late recycled crustal material overprints mantle previously enriched by earlier recycling events of the crust. Recently, light Mg isotopic composition of the basalts from North China Craton (NCC) and South China Block (SCB) has been attributed to recycled carbonate metasomatism from subducted Pacific slab (Yang et al., 2012; Huang et al., 2015). If this explanation is correct, the Cenozoic basalts from Northeast (NE) China should also contain light Mg isotopic compositions. The basalts from NE China have EMI Sr-Nd-Pb isotopic features that are distinct from the NCC and SCB basalts, indicating the contribution of an enriched mantle source (Choi et al., 2006; Chu et al., 2013). Therefore, Mg isotopic compositions of the Cenozoic basalts from NE China will help to determine the interaction between recycled sedimentary carbonates and an enriched mantle. Consistent with the hypothesis, our results show that the Cenozoic basalts from Wudalianchi and Erkeshan, NE China, have homogeneous and light Mg isotopic compositions (δ26Mg =-0.57 to -0.46‰). Based on the similarity to the basalts from NCC and SCB, their light Mg isotopic feature should also be derived from carbonate metasomatism (i.e. carbonated asthenosphere). In addition to that, a question arise that why the interaction between carbonated asthenosphere and the EM-I SLCM significantly modify the trace element and Sr-Nd-Pb isotopic composition of the mantle-derived melt, but have little effect on the Mg isotopes? The possible mechanism is the interaction between low SiO2 melt and peridotite, which converts pyroxene to olivine, as reported in previous studies (e.g., Kelemen et al., 1992; Edwards and Malpas, 1996; Zhou et al., 1996, 2014). During the interaction, the trace elements of the EM-I SCLM largely entered the melt, and all Mg was transferred from Opx and Cpx into the newly formed olivine. Consequently, the Wudalianchi and Erkeshan basalts preserve low δ26Mg and obtain EM-I Sr-Nd-Pb isotopic compositions (Fig. 1).

Isotope separation by photodissociation of Van der Waal's molecules

DOEpatents

Lee, Yuan T.

1977-01-01

A method of separating isotopes based on the dissociation of a Van der Waal's complex. A beam of molecules of a Van der Waal's complex containing, as one partner of the complex, a molecular species in which an element is present in a plurality of isotopes is subjected to radiation from a source tuned to a frequency which will selectively excite vibrational motion by a vibrational transition or through electronic transition of those complexed molecules of the molecular species which contain a desired isotope. Since the Van der Waal's binding energy is much smaller than the excitational energy of vibrational motion, the thus excited Van der Waal's complex dissociate into molecular components enriched in the desired isotope. The recoil velocity associated with vibrational to translational and rotational relaxation will send the separated molecules away from the beam whereupon the product enriched in the desired isotope can be separated from the constituents of the beam.

Experimental identification of mechanisms controlling calcium isotopic fractionations by the vegetation.

NASA Astrophysics Data System (ADS)

Cobert, Florian; Schimtt, Anne-Désirée.; Bourgeade, Pascale; Stille, Peter; Chabaux, François; Badot, Pierre-Marie; Jaegler, Thomas

2010-05-01

This study aims to better understand the role of vegetation on the Ca cycle at the level of the critical zone of the Earth, in order to specify the mechanisms controlling the Ca absorption by plants at the rock/plant interface. To do this, we performed experiments using hydroponic plant cultures in a way that we could control the co-occuring geochemical and physiological process and determine the impact of the nutritive solution on the Ca cycle within plants. A dicotyledon and calcicole plant with rapid growth, the French bean (Phaseolus vulgaris L.), has been chosen to have access to one complete growth cycle. Several experiments have been conducted with two Ca concentrations, 6 (L) and 60 (H) ppm and two pH values (4 and 6) in the nutritive solution, for which the Ca concentration was maintained constant, so its Ca content is considered as infinite. A second experiment (non infinite L6) allowed Ca depletion in the solution through time; therefore, response effects on the Ca isotopic signatures in the plant organs and in the nutritive solution were observed. We determined Ca concentrations and isotopic ratios in the nutritive solution and in different organs (main roots, secondary roots, old and young stems, old and young leaves and fruits) at two different growth stages (10 days and 6 weeks). Preliminary results show that: (1) the roots (main and secondary) were enriched in the light isotope (40Ca) compared to the nutritive solution, and leaves were enriched in the heavy isotope (44Ca) compared to stems. These results are in accord with previously published field studies (Wigand et al., 2005; Page et al., 2008; Cenki-Tok et al., 2009; Holmden and Bélanger, 2010). Leaves and secondary roots were however enriched in the heavy isotope (44Ca) compared to bean pods, stems and main roots. These results could be related to kinetic fractionation processes occurring either during the Ca root uptake, or during the Ca transport within the plant, or physiological mechanisms occurring first at the level of secondary roots, and second at the level of leaves. (2) No Ca isotope difference was observed neither between old and young organs, (except for H6 leaves), nor between the two growth stages (except for H6 roots). This suggest that the mechanisms controlling isotopic fractionations of Ca within common beans do not vary during growth, and that the nutrients stored in the cotyledons have only a minor effect on the Ca isotope fractionations of plants harvested after 10 days. (3) Strongest Ca isotope fractionations were observed at the nutritive solution/root interface. This implies that the mechanisms of light isotope enrichments in the plant are mainly due to transport processes taking place at this interface. (4) The non infinite L6 nutritive solution became enriched in 44Ca during the experiment compared to the infinite L6 nutritive solution and all the other solutions (L4, H4, and H6). This enrichment can be explained by Rayleigh fractionation or isotopic equilibrium. (5) Bean organs, from L4 and non infinite L6 experiment conditions, were enriched in 44Ca compared to stems and roots cultivated under H4, H6 and infinite L6 conditions. This might be due to the limited Ca in the nutritive solutions that cause smallest Ca isotope fractionations in the bean organs. All these results show that there is no simple correlation between Ca isotopic variations, Ca content and pH of the nutrient solution, and that physiological effects have also to be involved. They confirm the potential of the Ca isotopic system for tracing biological fractionations in natural ecosystems.

Geochemical Constrains on MORB Composition and Magma Sources at East Pacific Rise Between 1°S and 2°S

NASA Astrophysics Data System (ADS)

Zhang, Wei; Zeng, Zhigang; Cui, Lukai; Yin, Xuebo

2018-04-01

The East Pacific Rise (EPR) is a typical fast spreading ridge. To gain a better understanding of the magmatism under ridges, Mid Ocean Ridge Basalts (MORBs) with remarkably heterogeneous compositions are obtained from (EPR) 1°-2°S and multielement geochemical and radioisotope analyses are conducted. Results show that these MORBs have wide variation ranges in trace element concentrations and isotopic ratios. Sample 07 has low concentrations of incompatible elements, and very low 87Sr/86Sr, and high 143Nd/144Nd from 0.70213 to 0.702289 and 0.513234 to 0.513289, respectively. However, other samples show enrichment in incompatible elements to varying degrees, and medium values of 87Sr/86Sr and 143Nd/144Nd from 0.702440 to 0.702680 and 0.513086 to 0.513200, respectively. This study proposes that one depleted source and two enriched sources contribute to the formation of MORBs from EPR 1°-2°S. Samples 02 and 10 are formed by mixing between one enriched source and one depleted source, while sample 07 is crystallized from the depleted source with no mixing process involved. However, the formation of samples 06 and 11 are different, and thus further research is required to determine genesis.

COMPOUND-SPECIFIC CARBON AND HYDROGEN ISOTOPE ANALYSIS-FIELD EVIDENCE OF MTBE BIOREMEDIATION

EPA Science Inventory

Chemical reactions (including bio- and abiotic degradation) tend to favor molecules with the lighter isotopic species (e.g., 12C, 1H), resulting in enrichment of the heavier isotopic species (13C, D) in the unreacted substrate, referred to as isotopic fractionation. On the other ...

Effect of NO2(-) on stable isotope fractionation during bacterial sulfate reduction.

PubMed

Einsiedl, Florian

2009-01-01

The effects of low NO2(-) concentrations on stable isotope fractionation during dissimilatory sulfate reduction by strain Desulfovibrio desulfuricans were investigated. Nitrite, formed as an intermediate during nitrification and denitrification processes in marine and freshwater habitats, inhibits the reduction of the sulfuroxy intermediate SO3(2-) to H2S even at low concentrations. To gain an understanding of the inhibition effect of the reduction of the sulfuroxy intermediate on stable isotope fractionation in sulfur and oxygen during bacterial sulfate reduction, nitrite was added in the form of short pulses. In the batch experiments that contained 0.02, 0.05, and 0.1 mM nitrite, sulfur enrichment factors epsilon of -12 +/- 1.6, -15 +/- 1.1, and -26 +/- 1.3 per thousand, respectively were observed. In the control experiment (no addition of nitrite) a sulfur enrichment factor epsilon of around -11 per thousand was calculated. In the experiments that contained no 18O enriched water (delta18O: -10 per thousand) and nitrite concentrations of 0.02, 0.05, and 0.1 mM, delta18O values in the remaining sulfate were fairly constant during the experiments (delta18O sulfate: approximately equal to 10 per thousand) and were similar to those obtained from the control experiment (no nitrite and no enriched water). However, in the batch experiments that contained 18O enriched water (+700 per thousand) and nitrite concentrations of 0.05 and 0.1 mM increasing delta18O values in the remaining sulfate from around 15 per thousand to approximately 65 and 85 per thousand, respectively, were found. Our experiments that contained isotopic enriched water and nitrite show clear evidence that the ratio of forward and backward fluxes regulated by adenosine-5'-phosphosulfate reductase (APSR) controls the extent of sulfur isotope fractionation during bacterial sulfate reduction in strain Desulfovibrio desulfuricans. Since the metabolic sulfuroxy intermediate SO3(2-) exchanges with water, evidence of 18O enriched water in the remaining sulfate in the experiments that contained nitrite also demonstrates that SO3(2-) recycling to sulfate affects sulfur and oxygen isotope fractionation during bacterial sulfate reduction to some extent. Even though reduction of adenosine-5'-phosphosulfate (APS) to sulfite of -25 per thousand was not fully expressed, SO3(2-) was recycled to SO4(2-). On the basis of the results of this study a sulfur isotope fractionation for APSR of upto approximately -30 per thousand can be assumed. However, reported NO2(-) concentrations of up to 20 microM in freshwater and marine habitats may not significantly impact the ability to use stable isotope analysis in assessing bacterial sulfate reduction.

Origins of mass-dependent and mass-independent Ca isotope variations in meteoritic components and meteorites

NASA Astrophysics Data System (ADS)

Bermingham, K. R.; Gussone, N.; Mezger, K.; Krause, J.

2018-04-01

The Ca isotope composition of meteorites and their components may vary due to mass-dependent and/or -independent isotope effects. In order to evaluate the origin of these effects, five amoeboid olivine aggregates (AOAs), three calcium aluminum inclusions (CAIs), five chondrules (C), a dark inclusion from Allende (CV3), two dark fragments from North West Africa 753 (NWA 753; R3.9), and a whole rock sample of Orgueil (CI1) were analyzed. This is the first coupled mass-dependent and -independent Ca isotope dataset to include AOAs, a dark inclusion, and dark fragments. Where sample masses permit, Ca isotope data are reported with corresponding petrographic analyses and rare earth element (REE) relative abundance patterns. The CAIs and AOAs are enriched in light Ca isotopes (δ44/40Ca -5.32 to +0.72, where δ44/40Ca is reported relative to SRM 915a). Samples CAI 5 and AOA 1 have anomalous Group II REE patterns. These REE and δ44/40Ca data suggest that the CAI 5 and AOA 1 compositions were set via kinetic isotope fractionation during condensation and evaporation. The remaining samples show mass-dependent Ca isotope variations which cluster between δ44/40Ca +0.53 and +1.59, some of which are coupled with unfractionated REE abundance patterns. These meteoritic components likely formed through the coaccretion of the evaporative residue and condensate following Group II CAI formation or their chemical and isotopic signatures were decoupled (e.g., via nebular or parent-body alteration). The whole rock sample of Orgueil has a δ44/40Ca +0.67 ± 0.18 which is in agreement with most published data. Parent-body alteration, terrestrial alteration, and variable sampling of Ca-rich meteoritic components can have an effect on δ44/40Ca compositions in whole rock meteorites. Samples AOA 1, CAI 5, C 2, and C 4 display mass-independent 48/44Ca anomalies (ε48/44Ca +6 to +12) which are resolved from the standard composition. Other samples measured for these effects (AOA 5, CAI 1, CAI 2, C 3, D 1, D 2, D 3) possess the same 48/44Ca isotope composition as the standard within analytical uncertainty. These data indicate a heterogeneous distribution of 48Ca in the early solar nebula during formation of CAIs, AOAs, and chondrules. In a ε48/44Ca vs. δ44/40Ca plot, no strong correlation is evident which suggests that the thermal processing event which caused a heterogeneous distribution of ε48/44Ca in the solar nebula is unlikely to be directly related to the thermal processing event that caused coupled REE and Ca mass-dependent isotopic fractionation in meteoritic components.

Monitoring Microbial Mineralization Using Reverse Stable Isotope Labeling Analysis by Mid-Infrared Laser Spectroscopy

PubMed Central

2017-01-01

Assessing the biodegradation of organic compounds is a frequent question in environmental science. Here, we present a sensitive, inexpensive, and simple approach to monitor microbial mineralization using reverse stable isotope labeling analysis (RIL) of dissolved inorganic carbon (DIC). The medium for the biodegradation assay contains regular organic compounds and 13C-labeled DIC with 13C atom fractions (x(13C)DIC) higher than natural abundance (typically 2–50%). The produced CO2 (x(13C) ≈ 1.11%) gradually dilutes the initial x(13C)DIC allowing to quantify microbial mineralization using mass-balance calculations. For 13C-enriched CO2 samples, a newly developed isotope ratio mid-infrared spectrometer was introduced with a precision of x(13C) < 0.006%. As an example for extremely difficult and slowly degradable compounds, CO2 production was close to the theoretical stoichiometry for anaerobic naphthalene degradation by a sulfate-reducing enrichment culture. Furthermore, we could measure the aerobic degradation of dissolved organic carbon (DOC) adsorbed to granular activated carbon in a drinking water production plant, which cannot be labeled with 13C. Thus, the RIL approach can be applied to sensitively monitor biodegradation of various organic compounds under anoxic or oxic conditions. PMID:28903553

Comparison of Total Evaporation (TE) and Direct Total Evaporation (DTE) methods in TIMS by using NBL CRMs

NASA Astrophysics Data System (ADS)

Hasözbek, Altug; Mathew, Kattathu; Wegener, Michael

2013-04-01

The total evaporation (TE) is a well-established analytical method for safeguards measurement of uranium and plutonium isotope-amount ratios using the thermal ionization mass spectrometry (TIMS). High accuracy and precision isotopic measurements find many applications in nuclear safeguards, for e.g. assay measurements using isotope dilution mass spectrometry. To achieve high accuracy and precision in TIMS measurements, mass dependent fractionation effects are minimized by either the measurement technique or changes in the hardware components that are used to control sample heating and evaporation process. At NBL, direct total evaporation (DTE) method on the modified MAT261 instrument, uses the data system to read the ion signal intensity and its difference from a pre-determined target intensity, is used to control the incremental step at which the evaporation filament is heated. The feedback and control is achieved by proprietary hardware from SPECTROMAT that uses an analog regulator in the filament power supply with direct feedback of the detector intensity. Compared to traditional TE method on this instrument, DTE provides better precision (relative standard deviation, expressed as a percent) and accuracy (relative difference, expressed as a percent) of 0.05 to 0.08 % for low enriched and high enriched NBL uranium certified reference materials.

Stable isotope analysis of energy dynamics in aquatic ecosystems suggests trophic shifts following severe wildfire

NASA Astrophysics Data System (ADS)

Martens, A. M.; Silins, U.; Bladon, K. D.; Williams, C.; Wagner, M. J.; Luchkow, E.

2015-12-01

Wildfire alters landscapes and can have significant impacts on stream ecosystems. The 2003 Lost Creek wildfire was one of the most severe on Alberta's eastern rocky mountain slopes, resulting in elevated sediment production and nutrient (phosphorus, nitrogen, and carbon) export in impacted streams. These resulted in increased algal productivity and macroinvertebrate abundance and diversity, and as a result, fish in watersheds draining wildfire affected catchments were larger than those in the same age class from reference (unburned) watersheds. In the present investigation, stable isotope analysis of C and N was utilized to evaluate ecosystem energy dynamics and describe trophic relationships in those watersheds. Aquatic invertebrates from burned catchments showed enrichment in δ13C and δ15N relative to algae suggesting a reliance on algae (autochthony) as a primary source of energy. Invertebrates from unburned systems were depleted in δ13C relative to algae indicating reliance on allochthonous or terrestrial primary energy sources. Preliminary analysis of δ15N in macroinvertebrates showed slight enrichment in burned catchments suggesting a trophic shift. More comprehensive macroinvertebrate sampling and identification has been conducted; isotopic analysis will provide greater resolution of how specific families within feeding guilds have been affected by wildfire. This will provide more robust insights into how wildfires may impact stream ecology in mountain environments.

Using stable isotopes to examine watershed connectivity to ...

EPA Pesticide Factsheets

Water bodies within the USA are protected by the US Clean Water Act when they have a significant nexus to downstream navigable waters. As a research scientist with the US Environmental Protection Agency, I have used water stable isotopes to examine hydrologic connectivity dynamics. I will share two case studies. In the first case, we used the isotopic evaporation signal in water to examine wetland-stream hydrologic connectivity within the Pipestem Creek watershed, North Dakota, a watershed dominated by prairie-pothole wetlands. Prairie-Pothole wetlands are a special case of wetlands whose protection needs to be determined under the Clean Water Rule. Pipestem Creek exhibited an evaporated-water signal that had approximately half the isotopic-enrichment signal found in most evaporatively enriched prairie-pothole wetlands. Groundwater measured at the water table adjacent to Pipestem Creek had isotopic values that indicated recharge from winter precipitation and had no significant evaporative enrichment. Using isotopic theory and discharge data, we estimated the area of surface water necessary to generate the evaporation signal found within Pipestem Creek over two years. Our results indicated that prairie-pothole wetlands were important sources of stream flow in Pipestem Creek throughout the summer, as well as during snowmelt. They also demonstrated that at the lowest flows, the stream itself became disconnected from headwater stream reaches. In the second ca

Hydrogen and carbon isotope fractionation during degradation of chloromethane by methylotrophic bacteria

PubMed Central

Nadalig, Thierry; Greule, Markus; Bringel, Françoise; Vuilleumier, Stéphane; Keppler, Frank

2013-01-01

Chloromethane (CH3Cl) is a widely studied volatile halocarbon involved in the destruction of ozone in the stratosphere. Nevertheless, its global budget still remains debated. Stable isotope analysis is a powerful tool to constrain fluxes of chloromethane between various environmental compartments which involve a multiplicity of sources and sinks, and both biotic and abiotic processes. In this study, we measured hydrogen and carbon isotope fractionation of the remaining untransformed chloromethane following its degradation by methylotrophic bacterial strains Methylobacterium extorquens CM4 and Hyphomicrobium sp. MC1, which belong to different genera but both use the cmu pathway, the only pathway for bacterial degradation of chloromethane characterized so far. Hydrogen isotope fractionation for degradation of chloromethane was determined for the first time, and yielded enrichment factors (ε) of −29‰ and −27‰ for strains CM4 and MC1, respectively. In agreement with previous studies, enrichment in 13C of untransformed CH3Cl was also observed, and similar isotope enrichment factors (ε) of −41‰ and −38‰ were obtained for degradation of chloromethane by strains CM4 and MC1, respectively. These combined hydrogen and carbon isotopic data for bacterial degradation of chloromethane will contribute to refine models of the global atmospheric budget of chloromethane. PMID:24019296

Calcium and titanium isotopes in refractory inclusions from CM, CO, and CR chondrites

NASA Astrophysics Data System (ADS)

Kööp, Levke; Davis, Andrew M.; Krot, Alexander N.; Nagashima, Kazuhide; Simon, Steven B.

2018-05-01

Previous studies have shown that CV and CM chondrites incorporated Ca, Al-rich inclusions (CAIs) with different isotopic characteristics, which may represent different snapshots in the isotopic evolution of the early Solar System. To better understand how the isotopic characteristics of CAIs vary between different chondrite groups, we have studied calcium and titanium isotopes in CAIs from CM, CO, and CR chondrites. We show that all three chondrite groups contain CAIs with large anomalies in 48Ca and/or 50Ti (10s of ‰ or 100s of ε-units) as well as CAIs with no anomalies resolved beyond measurement uncertainties. Isotopically, the anomalous CO and CR chondrite CAIs resemble the platy hibonite crystals (PLACs) from CM chondrites, but they are more mineralogically complex. The new data are consistent with the well-established mutual exclusivity relationship between incorporation of 26Al and the presence of large anomalies in 48Ca and 50Ti. The two highly anomalous CO chondrite CAIs have correlated anomalies in 46Ti and 50Ti, while most other highly anomalous CAIs do not. This result could indicate that the reservoir with coupled 46Ti and 50Ti that was sampled by bulk meteorites and CV chondrite CAIs already existed before arrival and/or homogeneous distribution of 26Al in the protoplanetary disk. Among the studied CM chondrite CAIs are ten spinel-hibonite inclusions (SHIBs) with known oxygen isotopic compositions. Our results show that these objects sampled a reservoir that was well-mixed in oxygen, calcium, and titanium isotopes. We further show that SHIBs tend to be slightly enriched in the heavy calcium isotopes, suggesting that their formation history was different from CV chondrite CAIs.

The Mantle Isotopic Array: A Tale of Two FOZOs

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Evaluating Snowmelt Runoff Processes Using Stable Isotopes in a Permafrost Hillslope

NASA Astrophysics Data System (ADS)

Carey, S. K.

2004-05-01

Conceptual understanding of runoff generation in permafrost regions have been derived primarily from hydrometric information, with isotope and hydrochemical data having only limited application in delineating sources and pathways of water. Furthermore, when stable isotope data are used to infer runoff processes, it often provides conflicting results from hydrometric measurements. In a small subarctic alpine catchment within the Wolf Creek Research Basin, Yukon, Canada, experiments were conducted during the melt period of 2002 and 2003 to trace the stable isotopic signature (d18O) of meltwater from a melting snowpack into permafrost soils and laterally to the stream to identify runoff processes and evaluate sources of error for traditional hydrograph separation studies in snowmelt-dominated permafrost basins. Isotopic variability in the snowpack was recorded at 0.1 m depth intervals during the melt period and compared with the meltwater isotopic signature at the snowpack base collected in lysimeters. Throughout the melt period in both years, there was an isotopic enrichment of meltwater as the season progressed. A downslope transect of wells and piezometers were used to evaluate the influence of infiltrating meltwater and thawing ground on the subsurface d18O signature. As melt began, meltwater infiltrated the frozen porous organic layer, leading to liquid water saturation in the unsaturated pore spaces. Water sampled during this initial melt stage show soil water d18O mirroring that of the meltwater signal. As the melt season progressed, frozen soil began to melt, mixing enriched pre-melt soil water with meltwater. This mixing increased the overall value of d18O obtained from the soil, which gradually increased as thaw progressed. At the end of snowmelt, soil water had a d18O value similar to values from the previous fall, suggesting that much of the initial snowmelt water had been flushed from the hillslope. Results from the hillslope scale are compared with two-component hydrograph separations and sources of error are discussed.

New organic reference materials for hydrogen, carbon, and nitrogen stable isotope-ratio measurements: caffeines, n-alkanes, fatty acid methyl esters, glycines, L-valines, polyethylenes, and oils

USGS Publications Warehouse

Schimmelmann, Arndt; Qi, Haiping; Coplen, Tyler B.; Brand, Willi A.; Fong, Jon; Meier-Augenstein, Wolfram; Kemp, Helen F.; Toman, Blaza; Ackermann, Annika; Assonov, Sergey; Aerts-Bijma, Anita; Brejcha, Ramona; Chikaraishi, Yoshito; Darwish, Tamim; Elsner, Martin; Gehre, Matthias; Geilmann, Heike; Gröning, Manfred; Hélie, Jean-François; Herrero-Martín, Sara; Meijer, Harro A.J.; Sauer, Peter E.; Sessions, Alex L.; Werner, Roland A.

2016-01-01

An international project developed, quality-tested, and determined isotope−δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope−δ scales. The RMs span a range of δ2HVSMOW-SLAP values from −210.8 to +397.0 mUr or ‰, for δ13CVPDB-LSVEC from −40.81 to +0.49 mUr and for δ15NAir from −5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C16 n-alkanes, n-C20-fatty acid methyl esters (FAMEs), glycines, and l-valines, together with polyethylene powder and string, one n-C17-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a 2H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ2H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain 13C and carbon-bound organic 2H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies.

Volatile element content of the heterogeneous upper mantle

NASA Astrophysics Data System (ADS)

Shimizu, K.; Saal, A. E.; Hauri, E. H.; Forsyth, D. W.; Kamenetsky, V. S.; Niu, Y.

2014-12-01

The physical properties of the asthenosphere (e.g., seismic velocity, viscosity, electrical conductivity) have been attributed to either mineral properties at relevant temperature, pressure, and water content or to the presence of a low melt fraction. We resort to the geochemical studies of MORB to unravel the composition of the asthenosphere. It is important to determine to what extent the geochemical variations in axial MORB do represent a homogeneous mantle composition and variations in the physical conditions of magma generation and transport; or alternatively, they represent mixing of melts from a heterogeneous upper mantle. Lavas from intra-transform faults and off-axis seamounts share a common mantle source with axial MORB, but experience less differentiation and homogenization. Therefore they provide better estimates for the end-member volatile budget of the heterogeneous upper mantle. We present major, trace, and volatile element data (H2O, CO2, Cl, F, S) as well as Sr, Nd, and Pb isotopic compositions [1, 2] of basaltic glasses (MgO > 6.0 wt%) from the NEPR seamounts, Quebrada-Discovery-Gofar transform fault system, and Macquarie Island. The samples range from incompatible trace element (ITE) depleted (DMORB: Th/La<0.035) to enriched (EMORB: Th/La>0.07) spanning the entire range of EPR MORB. The isotopic composition of the samples correlates with the degree of trace element enrichment indicating long-lived mantle heterogeneity. Once shallow-level processes (degassing, crystallization, and crustal assimilation) have been considered, we conducted a two-component (DMORB- and EMORB-) mantle melting-mixing model. Our model reproduces the major, trace and volatile element contents and isotopic composition of our samples and suggests that (1) 90% of the upper mantle is highly depleted in ITE (DMORB source) with only 10% of an enriched component (EMORB source), (2) the EMORB source is peridotitic rather than pyroxenitic, and (3) NMORB do not represent an actual mantle source, but the product of magma mixing between D- and E-MORB. Finally we use the volatile to trace element ratios of our samples to estimate the volatile element budget of the end-member components of the upper mantle. [1] Niu, Y. et al. (2002) EPSL, 199, 327-345. [2] Kamenetsky, V. S. et al. (2000) J. Petrology, 41, 411-430.

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.

Gallium isotopic evidence for extensive volatile loss from the Moon during its formation

PubMed Central

Kato, Chizu; Moynier, Frédéric

2017-01-01

The distribution and isotopic composition of volatile elements in planetary materials holds a key to the characterization of the early solar system and the Moon’s formation. The Moon and Earth are chemically and isotopically very similar. However, the Moon is highly depleted in volatile elements and the origin of this depletion is still debated. We present gallium isotopic and elemental measurements in a large set of lunar samples to constrain the origin of this volatile depletion. We show that while Ga has a geochemical behavior different from zinc, both elements show a systematic enrichment in the heavier isotopes in lunar mare basalts and Mg-suite rocks compared to the silicate Earth, pointing to a global-scale depletion event. On the other hand, the ferroan anorthosites are isotopically heterogeneous, suggesting a secondary distribution of Ga at the surface of the Moon by volatilization and condensation. The isotopic difference of Ga between Earth and the Moon and the isotopic heterogeneity of the crustal ferroan anorthosites suggest that the volatile depletion occurred following the giant impact and during the lunar magma ocean phase. These results point toward a Moon that has lost its volatile elements during a whole-scale evaporation event and that is now relatively dry compared to Earth. PMID:28782027

Using stable isotopes to assess dietary changes of American black bears from 1980 to 2001.

PubMed

Teunissen van Manen, Jennapher L; Muller, Lisa I; Li, Zheng-hua; Saxton, Arnold M; Pelton, Michael R

2014-01-01

We measured stable carbon and nitrogen isotope ratios in 117 hair samples from American black bears (Ursus americanus) in Great Smoky Mountains National Park, Tennessee, during 1980-2001 from live-trapped bears. We also collected hair from bears with known diets to compare with the wild bears. We hypothesized that biological factors (age, mass, and sex), food availability (hard mast and wild hogs (Sus scrofa)), and nuisance status would influence food selection by black bears and changes in their feeding history would be measureable using stable isotopes. We developed a set of a priori models using nine variables to examine changes in black bear stable isotope values. We found no support for changes in δ(13)C values associated with any of the nine variables we analyzed. Bears had enriched (15)N in years with low white oak mast production and depleted (15)N when white oak mast was abundant. Subadults had enriched (15)N compared with adults and older adults. Variation in δ(15)N increased from 1980-1991 to 1992-2000 when hard mast production had greater fluctuations. Bears in a better physical condition appeared more likely to access foods with higher protein content. In years of low white oak acorn production, larger bears and subadults likely turned to alternative food sources. The long-term variation detected in this study was important in identifying which bears were potentially more susceptible to changes in availability of hard mast.

Zinc isotope fractionation during adsorption onto Mn oxyhydroxide at low and high ionic strength

NASA Astrophysics Data System (ADS)

Bryan, Allison L.; Dong, Shuofei; Wilkes, Elise B.; Wasylenki, Laura E.

2015-05-01

Marine ferromanganese sediments represent one of the largest sinks from global seawater for Zn, a critical trace metal nutrient. These sediments are variably enriched in heavier isotopes of Zn relative to deep seawater, and some are among the heaviest natural samples analyzed to date. New experimental results demonstrate that adsorption of Zn to poorly crystalline Mn oxyhydroxide results in preferential association of heavier isotopes with the sorbent phase. At low ionic strength our experimental system displayed a short-lived kinetic isotope effect, with light isotopes adsorbed to birnessite (Δ66/64Znadsorbed-dissolved ∼ -0.2‰). After 100 h the sense of fractionation was opposite, such that heavier isotopes were preferentially adsorbed at steady state, but the magnitude of Δ66/64Znadsorbed-dissolved was indistinguishable from zero (+0.05 ± 0.08‰). At high ionic strength, we observed preferential sorption of heavy isotopes, with a strong negative correlation between Δ66/64Znadsorbed-dissolved and the percentage of Zn on the birnessite. Values of Δ66/64Znadsorbed-dissolved ranged from nearly +3‰ at low surface loading to +0.16‰ at high surface loading. Based on previous EXAFS work we infer that Zn adsorbs first as tetrahedral, inner-sphere complexes at low surface loading, with preferential incorporation of heavier isotopes relative to the octahedral Zn species predominating in solution. As surface loading increases, so does the proportion of Zn adsorbing as octahedral complexes, thus diminishing the magnitude of fractionation between the dissolved and adsorbed pools of Zn. The magnitude of fractionation at high ionic strength is also governed by aqueous speciation of Zn in synthetic seawater; a substantial fraction of Zn ions reside in chloro complexes, which preferentially incorporate light Zn isotopes, and this drives the adsorbed pool to be heavier relative to the bulk solution than it was at low ionic strength. Our results explain the observation that ferromanganese sediments are enriched in heavier isotopes of Zn relative to deep seawater. This represents a step towards building a robust mass balance model for Zn isotopes in the oceans and potentially using Zn isotopes to trace biogeochemical cycling of this important element in the modern and ancient oceans.

Zinc isotopic fractionation in Phragmites australis in response to toxic levels of zinc

PubMed Central

Caldelas, Cristina; Dong, Shuofei; Araus, José Luis; Jakob Weiss, Dominik

2011-01-01

Stable isotope signatures of Zn have shown great promise in elucidating changes in uptake and translocation mechanisms of this metal in plants during environmental changes. Here this potential was tested by investigating the effect of high Zn concentrations on the isotopic fractionation patterns of Phragmites australis (Cav.) Trin. ex Steud. Plants were grown for 40 d in a nutritive solution containing 3.2 μM (sufficient) or 2 mM (toxic) Zn. The Zn isotopic composition of roots, rhizomes, shoots, and leaves was analysed. Stems and leaves were sampled at different heights to evaluate the effect of long-distance transport on Zn fractionation. During Zn sufficiency, roots, rhizomes, and shoots were isotopically heavy (δ66ZnJMC Lyon=0.2‰) while the youngest leaves were isotopically light (–0.5‰). During Zn excess, roots were still isotopically heavier (δ66Zn=0.5‰) and the rest of the plant was isotopically light (up to –0.5‰). The enrichment of heavy isotopes at the roots was attributed to Zn uptake mediated by transporter proteins under Zn-sufficient conditions and to chelation and compartmentation in Zn excess. The isotopically lighter Zn in shoots and leaves is consistent with long-distance root to shoot transport. The tolerance response of P. australis increased the range of Zn fractionation within the plant and with respect to the environment. PMID:21193582

Meteoritic Evidence for Multiple Early Enriched Reservoirs in the Martian Mantle

NASA Astrophysics Data System (ADS)

Armytage, R. M. G.; Debaille, V.; Brandon, A. D.; Agee, C. B.

2018-05-01

From isotopic systematics, the martian crustal reservoir represented by NWA 7034 cannot be the enriched end-member for the shergottites. This suggests multiple enriched reservoirs in the martian mantle formed by several differentiation events.

Characterization and quantification of odor-active compounds in unsaturated fatty acid/conjugated linoleic acid (UFA/CLA)-enriched butter and in conventional butter during storage and induced oxidation.

PubMed

Mallia, Silvia; Escher, Felix; Dubois, Sébastien; Schieberle, Peter; Schlichtherle-Cerny, Hedwig

2009-08-26

Dairy products enriched in unsaturated fatty acids (UFA) and conjugated linoleic acids (CLA) have a higher nutritional value and are suggested to have beneficial health effects. However, such acids are susceptible to oxidation, and off-flavors may be formed during storage. This study was aimed to compare the most important odorants in UFA/CLA-enriched butter to that of conventional butter during storage and induced oxidation. Volatiles were isolated by solvent-assisted flavor evaporation and identified by gas chromatography-olfactometry and mass spectrometry. Aroma extract dilution analysis revealed 18 odorants that were quantified by stable isotope dilution analysis. Another important odorant, 3-methyl-1H-indole (mothball-like odor), was quantified by high-performance liquid chromatography. After storage, UFA/CLA-enriched butter showed higher concentrations of pentanal (fatty), heptanal (green), butanoic acid (cheesy), and delta-decalactone (peach-like). Photo-oxidation of butter samples induced increases in heptanal, (E)-2-octenal, and trans-4,5-epoxy-(E)-2-decenal, especially in conventional butter. The higher vitamin content in UFA/CLA samples may protect this butter from oxidation.

A new feature in the internal heavy isotope distribution in ozone

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

Bhattacharya, S. K., E-mail: skbhatta1@gmail.com; Liang, Mao-Chang; Savarino, Joel

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition ({sup 18}O/{sup 16}O and {sup 17}O/{sup 16}O ratio) which does not follow normal mass fractionation rule: δ{sup 17}O ∼ 0.52{sup *}δ{sup 18}O, expressed as an anomaly Δ{sup 17}O = δ{sup 17}O − 0.52{sup *}δ{sup 18}O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ{sup 18}O (s) or δ{sup 18}O (as) (and similarly for δ{sup 17}O) as well asmore » position dependent isotope anomaly Δ{sup 17}O (s) and Δ{sup 17}O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ{sup 17}O (s) is zero. Consequently, Δ{sup 17}O (as) = 1.5 {sup *} Δ{sup 17}O (bulk) (named here simply as the “1.5 rule”) which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.« less

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

NASA Technical Reports Server (NTRS)

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

2016-01-01

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

MG Isotopic Measurement of FIB-Isolated Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

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

2010-01-01

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

Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm

NASA Astrophysics Data System (ADS)

Coutaud, Margot; Méheut, Merlin; Glatzel, Pieter; Pokrovski, Gleb S.; Viers, Jérôme; Rols, Jean-Luc; Pokrovsky, Oleg S.

2018-01-01

Despite the importance of phototrophic biofilms in metal cycling in freshwater systems, metal isotope fractionation linked to metal adsorption and uptake by biofilm remains very poorly constrained. Here, copper isotope fractionation by a mature phototrophic biofilm during Cu surface adsorption and incorporation was studied in batch reactor (BR) and open drip flow reactor (DFR) systems at ambient conditions. X-ray Absorption Spectroscopy (both Near Edge Structure, XANES, and Extended Fine Structure, EXAFS) at Cu K-edge of the biofilm after its interaction with Cu in BR experiments allowed characterizing the molecular structure of assimilated Cu and quantifying the degree of CuII to CuI reduction linked to Cu assimilation. For both BR and DFR experiments, Cu adsorption caused enrichment in heavy isotope at the surface of the biofilm relative to the aqueous solution, with an apparent enrichment factor for the adsorption process, ε65Cuads, of +1.1 ± 0.3‰. In contrast, the isotope enrichment factor during copper incorporation into the biofilm (ε65Cuinc) was highly variable, ranging from -0.6 to +0.8‰. This variability of the ε65Cuinc value was likely controlled by Cu cellular uptake via different transport pathways resulting in contrasting fractionation. Specifically, the CuII storage induced enrichment in heavy isotope, whereas the toxicity response of the biofilm to Cu exposure resulted in reduction of CuII to CuI, thus yielding the biofilm enrichment in light isotope. EXAFS analyses suggested that a major part of the Cu assimilated by the biofilm is bound to 5.1 ± 0.3 oxygen or nitrogen atoms, with a small proportion of Cu linked to sulfur atoms (NS < 0.6) of sulfhydryl groups. XANES analyses showed that the proportion of CuIIvs CuI, compared to the initial CuII/CuI ratio, decreased by 14% after the first hour of reaction and by 6% after 96 h of reaction. The value of ε65Cuinc of the biofilm exhibited a similar trend over time of exposure. Our study demonstrates the complexity of biological processes associated with live phototrophic biofilms, which produce large and contrasting isotope fractionations following rather small Cu redox and speciation changes during uptake, storage or release of the metal, i.e., favoring heavy isotopes during complexation with carboxylate ligands and light isotopes during reduction of CuII-O/N to CuI-sulfhydryl moieties.

Monitoring Natural Biodegradation of TCE in Fractured Sedimentary Rocks Using delta 13C of TCE and its Degradation Products: Estimating Isotopic Fractionation Factor under Field Conditions

NASA Astrophysics Data System (ADS)

Revesz, K.; Shapiro, A. M.; Tiedeman, C.; Goode, D. J.; Lacombe, P. J.; Imbrigiotta, T. E.

2008-12-01

The isotopic ratio of 13C/12C, expressed in delta13CVPDB per mill for trichloroethene (TCE), can differentiate between microbial degradation and other processes (dilution, dispersion, and sorption) that can also affect the concentration of TCE and its degradation products. The delta13C of TCE isotopically fractionates during microbial degradation; however, it remains practically unchanged during other processes. The isotope fractionation factor (alpha) estimated under laboratory conditions, however, may not be representative of microbial degradation in natural ground waters. Estimating alpha under field conditions provides evidence of the presence or absence of in situ microbial degradation and provides valuable information on the in situ processes that affect the fate and transport of chlorinated hydrocarbons. Our modified analytical method of analyzing for the isotopic ratio proved to be comparable to previously published methods. Isotope values were stable within analytical uncertainty in sample sizes ranging from 22 to 2200 nanomoles. Prepared standard mixtures of TCE and DCEs (trans- and cis- dichloroethene) were analyzed after every five field samples, and were stable during the time period that field samples were processed (a year). Water samples were collected from multiple boreholes completed in the fractured mudstone underlying the former Naval Air Warfare Center, West Trenton, NJ, and analyzed for delta13C of the chlorinated hydrocarbons. The results showed an ongoing natural microbial degradation following the typical dehalogenation pathway: TCE to DCE (trans- and cis-dichloroethene) to VC (vinyl chloride). The carbon isotope enrichment due to fractionation was smaller between TCE to DCE degradation than the enrichment between DCE to VC degradation, which is consistent with previous investigations. Results also showed a correlation between delta13C of TCE and the transmissivity of the boreholes where water samples were collected. We assumed that boreholes with extremely low transmissivity behaved analogously to microbial batch reactors. The value of alpha obtained from the borehole interval with the lowest transmissivity was 0.99345, which is in the range of published values: 0.9862 to 0.9934. We consider this value to represent the "field alpha" for microbial degradation in the absence of other processes. Values of alpha in other boreholes that differ from the field alpha could point to other processes affecting the delta13C and concentration of TCE. The value of alpha from the various monitored intervals is referred to as the "apparent alpha". The apparent alpha is characteristic of the borehole and the time at which the concentrations and the isotope values were measured. The difference between the apparent alpha and the field alpha provides insight into hydrologic conditions around the well. Results from one well showed fluctuation in the TCE concentrations, which were correlated with the calculated apparent alpha, and pointed to the recent introduction of TCE into the ground water that had not been significantly degraded. Recent drilling in the vicinity of this well may have remobilized free-phase TCE.

Measurement of strontium isotope ratio in nitric acid extract of peanut testa by ICP-Q-MS after removal of Rb by extraction with pure water.

PubMed

Zhu, Yanbei; Hioki, Akiharu; Chiba, Koichi

2014-02-01

The difference in the distributions of Sr and Rb in peanut seeds was utilized to develop a precise method for Sr isotope ratio measurement by inductively coupled plasma quadruple mass spectrometry (ICP-Q-MS). The testa instead of the whole peanut seed was selected as the sample because apparent enrichment of Sr in comparison to Rb was found in the testa. Furthermore, Rb in the testa was removed by pure water extraction with the aid of sonication to remove the isobaric interference in Sr isotope ratio measurement. The testa taken from one peanut seed was treated as one sample for the analysis. After optimization of the operating conditions, pure water (10 mL for each sample) extraction in 30 min with sonication was able to remove over 95% of Rb in the testa, while after the Rb removal Sr could be completely extracted using 10 mL of 0.3 mol L(-1) HNO3 for each sample. The integration time in ICP-Q-MS measurement was optimized to achieve a lower measurement uncertainty in a shorter time; the results showed that 1s was required and enough for the precise measurement of Sr isotope ratios giving a relative standard uncertainty (n=10) of ca. 0.1%. The present method was applied to peanut seeds grown in Japan, China, USA, India, and South Africa. © 2013 Published by Elsevier B.V.

Laser and gas centrifuge enrichment

NASA Astrophysics Data System (ADS)

Heinonen, Olli

2014-05-01

Principles of uranium isotope enrichment using various laser and gas centrifuge techniques are briefly discussed. Examples on production of high enriched uranium are given. Concerns regarding the possibility of using low end technologies to produce weapons grade uranium are explained. Based on current assessments commercial enrichment services are able to cover the global needs of enriched uranium in the foreseeable future.

Strontium isotope measurement of basaltic glasses by laser ablation multiple collector inductively coupled plasma mass spectrometry based on a linear relationship between analytical bias and Rb/Sr ratios.

PubMed

Zhang, Le; Ren, Zhong-Yuan; Wu, Ya-Dong; Li, Nan

2018-01-30

In situ strontium (Sr) isotope analysis of geological samples by laser ablation multiple collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) provides useful information about magma mixing, crustal contamination and crystal residence time. Without chemical separation, during Sr isotope analysis with laser ablation, many kinds of interference ions (such as Rb + and Kr + ) are on the Sr isotope spectrum. Most previous in situ Sr isotope studies only focused on Sr-enriched minerals (e.g. plagioclase, calcite). Here we established a simple method for in situ Sr isotope analysis of basaltic glass with Rb/Sr ratio less than 0.14 by LA-MC-ICP-MS. Seven Faraday cups, on a Neptune Plus MC-ICP-MS instrument, were used to receive the signals on m/z 82, 83, 84, 85, 86, 87 and 88 simultaneously for the Sr isotope analysis of basaltic glass. The isobaric interference of 87 Rb was corrected by the peak stripping method. The instrumental mass fractionation of 87 Sr/ 86 Sr was corrected to 86 Sr/ 88 Sr = 0.1194 with an exponential law. Finally, the residual analytical biases of 87 Sr/ 86 Sr were corrected with a relationship between the deviation of 87 Sr/ 86 Sr from the reference values and the measured 87 Rb/ 86 Sr. The validity of the protocol present here was demonstrated by measuring the Sr isotopes of four basaltic glasses, a plagioclase crystal and a piece of modern coral. The measured 87 Sr/ 86 Sr ratios of all these samples agree within 100 ppm with the reference values. In addition, the Sr isotopes of olivine-hosted melt inclusions from the Emeishan large igneous province (LIP) were measured to show the application of our method to real geological samples. A simple but accurate approach for in situ Sr isotope measurement by LA-MC-ICP-MS has been established, which should greatly facilitate the wider application of in situ Sr isotope geochemistry, especially to volcanic rock studies. Copyright © 2017 John Wiley & Sons, Ltd.

Box-modeling of 15N/14N in mammals.

PubMed

Balter, Vincent; Simon, Laurent; Fouillet, Hélène; Lécuyer, Christophe

2006-03-01

The 15N/14N signature of animal proteins is now commonly used to understand their physiology and quantify the flows of nutrient in trophic webs. These studies assume that animals are predictably 15N-enriched relative to their food, but the isotopic mechanism which accounts for this enrichment remains unknown. We developed a box model of the nitrogen isotope cycle in mammals in order to predict the 15N/14N ratios of body reservoirs as a function of time, N intake and body mass. Results of modeling show that a combination of kinetic isotope fractionation during the N transfer between amines and equilibrium fractionation related to the reversible conversion of N-amine into ammonia is required to account for the well-established approximately 4 per thousand 15N-enrichment of body proteins relative to the diet. This isotopic enrichment observed in proteins is due to the partial recycling of 15N-enriched urea and the urinary excretion of a fraction of the strongly 15N-depleted ammonia reservoir. For a given body mass and diet delta15N, the isotopic compositions are mainly controlled by the N intake. Increase of the urea turnover combined with a decrease of the N intake lead to calculate a delta15N increase of the proteins, in agreement with the observed increase of collagen delta15N of herbivorous animals with aridity. We further show that the low delta15N collagen values of cave bears cannot be attributed to the dormancy periods as it is commonly thought, but inversely to the hyperphagia behavior. This model highlights the need for experimental investigations performed with large mammals in order to improve our understanding of natural variations of delta15N collagen.

Geochemical and isotopic investigation of the Laiwu-Zibo carbonatites from western Shandong Province, China, and implications for their petrogenesis and enriched mantle source

NASA Astrophysics Data System (ADS)

Ying, Jifeng; Zhou, Xinhua; Zhang, Hongfu

2004-08-01

Major and trace element and Nd-Sr isotope data of the Mesozoic Laiwu-Zibo carbonatites (LZCs) from western Shandong Province, China, provide clues to the petrogenesis and the nature of their mantle source. The Laiwu-Zibo carbonatites can be petrologically classified as calcio-, magnesio- and ferro-carbonatites. All these carbonatites show a similarity in geochemistry. On the one hand, they are extremely enriched in Ba, Sr and LREE and markedly low in K, Rb and Ti, which are similar to those global carbonatites, on the other hand, they have extremely high initial 87Sr/ 86Sr (0.7095-0.7106) and very low ɛNd (-18.2 to -14.3), a character completely different from those global carbonatites. The small variations in Sr and Nd isotopic ratios suggest that crustal contamination can not modify the primary isotopic compositions of LZC magmas and those values are representatives of their mantle source. The Nd-Sr isotopic compositions of LZCs and their similarity to those of Mesozoic Fangcheng basalts imply that they derived from an enriched lithospheric mantle. The formation of such enriched lithospheric mantle is connected with the major collision between the North China Craton (NCC) and the Yangtze Craton. Crustal materials from the Yangtze Craton were subducted beneath the NCC and melts derived from the subducted crust of the Yangtze Craton produced an enriched Mesozoic mantle, which is the source for the LZCs and Fangcheng basalts. The absence of alkaline silicate rocks, which are usually associated with carbonatites suggest that the LZCs originated from the mantle by directly partial melting.

Effects of preservatives on stable isotope analyses of four marine species

NASA Astrophysics Data System (ADS)

Carabel, Sirka; Verísimo, Patricia; Freire, Juan

2009-04-01

The aim of the present study is to quantify the effect of formalin-ethanol preservation on the carbon and nitrogen stable isotope signatures of four taxonomical groups of marine species ( Himanthalia elongata, Anemonia sulcata, Mytilus galloprovincialis and Patella vulgata). To examine temporal changes in the effects of preservation and to determine if preservation induced predictable shifts in δ13C and δ15N signatures, repeated analyses were carried out after 6, 12 and 24 months of preservation. Data from our study showed highly variable effects of the formalin-ethanol preservation on carbon and nitrogen isotope signatures between species. The use of a general correction factor was not possible, or else it should be species-specific. Differences in nitrogen isotopic values between preserved and unpreserved samples were minor compared to the assumed enrichment between trophic levels. The combined use of data from preserved and unpreserved samples could lead to biases in the estimation of the trophic level of organisms. Changes that preservatives caused in carbon values were variable between species and not always small enough to be ignored. So the use of data from preserved samples could change the interpretation of the mixing models used to determine the importance of multiple sources of carbon. In order to elucidate the effects that preservatives have in other species, further studies will be necessary.

16O enrichments in aluminum-rich chondrules from ordinary chondrites

NASA Astrophysics Data System (ADS)

Russell, Sara S.; MacPherson, Glenn J.; Leshin, Laurie A.; McKeegan, Kevin D.

2000-12-01

The oxygen isotopic compositions of seven Al-rich chondrules from four unequilibrated ordinary chondrites were measured in situ using an ion microprobe. On an oxygen three isotope plot, the data are continuous with the ordinary chondrite ferromagnesian chondrule field but extend it to more 16O-enriched values along a mixing line of slope=0.83±0.09, with the lightest value recorded at δ18O=-15.7±1.8‰ and δ17O=-13.5±2.6‰. If Al-rich chondrules were mixtures of ferromagnesian chondrules and CAI material, their bulk chemical compositions would require them to exhibit larger 16O enrichments than we observe. Therefore, Al-rich chondrules are not simple mixtures of these two components. Three chondrules exhibit significant internal isotopic heterogeneity indicative of partial exchange with a gaseous reservoir. Porphyritic Al-rich chondrules are consistently 16O-rich relative to nonporphyritic ones, suggesting that degree of melting is a key factor and pointing to a nebular setting for the isotopic exchange process. Because Al-rich chondrules are closely related to ferromagnesian chondrules, their radiogenic Mg isotopic abundances can plausibly be applied to help constrain the timing or location of chondrule formation.

Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

NASA Technical Reports Server (NTRS)

Cooper, George W.; Thiemens, Mark H.; Jackson, Teresa L.; Chang, Sherwood

1997-01-01

Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

1987-01-01

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

1977-01-01

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, in the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

Novel hybrid isotope separation scheme and apparatus

DOEpatents

Maya, Jakob

1991-01-01

A method of yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which the specific isotope is to be isolated, radiating the gas with frequencies characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photoionization reaction of the desired isotope, and collecting the specific isotope ion by suitable ion collection means.

Method of separating boron isotopes

DOEpatents

Jensen, R.J.; Thorne, J.M.; Cluff, C.L.

1981-01-23

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)-dichloroborane as the feed material. The photolysis can readily by achieved with CO/sub 2/ laser radiation and using fluences significantly below those required to dissociate BCl/sub 3/.

Method of separating boron isotopes

DOEpatents

Jensen, Reed J.; Thorne, James M.; Cluff, Coran L.; Hayes, John K.

1984-01-01

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO.sub.2 laser radiation and using fluences significantly below those required to dissociate BCl.sub.3.

Doubly labelled water assessment of energy expenditure: principle, practice, and promise.

PubMed

Westerterp, Klaas R

2017-07-01

The doubly labelled water method for the assessment of energy expenditure was first published in 1955, application in humans started in 1982, and it has become the gold standard for human energy requirement under daily living conditions. The method involves enriching the body water of a subject with heavy hydrogen ( 2 H) and heavy oxygen ( 18 O), and then determining the difference in washout kinetics between both isotopes, being a function of carbon dioxide production. In practice, subjects get a measured amount of doubly labelled water ( 2 H 2 18 O) to increase background enrichment of body water for 18 O of 2000 ppm with at least 180 ppm and background enrichment of body water for 2 H of 150 ppm with 120 ppm. Subsequently, the difference between the apparent turnover rates of the hydrogen and oxygen of body water is assessed from blood-, saliva-, or urine samples, collected at the start and end of the observation interval of 1-3 weeks. Samples are analyzed for 18 O and 2 H with isotope ratio mass spectrometry. The doubly labelled water method is the indicated method to measure energy expenditure in any environment, especially with regard to activity energy expenditure, without interference with the behavior of the subjects. Applications include the assessment of energy requirement from total energy expenditure, validation of dietary assessment methods and validation of physical activity assessment methods with doubly labelled water measured energy expenditure as reference, and studies on body mass regulation with energy expenditure as a determinant of energy balance.

Noble gases in the Murchison meteorite - Possible relics of s-process nucleosynthesis

NASA Technical Reports Server (NTRS)

Srinivasan, B.; Anders, E.

1978-01-01

The Murchison carbonaceous chondrite contains a new type of xenon component, enriched by up to 50 percent in five of the nine stable xenon isotopes, mass numbers 128 to 132. This component is released at 1200 to 1600 C from a severely etched mineral fraction. Krypton shows a similar but smaller enrichment in the isotopes 80 and 82. Neon and helium released in the same interval also are quite anomalous, being highly enriched in the isotopes 22 and 3. These patterns are strongly suggestive of three nuclear processes believed to take place in red giants: the s process (neutron capture on a slow time scale), helium burning, and hydrogen shell burning. If this interpretation is correct, then primitive meteorites contain yet another kind of alien, presolar material: dust grains ejected from red giants.

Possible Nuclear Safeguards Applications: Workshop on Next-Generation Laser Compton Gamma Source

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

Durham, J. Matthew

2016-11-17

These are a set of slides for the development of a next-generation photon source white paper. The following topics are covered in these slides: Nuclear Safeguards; The Nuclear Fuel Cycle; Precise isotopic determination via NRF; UF 6 Enrichment Assay; and Non-Destructive Assay of Spent Nuclear Fuel. In summary: A way to non-destructively measure precise isotopics of ~kg and larger samples has multiple uses in nuclear safeguards; Ideally this is a compact, fieldable device that can be used by international inspectors. Must be rugged and reliable; A next-generation source can be used as a testing ground for these techniques as technologymore » develops.« less

Uranium Bio-accumulation and Cycling as revealed by Uranium Isotopes in Naturally Reduced Sediments from the Upper Colorado River Basin

NASA Astrophysics Data System (ADS)

Lefebvre, Pierre; Noël, Vincent; Jemison, Noah; Weaver, Karrie; Bargar, John; Maher, Kate

2016-04-01

Uranium (U) groundwater contamination following oxidized U(VI) releases from weathering of mine tailings is a major concern at numerous sites across the Upper Colorado River Basin (CRB), USA. Uranium(IV)-bearing solids accumulated within naturally reduced zones (NRZs) characterized by elevated organic carbon and iron sulfide compounds. Subsequent re-oxidation of U(IV)solid to U(VI)aqueous then controls the release to groundwater and surface water, resulting in plume persistence and raising public health concerns. Thus, understanding the extent of uranium oxidation and reduction within NRZs is critical for assessing the persistence of the groundwater contamination. In this study, we measured solid-phase uranium isotope fractionation (δ238/235U) of sedimentary core samples from four study sites (Shiprock, NM, Grand Junction, Rifle and Naturita, CO) using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). We observe a strong correlation between U accumulation and the extent of isotopic fractionation, with Δ238U up to +1.8 ‰ between uranium-enriched and low concentration zones. The enrichment in the heavy isotopes within the NRZs appears to be especially important in the vadose zone, which is subject to variations in water table depth. According to previous studies, this isotopic signature is consistent with biotic reduction processes associated with metal-reducing bacteria. Positive correlations between the amount of iron sulfides and the accumulation of reduced uranium underline the importance of sulfate-reducing conditions for U(IV) retention. Furthermore, the positive fractionation associated with U reduction observed across all sites despite some variations in magnitude due to site characteristics, shows a regional trend across the Colorado River Basin. The maximum extent of 238U enrichment observed in the NRZ proximal to the water table further suggests that the redox cycling of uranium, with net release of U(VI) to the groundwater by non-fractionating oxidation, is occurring within this zone. Thus, release of uranium from the NRZs may play a critical role in the persistence of groundwater contamination at these sites.

Chemical and isotopic evolution of a layered eastern U.S. snowpack and its relation to stream-water composition

USGS Publications Warehouse

Shanley, J.B.; Kendall, C.; Albert, M.R.; Hardy, J.P.

1995-01-01

The chemical, isotopic, and morphologic evolution of a layered snowpack was investigated during the winter of 1993-94 at Sleepers River Research Watershed in Danville, Vermont. The snowpack was monitored at two small basins: a forested basin at 525 m elevation, and an agricultural basin at 292 m elevation. At each site, the snowpack morphology was characterized and individual layers were sampled seven times during the season. Nitrate and 8d18O profiles in the snowpack remained relatively stable until peak accumulation in mid-March, except near the snow surface, where rain-on-snow events caused water and nitrate movement down to impeding ice layers. Subsequently, water and nitrate moved more readily through the ripening snowpack. As the snowpack evolved, combined processes of preferential ion elution, isotopic fractionation, and infiltration of isotopically heavy rainfall caused the pack to become depleted in solutes and isotopically enriched. The release of nitrate and isotopically depleted water was reflected in patterns of nitrate concentrations and ??18O of meltwater and stream water. Results supported data from the previous year which suggested that streamflow in the forested basin during snowmelt was dominated by groundwater discharge.

Carbon and nitrogen isotopic analysis of coral-associated nitrogen in rugose corals of the Middle Devonian, implications for paleoecology and paleoceanography.

NASA Astrophysics Data System (ADS)

Hickey, A. N.; Junium, C. K.; Uveges, B. T.; Ivany, L. C.; Martindale, R. C.

2017-12-01

The Middle Devonian Appalachian Basin of Central New York hosts an extraordinary diversity of well-studied fossil invertebrates within the shallow marine sequences of the Givetian Age, Hamilton Group. Of particular interest are a series of aerially expansive coral beds with diverse assemblages of rugose corals. These well-preserved specimens provide an excellent opportunity to test the feasibility of δ15N and δ13C analyses in rugose corals in an effort to resolve outstanding issues regarding their paleoecology and ontogeny as well environmental dynamics within the Devonian Appalachian Basin. Here we present carbon and nitrogen isotope analyses of the rugose corals Heliophyllum and Siphonophrentis from the Joshua Coral Bed. Corals were cleaned of the host calcareous shale and sonicated sequentially in deionized water and methanol, and then oxidatively cleaned. Cleaned corals were sectioned into 0.5cm billets to obtain enough residual organic material for analysis. The organic content of the corals is low, but nanoEA allows for serial sampling of 5-10 samples per coral. Coral sections were decarbonated and the residual organic material is filtered and dried prior to analysis. Coral organic matter is analyzed in triplicate using nanoEA, which is a cryo-trapping, capillary focusing technique for δ15N and δ13C. The δ15N of organic matter extracted from rugose corals is, on average, enriched by 2-4‰ relative to the bulk nitrogen in the host rock. As well, the δ13C of organic carbon from the corals is 13C-enriched relative to the bulk rock, but to a lesser degree (no more than 1.5‰). Assuming that the bulk rock carbon and nitrogen are largely representative of the long-term primary production background, the modest enrichment is consistent with a trophic effect, and that rugose corals are likely planktivores. In an individual coral, δ15N ranges by 3-4‰ over its length, and when adjusted for trophic enrichment varies around the average δ15N of bulk sedimentary organic matter (+2.0‰). There is no apparent trajectory in the isotopic composition of organic matter, which suggests that over the sampled life history of the corals we cannot resolve any ontogenetic trends. Therefore, the variability in the δ15N of the coral organic matter likely reflects short-term variability in basinal conditions or changes in coral food supply.

The geochemistry of primitive volcanic rocks of the Ankaratra volcanic complex, and source enrichment processes in the genesis of the Cenozoic magmatism in Madagascar

NASA Astrophysics Data System (ADS)

Melluso, L.; Cucciniello, C.; le Roex, A. P.; Morra, V.

2016-07-01

The Ankaratra volcanic complex in central Madagascar consists of lava flows, domes, scoria cones, tuff rings and maars of Cenozoic age that are scattered over 3800 km2. The mafic rocks include olivine-leucite-nephelinites, basanites, alkali basalts and hawaiites, and tholeiitic basalts. Primitive samples have high Mg# (>60), high Cr and Ni concentrations; their mantle-normalized patterns peak at Nb and Ba, have troughs at K, and smoothly decrease towards the least incompatible elements. The Ankaratra mafic rocks show small variation in Sr-Nd-Pb isotopic compositions (e.g., 87Sr/86Sr = 0.70377-0.70446, 143Nd/144Nd = 0.51273-0.51280, 206Pb/204Pb = 18.25-18.87). These isotopic values differ markedly from those of Cenozoic mafic lavas of northern Madagascar and the Comoro archipelago, typical Indian Ocean MORB and oceanic basalt end-members. The patterns of olivine nephelinitic magmas can be obtained through 3-10% partial melting of a mantle source that was enriched by a Ca-rich alkaline melt, and that contained garnet, carbonates and phlogopite. The patterns of tholeiitic basalts can be obtained after 10-12% partial melting of a source enriched with lower amounts of the same alkaline melt, in the spinel- (and possibly amphibole-) facies mantle, hence in volumes where carbonate is not a factor. The significant isotopic change from the northernmost volcanic rocks of Madagascar and those in the central part of the island implicates a distinct source heterogeneity, and ultimately assess the role of the continental lithospheric mantle as source region. The source of at least some volcanic rocks of the still active Comoro archipelago may have suffered the same time-integrated geochemical and isotopic evolution as that of the northern Madagascar volcanic rocks.

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.

Plume versus plate origin for the Shatsky Rise oceanic plateau (NW Pacific): Insights from Nd, Pb and Hf isotopes

NASA Astrophysics Data System (ADS)

Heydolph, Ken; Murphy, David T.; Geldmacher, Jörg; Romanova, Irina V.; Greene, Andrew; Hoernle, Kaj; Weis, Dominique; Mahoney, John

2014-07-01

Shatsky Rise, an early Cretaceous igneous oceanic plateau in the NW Pacific, comprises characteristics that could be attributed to either formation by shallow, plate tectonic-controlled processes or to an origin by a mantle plume (head). The plateau was drilled during Integrated Ocean Drilling Program (IODP) Expedition 324. Complementary to a recent trace element study (Sano et al., 2012) this work presents Nd, Pb and Hf isotope data of recovered lava samples cored from the three major volcanic edifices of the Shatsky Rise. Whereas lavas from the oldest edifice yield fairly uniform compositions, a wider isotopic spread is found for lavas erupted on the younger parts of the plateau, suggesting that the Shatsky magma source became more heterogeneous with time. At least three isotopically distinct components can be identified in the magma source: 1) a volumetrically and spatially most common, moderately depleted component of similar composition to modern East Pacific Ridge basalt but with low 3He/4He, 2) an isotopically very depleted component which could represent local, early Cretaceous (entrained) depleted upper mantle, and 3) an isotopically enriched component, indicating the presence of (recycled) continental material in the magma source. The majority of analyzed Shatsky lavas, however, possess Nd-Hf-Pb isotope compositions consistent with a derivation from an early depleted, non-chondritic reservoir. By comparing these results with petrological and trace element data of mafic volcanic rock samples from all three massifs (Tamu, Ori, Shirshov), we discuss the origin of Shatsky Rise magmatism and evaluate the possible involvement of a mantle plume (head).

The record of mantle heterogeneity preserved in Earth's oceanic crust

NASA Astrophysics Data System (ADS)

Burton, K. W.; Parkinson, I. J.; Schiano, P.; Gannoun, A.; Laubier, M.

2017-12-01

Earth's oceanic crust is produced by melting of the upper mantle where it upwells beneath mid-ocean ridges, and provides a geographically widespread elemental and isotopic `sample' of Earth's mantle. The chemistry of mid-ocean ridge basalts (MORB), therefore, holds key information on the compositional diversity of the upper mantle, but the problem remains that mixing and reaction during melt ascent acts to homogenise the chemical variations they acquire. Nearly all isotope and elemental data obtained thus far are for measurements of MORB glass, and this represents the final melt to crystallise, evolving in an open system. However, the crystals that are present are often not in equilibrium with their glass host. Melts trapped in these minerals indicate that they crystallised from primitive magmas that possess diverse compositions compared to the glass. Therefore, these melt inclusions preserve information on the true extent of the mantle that sources MORB, but are rarely amenable to precise isotope measurement. An alternative approach is to measure the isotope composition of the primitive minerals themselves. Our new isotope data indicates that these minerals crystallised from melts with significantly different isotope compositions to their glass host, pointing to a mantle source that has experienced extreme melt depletion. These primitive minerals largely crystallised in the lower oceanic crust, and our preliminary data for lower crustal rocks and minerals shows that they preserve a remarkable range of isotope compositions. Taken together, these results indicate that the upper mantle sampled by MORB is extremely heterogeneous, reflecting depletion and enrichment over much of Earth's geological history.

Ca, Sr and Ba stable isotopes reveal the fate of soil nutrients along a tropical climosequence

USGS Publications Warehouse

Bullen, Thomas D.; Chadwick, Oliver A.

2016-01-01

Nutrient biolifting is an important pedogenic process in which plant roots obtain inorganic nutrients such as phosphorus (P) and calcium (Ca) from minerals at depth and concentrate those nutrients at the surface. Here we use soil chemistry and stable isotopes of the alkaline earth elements Ca, strontium (Sr) and barium (Ba) to test the hypothesis that biolifting of P has been an important pedogenic process across a soil climosequence developed on volcanic deposits at Kohala Mountain, Hawaii. The geochemical linkage between these elements is revealed as generally positive site-specific relationships in soil mass gains and losses, particularly for P, Ba and Ca, using the ratio of immobile elements titanium and niobium (Ti/Nb) to link individual soil samples to a restricted compositional range of the chemically and isotopically diverse volcanic parent materials. At sites where P is enriched in surface soils relative to abundances in deeper soils, the isotope compositions of exchangeable Ca, Sr and Ba in the shallowest soil horizons (< 10 cm depth) are lighter than those of the volcanic parent materials and trend toward those of plants growing on fresh volcanic deposits. In contrast the isotope composition of exchangeable Ba in deeper soil horizons (> 10 cm depth) at those sites is consistently heavier than the volcanic parent materials. The isotope compositions of exchangeable Ca and Sr trend toward heavier compositions with depth more gradually, reflecting increasing leakiness from these soils in the order Ba < Sr < Ca and downward transfer of light biocycled Ca and Sr to deeper exchange sites. Given the long-term stability of ecosystem properties at the sites where P is enriched in surface soils, a simple box model demonstrates that persistence of isotopically light exchangeable Ca, Sr and Ba in the shallowest soil horizons requires that the uptake flux to plants from those near-surface layers is less than the recycling flux returned to the surface as litterfall. This observation implicates an uptake flux from an additional source which we attribute to biolifting. We view the heavy exchangeable Ba relative to soil parent values in deeper soils at sites where P is enriched in surface soils, and indeed at all but the wettest site across the climosequence, to represent the complement of an isotopically light Ba fraction removed from these soils by plant roots consistent with the biolifting hypothesis. We further suggest that decreasing heaviness of depth-integrated exchangeable Ba in deeper soils with increasing median annual precipitation across the climosequence reflects greater reliance on shallow nutrient sources as site water balance increases. While the Ca, Sr and Ba isotopes considered together were useful in confirming an important role for nutrient biolifting across the climosequence, the Ba isotopes provided the most robust tracer of biolifting and have the greatest potential to find application as an isotopic proxy for P dynamics in soils.

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

NASA Astrophysics Data System (ADS)

Bizimis, Michael; Salters, Vincent

2010-05-01

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

Increase in soil stable carbon isotope ratio relates to loss of organic carbon: results from five long-term bare fallow experiments.

PubMed

Menichetti, Lorenzo; Houot, Sabine; van Oort, Folkert; Kätterer, Thomas; Christensen, Bent T; Chenu, Claire; Barré, Pierre; Vasilyeva, Nadezda A; Ekblad, Alf

2015-03-01

Changes in the (12)C/(13)C ratio (expressed as δ(13)C) of soil organic C (SOC) has been observed over long time scales and with depth in soil profiles. The changes are ascribed to the different reaction kinetics of (12)C and (13)C isotopes and the different isotopic composition of various SOC pool components. However, experimental verification of the subtle isotopic shifts associated with SOC turnover under field conditions is scarce. We determined δ(13)C and SOC in soil sampled during 1929-2009 in the Ap-horizon of five European long-term bare fallow experiments kept without C inputs for 27-80 years and covering a latitudinal range of 11°. The bare fallow soils lost 33-65% of their initial SOC content and showed a mean annual δ(13)C increase of 0.008-0.024‰. The (13)C enrichment could be related empirically to SOC losses by a Rayleigh distillation equation. A more complex mechanistic relationship was also examined. The overall estimate of the fractionation coefficient (ε) was -1.2 ± 0.3‰. This coefficient represents an important input to studies of long-term SOC dynamics in agricultural soils that are based on variations in (13)C natural abundance. The variance of ε may be ascribed to site characteristics not disclosed in our study, but the very similar kinetics measured across our five experimental sites suggest that overall site-specific factors (including climate) had a marginal influence and that it may be possible to isolate a general mechanism causing the enrichment, although pre-fallow land use may have some impact on isotope abundance and fractionation.

In situ experiments for element species-specific environmental reactivity of tin and mercury compounds using isotopic tracers and multiple linear regression.

PubMed

Rodriguez-Gonzalez, Pablo; Bouchet, Sylvain; Monperrus, Mathilde; Tessier, Emmanuel; Amouroux, David

2013-03-01

The fate of mercury (Hg) and tin (Sn) compounds in ecosystems is strongly determined by their alkylation/dealkylation pathways. However, the experimental determination of those transformations is still not straightforward and methodologies need to be refined. The purpose of this work is the development of a comprehensive and adaptable tool for an accurate experimental assessment of specific formation/degradation yields and half-lives of elemental species in different aquatic environments. The methodology combines field incubations of coastal waters and surface sediments with the addition of species-specific isotopically enriched tracers and a mathematical approach based on the deconvolution of isotopic patterns. The method has been applied to the study of the environmental reactivity of Hg and Sn compounds in coastal water and surface sediment samples collected in two different coastal ecosystems of the South French Atlantic Coast (Arcachon Bay and Adour Estuary). Both the level of isotopically enriched species and the spiking solution composition were found to alter dibutyltin and monomethylmercury degradation yields, while no significant changes were measurable for tributyltin and Hg(II). For butyltin species, the presence of light was found to be the main source of degradation and removal of these contaminants from surface coastal environments. In contrast, photomediated processes do not significantly influence either the methylation of mercury or the demethylation of methylmercury. The proposed method constitutes an advancement from the previous element-specific isotopic tracers' approaches, which allows for instance to discriminate the extent of net and oxidative Hg demethylation and to identify which debutylation step is controlling the environmental persistence of butyltin compounds.

Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

NASA Technical Reports Server (NTRS)

Mahaffy, P.; Niemann, Hasso (Technical Monitor)

2001-01-01

Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

NASA Astrophysics Data System (ADS)

Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

2016-08-01

In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs.

Preparation of Authigenic Pyrite from Methane-bearing Sediments for In Situ Sulfur Isotope Analysis Using SIMS.

PubMed

Lin, Zhiyong; Sun, Xiaoming; Peckmann, Jörn; Lu, Yang; Strauss, Harald; Xu, Li; Lu, Hongfeng; Teichert, Barbara M A

2017-08-31

Different sulfur isotope compositions of authigenic pyrite typically result from the sulfate-driven anaerobic oxidation of methane (SO4-AOM) and organiclastic sulfate reduction (OSR) in marine sediments. However, unravelling the complex pyritization sequence is a challenge because of the coexistence of different sequentially formed pyrite phases. This manuscript describes a sample preparation procedure that enables the use of secondary ion mass spectroscopy (SIMS) to obtain in situ δ 34 S values of various pyrite generations. This allows researchers to constrain how SO4-AOM affects pyritization in methane-bearing sediments. SIMS analysis revealed an extreme range in δ 34 S values, spanning from -41.6 to +114.8‰, which is much wider than the range of δ 34 S values obtained by the traditional bulk sulfur isotope analysis of the same samples. Pyrite in the shallow sediment mainly consists of 34 S-depleted framboids, suggesting early diagenetic formation by OSR. Deeper in the sediment, more pyrite occurs as overgrowths and euhedral crystals, which display much higher SIMS δ 34 S values than the framboids. Such 34 S-enriched pyrite is related to enhanced SO4-AOM at the sulfate-methane transition zone, postdating OSR. High-resolution in situ SIMS sulfur isotope analyses allow for the reconstruction of the pyritization processes, which cannot be resolved by bulk sulfur isotope analysis.

The Hadean upper mantle conundrum: evidence for source depletion and enrichment from Sm-Nd, Re-Os, and Pb isotopic compositions in 3.71 Gy boninite-like metabasalts from the Isua Supracrustal Belt, Greenland

NASA Astrophysics Data System (ADS)

Frei, Robert; Polat, Ali; Meibom, Anders

2004-04-01

Here we present Sm-Nd, Re-Os, and Pb isotopic data of carefully screened, least altered samples of boninite-like metabasalts from the Isua Supracrustal Belt (ISB, W Greenland)that characterize their mantle source at the time of their formation. The principal observations of this study are that by 3.7-3.8 Ga melt source regions existed in the upper mantle with complicated enrichment/depletion histories. Sm-Nd isotopic data define a correlation line with a slope corresponding to an age of 3.69 ± 0.18 Gy and an initial εNd value of +2.0 ± 4.7. This Sm-Nd age is consistent with indirect (but more precise) U-Pb geochronological estimates for their formation between 3.69-3.71 Ga. Relying on the maximum formation age of 3.71 Gy defined by the external age constraints, we calculate an average εNd [T = 3.71 Ga] value of +2.2 ± 0.9 (n = 18, 1σ) for these samples, which is indicative of a strongly depleted mantle source. This is consistent with the high Os concentrations, falling in the range between 1.9-3.4 ppb, which is similar to the estimated Os concentration for the primitive upper mantle. Re-Os isotopic data (excluding three outliers) yield an isochron defining an age of 3.76 ± 0.09 Gy (with an initial γOs value of 3.9 ± 1.2), within error consistent with the Sm-Nd age and the indirect U-Pb age estimates. An average initial γOs [T = 3.71 Ga] value of + 4.4 ± 1.2 (n = 8; 2σ) is indicative of enrichment of their source region during, or prior to, its melting. Thus, this study provides the first observation of an early Archean upper mantle domain with a distinctly radiogenic Os isotopic signature. This requires a mixing component characterized by time-integrated suprachondritic Re/Os evolution and a Os concentration high enough to strongly affect the Os budget of the mantle source; modern sediments, recycled basaltic crust, or the outer core do not constitute suitable candidates. At this point, the nature of the mantle or crustal component responsible for the radiogenic Os isotopic signature is not known. Compared with the Sm-Nd and Re-Os isotope systems, the Pb isotope systematics show evidence for substantial perturbation by postformational hydrothermal-metasomatic alteration processes accompanying an early Archean metamorphic event at 3510 ± 65 Ma and indicate that the U-Th-Pb system was partially opened to Pb-loss on a whole rock scale. Single stage mantle evolution models fail to provide a solution to the Pb isotopic data, which requires that a high-μ component was mixed with the depleted mantle component before or during the extrusion of the basalts. Relatively high 207Pb/204Pb ratios (compared to contemporaneous mantle), support the hypothesis that erosion products of the ancient terrestrial protocrust existed for several hundred My before recycling into the mantle before ∼3.7 Ga. Our results are broadly consistent with models favoring a time-integrated Hadean history of mantle depletion and with the existence of an early Hadean protocrust, the complement to the Hadean depleted mantle, which after establishment of subduction-like processes was, at least locally, recycled into the upper mantle before 3.7 Ga. Thus, already in the Hadean, the upper mantle seems to be characterized by geochemical heterogeneity on a range of length scales; one property that is shared with the modern upper mantle. However, a simple two component mixing scenario between depleted mantle and an enriched-, crustal component with a modern analogue can not account for the complicated and contradictory geochemical properties of this particular Hadean upper mantle source.

Lithium and boron in late-orogenic granites - Isotopic fingerprints for the source of crustal melts?

NASA Astrophysics Data System (ADS)

Romer, Rolf L.; Meixner, Anette; Förster, Hans-Jürgen

2014-04-01

Geochemically diverse late- and post-Variscan granites of the Erzgebirge-Vogtland, the Saxon Granulite Massif, and Thuringia (Germany) formed by anatectic melting of Palaeozoic sedimentary successions and associated mafic to felsic volcanic rocks. The compositional diversity of the least evolved of these granites is largely inherited from the protoliths. We present Li and B-isotopic data of these granites and compare them with the isotopic composition of their protoliths, to investigate whether (i) there exist systematic differences in the Li and B-isotopic composition among different granite types and (ii) Li and B-isotopic compositions provide information on the granite sources complementary to information from the isotopic composition of Sr, Nd, and Pb and the trace-element signatures. Low-F biotite and two-mica granite types have flat upper continental crust (UCC)-normalized trace-element pattern with variable enrichments in Li, Rb, Cs, Sn, and W and depletions in Sr, Ba, and Eu. These signatures are least pronounced for the Niederbobritzsch biotite granite, which has the largest contribution of mafic material, and most pronounced for the two-mica granites. The granites show a relatively narrow range of δ7Li values (-3.0 to -0.5) and a broad range of δ11B values (-13.4 to +20.1). The δ11B values are lower in rocks with distinctly higher contents of Li, Rb, Cs, and Sn. The high δ11B of the Niederbobritzsch granite may be explained by the melting of former altered oceanic crust in its source. Relative to UCC, intermediate-F to high-F low-P granites show strong depletions in Sr, Ba, Eu as well as Zr and Hf, strong enrichments in Li, Rb, and Cs as well as Nb, Sn, Ta, and W, and REE pattern with stronger enrichments for HREE than for LREE. These granites show narrow ranges of δ7Li (-2.0 to +1.6) and δ11B values (-14.7 to -9.1), reflecting the smaller variability of the Li and B-isotopic composition in their source lithologies. The anomalously high δ7Li value (14.7) of one granite sample (Burgberg), which is similar to δ7Li values of its wall rocks (up to 14.5), may indicate late-magmatic fluid-rock interaction with external, wall rock-derived fluids. Because of the small compositional range of most source lithologies, the Li and B-isotopic variation in the granites is also small indicating that the isotopic composition of Li and B does not represent a particularly sensitive source tracer, with the exception of source lithologies characterized by extreme δ7Li or δ11B values.

Unradiogenic Pb Anomalies in Historical Lavas of Piton de la Fournaise (Reunion Island)

NASA Astrophysics Data System (ADS)

Vlastelic, I.

2008-12-01

A detailed investigation (218 samples) of Pb isotope variations in the most recent (1975-2007), well- documented and densely sampled eruptions of Piton de la Fournaise has been undertaken (Vlastelic et al, in press). Lead isotopes exhibit smooth temporal fluctuations (18.87<206Pb/204Pb<18.94) on which superimpose rare (5), but pronounced unradiogenic spikes (206Pb/204Pb down to 17.63). In 208Pb/204Pb vs. 206Pb/204Pb space, normal and anomalous samples plot along a single linear array. In 207Pb/204Pb vs. 206Pb/204Pb space, normal samples define an array whose slope (0.16) is commonly observed in ocean island basalts, whereas anomalous samples define less steep arrays (slopes down to 0.04). It follows that some of the anomalous samples have unusually high 207Pb/204Pb for their 206Pb/204Pb. These latter are enriched in Pb by a factor three. The lack of reproducibility of isotopic analyses suggests that samples are heterogeneous at a sub-millimeter scale. The origin of the unradiogenic anomalies is enigmatic. Leaching experiments rule out anthropogenic contamination. Interaction of plume melts with a contaminant genetically unrelated to the Reunion plume is possible although not supported by trace-element and Sr-Nd isotope signatures indistinguishable from normal lavas. On the other hand, interaction with or entrainment of Pb-rich, most likely unradiogenic sulfides could affect specifically Pb isotope compositions. Inspection of the well-know eruptions history reveals that the isotopic anomalies coincide with transitions from basalts to oceanites (lavas rich in cumulative olivine). Olivine and sulfides, which are both denser than silicate melts, could be entrained with magma pulses, which give rise to high-flux oceanite eruptions. Some sulfides may originate from the oceanic crust. Others may originate from sulfide solidus depth (c.a. 160 km) where sulfides melts are expected to pond (Hart and Gaetani, 2006). These deep sulfides melts could be remnants of past melting events of the Reunion plume. References Hart, S.R., Gaetani, G.A., 2006. Contrib. Mineral. Petrol. 152, 295-308. Vlastelic, I., et al., 2008. J. Volcanol. Geotherm. Res., in press.

Paleoproterozoic mantle enrichment beneath the Fennoscandian Shield: Isotopic insight from carbonatites and lamprophyres

NASA Astrophysics Data System (ADS)

Woodard, Jeremy; Huhma, Hannu

2015-11-01

The isotope geochemistry of carbonatite from Naantali, southwest Finland as well as lamprophyres from North Savo, eastern Finland and the NW Ladoga region, northwest Russia has been investigated. These Paleoproterozoic dykes represent melting of an enriched mantle source spread over a 96,000 km2 area within the Fennoscandian Shield and intruded during post-collisional extension. The carbonatites have εNd(T) ranging from -0.8 to + 0.4, while lamprophyres have εNd(T) between -0.8 and + 0.3. 87Sr/86Sr ratios from the primary carbonatite samples from Naantali form a tight cluster between 0.70283 and 0.70303. For the lamprophyres, 87Sr/86Sr ratios range from 0.70327-0.70339 from NW Ladoga and 0.70316-0.70327 from North Savo. These characteristics are consistent with derivation from an enriched mantle showing an EMII trend, formed when sediments of mixed Archean and Proterozoic provenance were recycled back into the mantle via subduction during the preceding Svecofennian orogeny. Linear mixing of these subducted sediments and depleted mantle shows that a multistage process of enrichment is required to produce the observed isotope compositions. Batch melting of the subducted sediment first generated hydrous alkaline silicate melt, which crystallised as mica- and amphibole-rich veins in the mantle wedge. Continued melting of the subducted material under higher P-T conditions produced carbonatite melt, which infiltrated preferentially into this vein network. Assuming the silicate melt exerts greater influence on 87Sr/86Sr ratios while the carbonatite more greatly affects 143Nd/144Nd ratios, the model predicts significant regional variation in the silicate metasomatism with more consistent carbonatite metasomatism throughout the Fennoscandian subcontinental lithospheric mantle. The subducted sediments were likely also rich in organic matter, resulting in highly negative δ13C in mantle carbonates. The model predicts a higher content of organic carbon in the sediments in close proximity to the Archean continent, decreasing with distance.

Kinetic fractionation processes recorded in the stalagmites of some limestone caves in Korea

NASA Astrophysics Data System (ADS)

Woo, K. S.; Jo, K.; Edwards, L. R.; Cheng, H.; Wang, Y.; Yoon, H.

2006-12-01

Stable isotope data (oxygen and carbon) of carbonate minerals (mostly calcite, but sometimes aragonite) in stalagmites have been the most commonly and widely used proxies for paleoclimatic research. This is based upon the assumption that carbonate minerals precipitated in isotopic equilibrium with dripping waters from stalactites, thus should reflect paleoclimatic variations. The state of equilibrium, so called "Hendy Test", has been commonly used. Hendy (1971) showed that during kinetic fractionation both oxygen and carbon isotopes behaves in a similar way due to faster degassing rate of cabon dioxide, resulting in the enrichment of both isotopes. The stalagmites from three limestone caves (Gwaneum, Eden and Daeya Caves) in Korea were investigated to understand the effects of kinetic fractionation during their growth. The stalagmites are mostly composed of columnar calcites, but contains the layers of cave coral that is composed of fibrous calcite. The cave coral layers should have grown when the supply rate of dripping water decreased significantly. Stable isotope pattern in three stalagmites do not show the same pattern of disequilibrium process. The cave corals in the Eden stalagmite show the enriched carbon and oxygen isotope values (15 and 5 per mil, respectively) that has the same bimodal pattern as suggested by Hendy (1971). However, the cave corals in the Gwaneum stalagmites show the enriched carbon, but depleted oxygen isotope values (3 and 1 per mil, respectively). Also, the calcite layer precipitated in disequilibrium in the Daeya stalagmite show more enriched carbon isotope values by up to 6 per mil, but show more or less the same oxygen isotopic values, compared to the columnar calcite which was precipitated in equilibrium. Therefore, caution should be made to determine the state of equilibrium precipitation of carbonate minerals in stalagmites. The "Hendy Test" may not be the only solution because other types of speleothems can be formed in stalagmites as the supply rate of dripping water changes. Also, different texture in stalagmites can be used as another criteria to determine the degree of equilibrium.

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, Christopher A.; Worden, Earl F.

1995-01-01

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of .sup.167 Er. The hyperfine structure of .sup.167 Er was used to find two three-step photoionization pathways having a common upper energy level.

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.

Tracing water sources of terrestrial animal populations with stable isotopes: laboratory tests with crickets and spiders.

PubMed

McCluney, Kevin E; Sabo, John L

2010-12-31

Fluxes of carbon, nitrogen, and water between ecosystem components and organisms have great impacts across levels of biological organization. Although much progress has been made in tracing carbon and nitrogen, difficulty remains in tracing water sources from the ecosystem to animals and among animals (the "water web"). Naturally occurring, non-radioactive isotopes of hydrogen and oxygen in water provide a potential method for tracing water sources. However, using this approach for terrestrial animals is complicated by a change in water isotopes within the body due to differences in activity of heavy and light isotopes during cuticular and transpiratory water losses. Here we present a technique to use stable water isotopes to estimate the mean mix of water sources in a population by sampling a group of sympatric animals over time. Strong correlations between H and O isotopes in the body water of animals collected over time provide linear patterns of enrichment that can be used to predict a mean mix of water sources useful in standard mixing models to determine relative source contribution. Multiple temperature and humidity treatment levels do not greatly alter these relationships, thus having little effect on our ability to estimate this population-level mix of water sources. We show evidence for the validity of using multiple samples of animal body water, collected across time, to estimate the isotopic mix of water sources in a population and more accurately trace water sources. The ability to use isotopes to document patterns of animal water use should be a great asset to biologists globally, especially those studying drylands, droughts, streamside areas, irrigated landscapes, and the effects of climate change.

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.

Trace Element Study of MORB Glasses from 14¡ã-16¡ãN along Mid-Atlantic Ridge by LA-ICP- MS

NASA Astrophysics Data System (ADS)

Barzoi, C. A.; Casey, J. F.; Gao, Y.; Lapen, T.

2007-12-01

A comparison of 20 MORB glasses from 14°-16° N along the Mid-Atlantic Ridge using both solution-based and in situ laser ablation-based ICP-MS trace element analyses on the same samples was conducted. Li, Be, Sc, Ti, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Tb, Gd, Dy, Ho, Er, Tm, Yb,Lu, Hf, Ta, Pb, Th, and U were analyzed using the Varian 810 quadrupole ICP-MS. The instrument features a 90 degree ion mirror and low noise double-off-axis quadrupole that allows high sensitivity and low backgrounds. Precision in term of relative standard deviation (RSD) of the measurements for both methods based on repeated analyses of USGS BIR-1G and BHVO-2G glass standards and Max Planck KL-2G glass standard is within 5 % for all trace elements with the exception of Pb, which averaged 12 %. Measured trace element abundances are within 2% of recommended standard values using both solution and laser ablation methods. Comparison between the analyte concentrations obtained by solution-based ICP-MS and in situ microanalysis by laser ablation reveals little systematic differences in abundances(<5% for all elements). The two-method correlation and strong repeatability of the results indicate that rapid in situ trace element analysis by laser ablation ICP-MS is likely to become a preferred method of trace element analysis for MORB glasses. Our geochemical results and previous studies of MORB glasses in the region of the MAR between 14°-16°N show that basalts are characterized isotopic and incompatible element enrichment.The nature of the enrichment has been the topic of significant discussion and speculation because a specific mantle plume is not well defined in the region. Likewise the magma supply is probably small in the region as the magmatic crust is interpreted to be very thin in most of the area studied. Integrated studies of major element, trace element, and isotopic variations among basalts, gabbroic rocks and igneous and residual ultramafic rocks in the region indicate that 1) the enriched basalts have positive Ta-Nb anomalies, enriched relative to U, Th, and La 2) basalts have relatively high SiO2 abundances compared to the global average, 3) basalts show a HIMU isotopic signature, and 4) bulk major element abundances and mineral chemistry in mantle rocks indicate that they are among the most depleted,although variably refertilized, residual mantle assemblages sampled to date along MORs.We suggest that much of the regional variation in major and trace element data, as well as isotopic data and the unusual regional geology (multiple core complexes) can be explained by melting of a sub-axial mantle that contains two end members, one highly depleted and the other enriched. These components appear to involve ancient recycled ocean crust and lithospheric mantle.

Novel hybrid isotope separation scheme and apparatus

DOEpatents

Maya, J.

1991-06-18

A method is described for yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which the specific isotope is to be isolated, radiating the gas with frequencies characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photoionization reaction of the desired isotope, and collecting the specific isotope ion by suitable ion collection means. 3 figures.

Baseline study on trace and rare earth elements in marine sediments collected along the Namibian coast.

PubMed

Orani, Anna Maria; Vassileva, Emilia; Wysocka, Irena; Angelidis, Michael; Rozmaric, Martina; Louw, Deon

2018-06-01

Namibia is a fast-growing country with extensive mineral extraction activities used in diamond, fluorspar, uranium, and metals production. To assess the impact of land based human activities on the Namibian coastal marine environment, 25 elements were analyzed in 22 surface sediments samples collected along the coast. After applying a variety of pollution assessment indices (Enrichment Factor, Igeo and Pollution Load Indexes) was concluded that As, Cd and Sb were considerably enriched in the sediments from several sites, while Cu, Pb and Zn showed very high enrichment near the Walvis Bay harbor. Pearson's correlation and Principal Component Analysis were used to investigate common metal sources. Additionally, the determination of Pb isotope ratios confirmed the contribution of land based human activities at Walvis Bay and Lüderitz as sources of pollution. The analysis of REEs did not reveal any important enrichment due to anthropogenic activities, but provides a needed baseline for further investigations. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Nondispersive infrared spectrometry for 13CO2/12CO2-measurements: a clinically feasible analyzer for stable isotope breath tests in gastroenterology.

PubMed

Braden, B; Caspary, W F; Lembcke, B

1999-06-01

13C-urea breath tests have become clinical routine for the diagnosis of Helicobacter pylori infection and other isotope breath tests have been invented e.g. for gastric emptying or quantitative liver function testing. Recently, isotope-selective nondispersive infrared spectrometers (NDIRS) have been developed for the analysis of the 13CO2/12CO2-enrichment in breath. In this study, we prospectively tested the validity of a newly developed NDIRS in comparison to isotope ratio mass spectrometry (IRMS). 142 patients with dyspeptic symptoms were tested for Helicobacter pylori infection using the 13C-urea breath test. The isotope ratio analysis of the breath samples was performed in duplicate both using IRMS and NDIRS. The results of the baseline-corrected 13CO2-exhalation values between IRMS and NDIRS were in excellent agreement. The mean difference between both methods was 0.28 +/- 1.93 delta/1000. Evaluating the qualitative urea breath test results in reference to IRMS as the reference the NDIRS had a sensitivity of 97.8% and a specificity of 98.9%. The isotope-selective nondispersive infrared spectroscopy is going to become a reliable, but low-cost and easy-to-operate alternative to expensive isotope ratio mass spectrometry in the analysis of 13C-breath tests.

Identifying the origins of local atmospheric deposition in the steel industry basin of Luxembourg using the chemical and isotopic composition of the lichen Xanthoria parietina.

PubMed

Hissler, Christophe; Stille, Peter; Krein, Andreas; Geagea, Majdi Lahd; Perrone, Thierry; Probst, Jean-Luc; Hoffmann, Lucien

2008-11-01

Trace metal atmospheric contamination was assessed in one of the oldest European industrial sites of steel production situated in the southern part of the Grand-Duchy of Luxembourg. Using elemental ratios as well as Pb, Sr, and Nd isotopic compositions as tracers, we found preliminary results concerning the trace metal enrichment and the chemical/isotopic signatures of the most important emission sources using the lichen Xanthoria parietina sampled at 15 sites along a SW-NE transect. The concentrations of these elements decreased with increasing distance from the historical and actual steel-work areas. The combination of the different tracers (major elements, Rare Earth Element ratios, Pb, Sr and Nd isotopes) enabled us to distinguish between three principal sources: the historical steel production (old tailings corresponding to blast-furnace residues), the present steel production (industrial sites with arc electric furnace units) and the regional background (baseline) components. Other anthropogenic sources including a waste incinerator and major roads had only weak impacts on lichen chemistry and isotopic ratios. The correlation between the Sr and Nd isotope ratios indicated that the Sr-Nd isotope systems represented useful tools to trace atmospheric emissions of factories using scrap metal for steel production.

Controls on ecohydrological dynamics of riparian zones in Alpine catchments: A comparison study of two rivers in the Eastern Italian Alps

NASA Astrophysics Data System (ADS)

Engel, Michael; Penna, Daniele; Frentress, Jay; Andreoli, Andrea; Hecher, Peter; Van Meerveld, Ilja; Comiti, Francesco

2017-04-01

In recent decades, restauration actions have been implemented in mountain rivers to face widespread morphological changes. Such natural and anthropogenic modifications can have relevant impacts on the ecological and ecohydrological functioning of riparian vegetation. Understanding the water sources used by riparian vegetation is important for the implementation of effective river restoration initiatives. Therefore, more ecohydrological research is needed to quantify the complex interactions between hydrology and vegetation in different alpine river systems. In this study we used water stable isotopes and electrical conductivity (EC) as tracers to better understand the hydrological and ecohydrological relationship between the riparian vegetation and the river bed of alpine river systems. We choose two catchments, Ahr/Aurino River and Mareit/Ridanna River catchments (South Tyrol, Italy) as study sites. In both catchments, we selected two sites comprising a younger (< 5 years) and an older (> 10 years) alder (Alnus incana) stand. At each site, soil moisture at different depths and groundwater levels were monitored. Suction lysimeters were installed at the same depths than the soil moisture sensors. Samples for tracer analysis were collected since June 2016 on a bi-weekly or monthly basis from precipitation, soil water, groundwater and stream water. EC was continuously measured in a piezometer at the Mareit River. In addition, we extracted sap water for isotopic analysis from alder trees. First results show that all water types sampled in both catchments fell along the global meteoric water line showing no evaporative enrichments. Sap samples are expected to deviate from the meteoric line but they have not been analysed yet. At both sites in the Ahr catchment, soil water seemed to be more variable and isotopically more enriched at 10 cm depth (δ2H: - 34 to -69 ‰) than at 50 cm (δ2H: -45 to -71 ‰), indicating a decreasing influence of precipitation with increasing soil depth. In contrast, soil water at Mareit River seemed to depend stronger on the topographical location of the site than on the soil depth. Groundwater in the Ahr catchment at the end of July 2016 showed isotopic depletion (δ2H: -89 ‰), which occurred about one month later than the isotopic depletion observed in the stream (δ2H: -96 ‰). This may indicate a stream-groundwater connectivity with a specific time lag. These observations may provide a first insight into the main controls on the complex interactions between stream and vegetation in the riparian zone. Keywords: stable isotopes of water; sap; alpine rivers; riparian zone connectivity; ecohydrology

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

NASA Astrophysics Data System (ADS)

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

2001-12-01

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

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

NASA Astrophysics Data System (ADS)

Nelson, D. B.; Kahmen, A.

2017-12-01

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

Uranium isotope separation from 1941 to the present

NASA Astrophysics Data System (ADS)

Maier-Komor, Peter

2010-02-01

Uranium isotope separation was the key development for the preparation of highly enriched isotopes in general and thus became the seed for target development and preparation for nuclear and applied physics. In 1941 (year of birth of the author) large-scale development for uranium isotope separation was started after the US authorities were warned that NAZI Germany had started its program for enrichment of uranium and might have confiscated all uranium and uranium mines in their sphere of influence. Within the framework of the Manhattan Projects the first electromagnetic mass separators (Calutrons) were installed and further developed for high throughput. The military aim of the Navy Department was to develop nuclear propulsion for submarines with practically unlimited range. Parallel to this the army worked on the development of the atomic bomb. Also in 1941 plutonium was discovered and the production of 239Pu was included into the atomic bomb program. 235U enrichment starting with natural uranium was performed in two steps with different techniques of mass separation in Oak Ridge. The first step was gas diffusion which was limited to low enrichment. The second step for high enrichment was performed with electromagnetic mass spectrometers (Calutrons). The theory for the much more effective enrichment with centrifugal separation was developed also during the Second World War, but technical problems e.g. development of high speed ball and needle bearings could not be solved before the end of the war. Spying accelerated the development of uranium separation in the Soviet Union, but also later in China, India, Pakistan, Iran and Iraq. In this paper, the physical and chemical procedures are outlined which lead to the success of the project. Some security aspects and Non-Proliferation measures are discussed.

Insights into nutrient assimilation and export in naturally iron-fertilized waters of the Southern Ocean from nitrogen, carbon and oxygen isotopes

NASA Astrophysics Data System (ADS)

Trull, Thomas W.; Davies, Diana; Casciotti, Karen

2008-03-01

The KErguelen Ocean and Plateau compared Study (KEOPS) documented enhanced iron input and phytoplankton biomass over the deep Kerguelen plateau in comparison to surrounding high-nutrient low-chlorophyll (HNLC) waters in late summer 2005. We examined the influence of this iron on nitrogen and carbon metabolism by the microbial food-web, by comparing samples from on-plateau and off-plateau. Suspended particulate organic carbon (POC) was ˜5 times more abundant on-plateau and exhibited greater POC/PON (˜6.5 vs. ˜5.5), δ13C-POC (˜-21.5 vs. ˜-24.5‰) and δ15N-PON (˜+2 vs. ˜0‰) than off-plateau. These differences arose in part from changes in ecosystem structure as demonstrated by size-fractionation (1, 5, 20, 55, 210, and 335-μm filters in series), which revealed large isotopic variations with size ( δ13C-POC ranged from -28 to -19‰ and δ15N-PON from -3 to +5‰) and greater abundances of 13C- and 15N-enriched large phytoplankton over the plateau. The 13C enrichment in POC reflected faster growth rates and greater draw-down of dissolved inorganic carbon over the plateau. Quantitative comparison to the δ15N of dissolved nitrate indicates that the δ15N-PON enrichment derived from increased assimilation of nitrate, corresponding to new production f-ratios of 0.7-0.9 on-plateau vs. 0.4-0.6 off-plateau. Results from a sparse set of free-drifting sediment trap samples suggest control of export by zooplankton grazing. The 15N and 18O enrichments in dissolved nitrate exhibited a 1:1 correlation, indicating that phytoplankton assimilation controls nitrate availability and only a relatively small amount of nitrate was regenerated by nitrification. The δ15N-NO 3 values yield indistinguishable isotopic fractionation factors on and off the plateau ( 15ɛ of 4-5‰). This suggests that variations in iron availability may not bias the interpretation of paleo-environmental 15N records, and leaves intact the view that higher sedimentary δ15N-PON values during the last glacial maximum indicate greater fractional nitrate depletion in the Southern Ocean.

Quantitation of (R)- and (S)-linalool in beer using solid phase microextraction (SPME) in combination with a stable isotope dilution assay (SIDA).

PubMed

Steinhaus, Martin; Fritsch, Helge T; Schieberle, Peter

2003-11-19

A stable isotope dilution assay (SIDA) was developed for the quantitation of both linalool enantiomers using synthesized [2H(2)]R/S-linalool as the internal standard. For enrichment of the target compound from beer, a solid phase microextraction method (SPME) was developed. In comparison to the more time-consuming extraction/distillation cleanup of the beer samples, the results obtained by SPME/SIDA were very similar, even under nonequilibration conditions. Analysis of five different types of beer showed significant differences in the linalool concentrations, which were clearly correlated with the intensity of the hoppy aroma note as evaluated by a sensory panel. In addition, significant differences in the R/S ratios were measured in the beers. The SPME/SIDA yielded exact data independently from headspace sampling parameters, such as exposure time or ionic strength of the solution.

Compilation of gas geochemistry and isotopic analyses from The Geysers geothermal field: 1978-1991

USGS Publications Warehouse

Lowenstern, Jacob B.; Janik, Cathy; Fahlquist, Lynne; Johnson, Linda S.

1999-01-01

We present 45 chemical and isotopic analyses from well discharges at The Geysers geothermal field and summarize the most notable geochemical trends. H2 and H2S concentrations are highest in the Southeast Geysers, where steam samples have δD and δ18O values that reflect replenishment by meteoric water. In the Northwest Geysers, samples are enriched in gas/steam, CO2, CH4, and N2/Ar relative to the rest of the field, and contain steam that is elevated in δD and δ18O, most likely due to substantial contributions from Franciscan-derived fluids. The δ13C of CO2, trends in CH4 vs. N2, and abundance of NH3 indicate that the bulk of the non-condensable gases are derived from thermal breakdown of organic materials in Franciscan meta-sediments.

Rhenium-osmium concentration and isotope systematics in group IIAB iron meteorites

USGS Publications Warehouse

Morgan, J.W.; Horan, M.F.; Walker, R.J.; Grossman, J.N.

1995-01-01

Rhenium and osmium abundances, and osmium isotopic compositions were measured by negative thermal ionization mass spectrometry in thirty samples, including replicates, of five IIA and eight IIB iron meteorites. Log plots of Os vs. Re abundances for IIA and IIB irons describe straight lines that approximately converge on Lombard, which has the lowest Re and Os abundances and highest 187Re/188Os measured in a IIA iron to date. The linear IIA trend may be exactly reproduced by fractional crystallization, but is not well fitted using variable partition coefficients. The IIB iron trend, however, cannot be entirely explained by simple fractional crystallization. One explanation is that small amounts of Re and Os were added to the asteroid core during the final stages of crystallization. Another possibility is that diffusional enrichment of Os may have occurred in samples most depleted in Re and Os. -from Authors

Heat deposition analysis for the High Flux Isotope Reactor’s HEU and LEU core models

DOE PAGES

Davidson, Eva E.; Betzler, Benjamin R.; Chandler, David; ...

2017-08-01

The High Flux Isotope Reactor at Oak Ridge National Laboratory is an 85 MW th pressurized light-water-cooled and -moderated flux-trap type research reactor. The reactor is used to conduct numerous experiments, advancing various scientific and engineering disciplines. As part of an ongoing program sponsored by the US Department of Energy National Nuclear Security Administration Office of Material Management and Minimization, studies are being performed to assess the feasibility of converting the reactor’s highly enriched uranium fuel to low-enriched uranium fuel. To support this conversion project, reference models with representative experiment target loading and explicit fuel plate representation were developed andmore » benchmarked for both fuels to (1) allow for consistent comparison between designs for both fuel types and (2) assess the potential impact of low-enriched uranium conversion. These high-fidelity models were used to conduct heat deposition analyses at the beginning and end of the reactor cycle and are presented herein. This article (1) discusses the High Flux Isotope Reactor models developed to facilitate detailed heat deposition analyses of the reactor’s highly enriched and low-enriched uranium cores, (2) examines the computational approach for performing heat deposition analysis, which includes a discussion on the methodology for calculating the amount of energy released per fission, heating rates, power and volumetric heating rates, and (3) provides results calculated throughout various regions of the highly enriched and low-enriched uranium core at the beginning and end of the reactor cycle. These are the first detailed high-fidelity heat deposition analyses for the High Flux Isotope Reactor’s highly enriched and low-enriched core models with explicit fuel plate representation. Lastly, these analyses are used to compare heat distributions obtained for both fuel designs at the beginning and end of the reactor cycle, and they are essential for enabling comprehensive thermal hydraulics and safety analyses that require detailed estimates of the heat source within all of the reactor’s fuel element regions.« less

Stable isotope ratios in rainfall and water vapour at Bangalore, Southern India during the monsoon period of 2013

NASA Astrophysics Data System (ADS)

Peethambaran, Rahul; Ghosh, Prosenjit

2015-04-01

Rainwater and water vapour were collected during monsoon rainfall from Bangalore station to identifying the signature of moisture sources. Moisture responsible for the rainfall originates from Arabian Sea and Bay of Bengal and advected to the station together with vapour generated from the local . Total no of samples includes 72 for water vapour and 81 for rainwater respectively. The mean difference between water vapour and rainwater was found to be -13.27±2.5 ‰ for δ18O, -100±9 ‰ for δD, which was calculated from monthly mean values of water vapour and rainwater. The most enriched samples of rainwater and water vapour were found during the pre monsoon months which correspond to temperature maximum at the study location. Lighter isotopic ratios were recorded in samples collected during the starting of monsoon showers which goes to further depletion in δ18O during the period of post monsoon. This was mainly due to the change in the prevailing wind direction from southwest to northeast. Local Meteoric Water Line (LMWL) generated for rainwater (d = 7.49 δ 18O + 5.2555, R² = 0.93) equation suggesting enrichment due to evaporation. Local Vapour Line (LVL) (d = 7.5248 δ 18O + 6.6534,R² = 0.8957) indicates the dominance of vapor from local source. The time series of d-xcess of rainwater and water vapor reveals large variability, coinciding with the presence of transported and local sources. It was observed that rainwater and water vapor exhibits higher values indicating re-evaporation from the region. Repetition of this feature demonstrated pattern of moisture recycling in the atmosphere and the contribution of continental evaporation and transpiration. The sensitivity of isotopes to the sudden change in wind direction was documented by an abrupt variations in the isotope values. Such changes in wind patterns were mostly associated with the prevalence of low pressure depression systems during the monsoon periods. Detailed analysis on role of wind patterns and air parcel trajectories, atmospheric parameters such as rainfall, temperature and relative humidity and quantitative estimation of local source moisture source contributions will be discussed at the time of presentation.

Comparison of the oxygen and hydrogen isotopes in the juices of fast-growing vegetables and slow-growing fruits.

PubMed

Bong, Yeon-Sik; Lee, Kwang-Sik; Shin, Woo-Jin; Ryu, Jong-Sik

2008-09-01

We have analyzed the oxygen and hydrogen isotopic composition of juices from fruits and vegetables collected from a small orchard in order to investigate the differences in isotopic enrichment and evaporation intensity between fast-growing vegetables and slow-growing fruits grown under the same climatic conditions. The oxygen and hydrogen isotope levels were much higher in the juices of the fruits and vegetables than in the source waters in which they grew because of evaporation effects. According to our data, fast-growing vegetables are subject to greater evaporation than slow-growing fruits. An evaporation experiment using the source water showed that the oxygen and hydrogen isotopic composition of the 60-80% residual fraction was similar to that of the isotopically enriched grape juice, whereas those of the plume and tomato juices were very close to that of the 80-90% residual fraction, thus proving the effect of evaporation. Copyright (c) 2008 John Wiley & Sons, Ltd.

Relationships between mercury concentration and food selectivity of many kinds of fishes in Minamata Bay

NASA Astrophysics Data System (ADS)

Mori, K.; Kanaya, G.

2016-02-01

Serious injuries occurred in residents who consumed fish and shellfishes in Minamata Bay polluted by high-concentration methyl-mercury in the 1950s. Pollution has fallen to a safe level because of the pollution prevention project (dredging etc.) carried out from 1977 to 1990. From 2010 we have been researching the bioaccumulation of mercury in several fishes in Minamata Bay and surrounding areas. We selected several sampling points that showed different environmental conditions, species composition and food web patterns. For the determination of feeding types of 60 species fishes (600 samples) sampled by gill net, we measured mercury levels of each sample and directly checked food items in gut, and distinguished carnivore, omnivore, herbivore and detritivore. At this time, we introduced a stable isotope analysis for checking the food history and feeding habits of dominant fish. In about 300 individuals of 30 species of dominant fish selected from the 600 samples, we measured the stable nitrogen and carbon isotope ratios (δ15N, δ13C) of each sample. Checking the food items in gut of fishes, more than 80% of fishes were carnivorous, and showed different selectivity of food items, such as fish, crustacean and so on. From the results of stable isotope ratios, benthic fish tended to show a higher ratio of δ13C. Usually benthic microalgae evidenced a higher ratio of δ13C than planktonic microalgae, and the ratio conservative through the food chain. In general, δ15N increases through the food chain with +3 to +4 ‰ enrichment per trophic step. In these data, carnivorous fishes of benthic and pelagic type showed medium and high ratios of δ15N. From comparing the stable isotope ratio to the mercury concentration of fishes, all of the high-mercury fishes belonged to benthic and carnivorous types. We consider the joint method of food web analysis and stable isotope analysis to be useful for understanding the mechanism of mercury bioaccumulation through the food web

Hydrologic Contributions of Springs to the Logan River, Utah

NASA Astrophysics Data System (ADS)

Gooseff, M. N.; Evans, J.; Kolesar, P.; Lachmar, T.; Payn, R.

2005-05-01

The Logan River flows through a fractured karst watershed of the Bear River mountain range in northern Utah, and provides significant water supply to the city of Logan, Utah. Springs flowing into the Logan River are important sources of water after annual snowmelt has been exhausted. In this work, we present results from a year of monitoring water chemistry and stable isotopes (D, 18O, and 13C) in two major springs and in the Logan River upstream and downstream of the combined spring inputs. The two springs, DeWitt and Spring Hollow, flow into the river within 1.5 km of each other. Annual patterns of Si and Mg suggest a flushing pattern, with reduced concentrations during snowmelt, and increasing concentrations throughout baseflow recession, at all for sampling locations. Cl concentrations are likewise greatly depressed after the snowmelt pulse but afterward remain consistently low at all four sites. Stable isotope data show that spring water is generally more enriched in D and 18O than river water, with an enriching pattern throughout annual stream flow recession.

Isotopic composition in precipitation and groundwater in the northern mountainous region of the Central Valley of Costa Rica.

PubMed

Sánchez-Murillo, Ricardo; Esquivel-Hernández, Germain; Sáenz-Rosales, Oscar; Piedra-Marín, Gilberto; Fonseca-Sánchez, Alicia; Madrigal-Solís, Helga; Ulloa-Chaverri, Franz; Rojas-Jiménez, Luis D; Vargas-Víquez, José A

2017-03-01

The linkage between precipitation and recharge is still poorly understood in the Central America region. This study focuses on stable isotopic composition in precipitation and groundwater in the northern mountainous region of the Central Valley of Costa Rica. During the dry season, rainfall samples corresponded to enriched events with high deuterium excess. By mid-May, the Intertropical Convergence Zone poses over Costa Rica resulting in a depletion of 18 O/ 16 O and 2 H/H ratios. A parsimonious four-variable regression model (r 2  = 0.52) was able to predict daily δ 18 O in precipitation. Air mass back trajectories indicated a combination of Caribbean Sea and Pacific Ocean sources, which is clearly depicted in groundwater isoscape. Aquifers relying on Pacific-originated recharge exhibited a more depleted pattern, whereas recharge areas relying on Caribbean parental moisture showed an enrichment trend. These results can be used to enhance modelling efforts in Central America where scarcity of long-term data limits water resources management plans.

Petrogenesis and origin of the Upper Jurassic-Lower Cretaceous magmatism in Central High Atlas (Morocco): Major, trace element and isotopic (Sr-Nd) constraints

NASA Astrophysics Data System (ADS)

Essaifi, Abderrahim; Zayane, Rachid

2018-01-01

During an uplift phase, which lasted ca. 40 Ma, from the Late Jurassic (165 Ma) to the Early Cretaceous (125 Ma), transitional to moderately alkaline magmatic series were emplaced in the Central High Atlas. The corresponding magmatic products include basaltic lava flows erupted within wide synclines and intrusive complexes composed of layered mafic intrusions and monzonitic to syenitic dykes emplaced along narrow anticlinal ridges. The igneous rock sequence within the intrusive complexes is composed of troctolites, olivine-gabbros, oxide-gabbros, monzonites and syenites. The chemical compositions of the various intrusive rocks can be accounted for by crystal accumulation, fractional crystallization and post-magmatic remobilization. The evolution from the troctolites to the syenites was mainly controlled by a fractional crystallization process marked by early fractionation of olivine, plagioclase and clinopyroxene, followed by separation of biotite, amphibole, apatite, and Ti-magnetite. Hydrothermal activity associated with emplacement of the intrusions within the Jurassic limestones modified the elemental and the Sr isotopic composition of the hydrothermally altered rocks In particular the monzonitic to syenitic dykes underwent an alkali metasomatism marked by depletion in K and Rb and enrichment in Na and Sr. As a result, their Sr isotopic composition was shifted towards higher initial Sr isotopic ratios (0.7067-0.7075) with respect to the associated gabbros (0.7036-0.7046). On the contrary, the Nd isotopic compositions were preserved from isotope exchange with the limestones and vary in a similar range to those of the gabbros (+1.6 < εNdi < +4.1). The isotopic and the trace element ratios of the uncontaminated samples were used to constrain the source characteristics of this magmatism. The Sr-Nd isotopic data and the incompatible element ratios (e.g. La/Nb, Zr/Nb, Th/U, Ce/Pb) are consistent with generation from an enriched upper mantle similar to an ocean island basalt source. Melting of the subcontinental metasomatized lithosphere is tentatively related to small-scale shallow mantle upwelling and asthenospheric uprise at the triple junction between the western High Atlas, the Middle Atlas and the eastern High Atlas domains during a period of relative tectonic quiescence.

Process for preparing a chemical compound enriched in isotope content

DOEpatents

Michaels, Edward D.

1982-01-01

A process to prepare a chemical enriched in isotope content which includes: (a) A chemical exchange reaction between a first and second compound which yields an isotopically enriched first compound and an isotopically depleted second compound; (b) the removal of a portion of the first compound as product and the removal of a portion of the second compound as spent material; (c) the conversion of the remainder of the first compound to the second compound for reflux at the product end of the chemical exchange reaction region; (d) the conversion of the remainder of the second compound to the first compound for reflux at the spent material end of the chemical exchange region; and the cycling of the additional chemicals produced by one conversion reaction to the other conversion reaction, for consumption therein. One of the conversion reactions is an oxidation reaction, and the energy that it yields is used to drive the other conversion reaction, a reduction. The reduction reaction is carried out in a solid polymer electrolyte electrolytic reactor. The overall process is energy efficient and yields no waste by-products.

Quantifying MTBE biodegradation in the Vandenberg Air Force Base ethanol release study using stable carbon isotopes

NASA Astrophysics Data System (ADS)

McKelvie, Jennifer R.; Mackay, Douglas M.; de Sieyes, Nicholas R.; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

2007-12-01

Compound-specific isotope analysis (CSIA) was used to assess biodegradation of MTBE and TBA during an ethanol release study at Vandenberg Air Force Base. Two continuous side-by-side field releases were conducted within a preexisting MTBE plume to form two lanes. The first involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene ("No ethanol lane"), while the other involved the continuous injection of site groundwater amended with benzene, toluene and o-xylene and ethanol ("With ethanol lane"). The δ 13C of MTBE for all wells in the "No ethanol lane" remained constant during the experiment with a mean value of - 31.3 ± 0.5‰ ( n = 40), suggesting the absence of any substantial MTBE biodegradation in this lane. In contrast, substantial enrichment in 13C of MTBE by 40.6‰, was measured in the "With ethanol lane", consistent with the effects of biodegradation. A substantial amount of TBA (up to 1200 μg/L) was produced by the biodegradation of MTBE in the "With ethanol lane". The mean value of δ 13C for TBA in groundwater samples in the "With ethanol lane" was - 26.0 ± 1.0‰ ( n = 32). Uniform δ 13C TBA values through space and time in this lane suggest that substantial anaerobic biodegradation of TBA did not occur during the experiment. Using the reported range in isotopic enrichment factors for MTBE of - 9.2‰ to - 15.6‰, and values of δ 13C of MTBE in groundwater samples, MTBE first-order biodegradation rates in the "With ethanol lane" were 12.0 to 20.3 year - 1 ( n = 18). The isotope-derived rate constants are in good agreement with the previously published rate constant of 16.8 year - 1 calculated using contaminant mass-discharge for the "With ethanol lane".

Groundwater salinization in the Saloum (Senegal) delta aquifer: minor elements and isotopic indicators.

PubMed

Faye, Serigne; Maloszewski, Piotr; Stichler, Willibald; Trimborn, Peter; Cissé Faye, Seynabou; Bécaye Gaye, Cheikh

2005-05-01

The hydrochemistry of minor elements bromide (Br), boron (B), strontium (Sr), environmental stable isotopes (18O and 2H) together with major-ion chemistry (chloride, sodium, calcium) has been used to constrain the source(s), relative age, and processes of salinization in the Continental Terminal (CT) aquifer in the Saloum (mid-west Senegal) region. Seventy-one groundwater wells which include 24 wells contaminated by saltwater and three sites along the hypersaline Saloum River were sampled to obtain additional information on the hydrochemical characteristics of the groundwater defined in previous studies. Use of Br against Cl confirms the Saloum River saline water intrusion up to a contribution of 7% into the aquifer. In addition to this recent intrusion, a relatively ancient intrusion of the Saloum River water which had reached at least as far as 20 km south from the source was evidenced. The high molar ratio values of Sr/Cl and Sr/Ca indicate an additional input of strontium presumably derived from carbonate precipitation/dissolution reactions and also via adsorption reactions. The variable B concentrations (7-650 microg/L) found in the groundwater samples were tested against the binary mixing model to evaluate the processes of salinization which are responsible for the investigated system. Sorption of B and depletion of Na occur as the Saloum river water intrudes the aquifer (salinization) in the northern part of the region, whereas B desorption and Na enrichment occur as the fresh groundwater flushing displaces the saline waters in the coastal strip (refreshening). In the central zone where ancient intrusion prevailed, the process of freshening of the saline groundwater is indicated by the changes in major-ion chemistry as well as B desorption and Na enrichment. In addition to these processes, stable isotopes reveal that mixing with recently infiltrating waters and evaporation contribute to the changes in isotopic signature.