Stable isotopes in mid-ocean ridge hydrothermal systems: Interactions between fluids, minerals, and organisms

USGS Publications Warehouse

Shanks, Wayne C.; Böhlke, John Karl; Seal, Robert R.; Humphries, S.D.; Zierenberg, Robert A.; Mullineaux, Lauren S.; Thomson, Richard E.

1995-01-01

Studies of abundance variations of light stable isotopes in nature have had a tremendous impact on all aspects of geochemistry since the development, in 1947, of a gas source isotope ratio mass spectrometer capable of measuring small variations in stable isotope ratios (Nice, 1947]. Stable isotope geochemistry is now a mature field, as witnessed by the proliferation of commercially available mass spectrometers installed at virtually every major academic, government, and private-sector research geochemistry laboratory. A recent search of a literature database revealed over 3,000 articles that utilized stable isotope geochemistry over the last 20 years. Nonetheless, many exciting new technical developments are leading to exciting new discoveries and applications. In particular, micro-analytical techniques involving new generations of laser- and ion-microprobes are revolutionizing the types of analyses that can be done on spot sizes as small as a few tens of micrometers [Shanks and Criss, 1989]. New generations of conventional gas source and thermal ionization mass spectrometers, with high levels of automation and increased sensitivity and precision, are allowing analyses of large numbers of samples, like those needed for stable isotope stratigraphy in marine sediments, and are enabling the development and application of new isotopic systems.

Lead isotope data bank; 2,624 samples and analyses cited

USGS Publications Warehouse

Doe, Bruce R.

1976-01-01

The Lead Isotope Data Bank (LIDB) was initiated to facilitate plotting data. Therefore, the Bank reflects data most often used in plotting rather than comprises a comprehensive tabulation of lead isotope data. Up until now, plotting was done using card decks processed by computer with tapes plotted by a Gerber plotter and more recently a CRT using a batch mode. Lack of a uniform format for sample identification was not a great impediment. With increase in the size of the bank, hand sorting is becoming prohibitive and ·plans are underway to put the bank into a uniform format on DISK with a card backup so that it may be accessed by use of IRIS on the DECK 10 computer at the U.S.G.S. facility in Denver. Plots will be constructed on a CRT. Entry of the bank into the IRIS accessing program is scheduled for completion in FY 1976

Particular geoscientific perspectives on stable isotope analysis in the arboreal system

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

An update of the Pb isotope inventory in post leaded-petrol Singapore environments.

PubMed

Carrasco, Gonzalo; Chen, Mengli; Boyle, Edward A; Tanzil, Jani; Zhou, Kuanbo; Goodkin, Nathalie F

2018-02-01

Pb is a trace metal that tracks anthropogenic pollution in natural environments. Despite recent leaded petrol phase out around Southeast Asia, the region's growth has resulted in continued exposure of Pb from a variety of sources. In this study, sources of Pb into Singapore, a highly urbanised city-state situated in the central axis of Southeast Asia, are investigated using isotopic ratios and concentrations. We compiled data from our previous analyses of aerosols, incineration fly ash and sediments, with new data from analyses of soil from gas stations, water from runoff and round-island coastal seawater to obtain a spatio-temporal overview of sources of Pb into the Singapore environment. Using 206 Pb/ 207 Pb ratio, we identified three main Pb source origins: natural Pb (1.215 ± 0.001), historic/remnant leaded petrol (1.123 ± 0.013), and present-day industrial and incinerated waste (1.148 ± 0.005). Deep reservoir sediments bore larger traces of Pb from leaded petrol, but present-day runoff waters and coastal seawater were a mix of industrial and natural sources with somewhat variable concentrations. We found temporal variability in Pb isotopic ratio in aerosols indicating alternating transboundary Pb sources to Singapore that correspond to seasonal changes in monsoon winds. By contrast, seasonal monsoon circulation did not significantly influence isotopic ratios of coastal seawater Pb. Instead, seawater Pb was driven more by location differences, suggesting stronger local-scale drivers of Pb such as point sources, water flushing, and isotope exchange. The combination of multiple historic and current sources of Pb shown in this study highlights the need for continued monitoring of Pb in Southeast Asia, especially in light of emerging industries and potential large sources of Pb such as coal combustion. Copyright © 2017 Elsevier Ltd. All rights reserved.

DISSOLUTION AND ANALYSIS OF YELLOWCAKE COMPONENTS FOR FINGERPRINTING UOC SOURCES

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

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

2012-01-01

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

Tracing changes in atmospheric sources of lead contamination using lead isotopic compositions in Australian red wine.

PubMed

Kristensen, Louise Jane; Taylor, Mark Patrick; Evans, Andrew James

2016-07-01

Air quality data detailing changes to atmospheric composition from Australia's leaded petrol consumption is spatially and temporally limited. In order to address this data gap, wine was investigated as a potential proxy for atmospheric lead conditions. Wine spanning sixty years was collected from two wine regions proximal to the South Australian capital city, Adelaide, and analysed for lead concentration and lead and strontium isotopic composition for source apportionment. Maximum wine lead concentrations (328 μg/L) occur prior to the lead-in-air monitoring in South Australia in the later 1970s. Wine lead concentrations mirror available lead-in-air measurements and show a declining trend reflecting parallel reductions in leaded petrol emissions. Lead from petrol dominated the lead in wine ((206)Pb/(207)Pb: 1.086; (208)Pb/(207)Pb: 2.360) until the introduction of unleaded petrol, which resulted in a shift in the wine lead isotopic composition closer to vineyard soil ((206)Pb/(207)Pb: 1.137; (208)Pb/(207)Pb: 2.421). Current mining activities or vinification processes appear to have no impact with recent wine samples containing less than 4 μg/L of lead. This study demonstrates wine can be used to chronicle changes in environmental lead emissions and is an effective proxy for atmospherically sourced depositions of lead in the absence of air quality data. Copyright © 2016 Elsevier Ltd. All rights reserved.

Two-step extraction method for lead isotope fractionation to reveal anthropogenic lead pollution.

PubMed

Katahira, Kenshi; Moriwaki, Hiroshi; Kamura, Kazuo; Yamazaki, Hideo

2018-05-28

This study developed the 2-step extraction method which eluted the Pb adsorbing on the surface of sediments in the first solution by aqua regia and extracted the Pb absorbed inside particles into the second solution by mixed acid of nitric acid, hydrofluoric acid and hydrogen peroxide solution. We applied the method to sediments in the enclosed water area and found out that the isotope ratios of Pb in the second solution represented those of natural origin. This advantage of the method makes it possible to distinguish the Pb between natural origin and anthropogenic source on the basis of the isotope ratios. The results showed that the method was useful to discuss the Pb sources and that anthropogenic Pb in the sediment samples analysed was mainly derived from China because of transboundary air pollution.

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

NASA Astrophysics Data System (ADS)

Potra, Adriana; Macfarlane, Andrew W.

2014-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Metallurgical characterization of brass objects from the Akko 1 shipwreck, Israel

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

Ashkenazi, D., E-mail: dana@eng.tau.ac.il; Cvikel, D.; Stern, A.

2014-06-01

The Akko 1 shipwreck was a small Egyptian armed vessel or auxiliary naval brig built in the eastern Mediterranean at the beginning of the 19th century. During the underwater excavations, about 230 brass hook-and-eye closures were found, mainly in the bow area. In addition, 158 brass cases were found, mainly between midships and the aft extremity of the shipwreck. Metallurgical non-destructive and destructive characterizations of selected items were performed, including radiographic testing, XRF, lead isotope analysis, optical microscopy, SEM–EDS and microhardness tests. The hook-and-eye closures and the cases were both found to be made of binary copper–zinc alloy (about 30more » wt.% zinc). While the brass cases were made from rolled sheets, hand-made using simple tools, and joined by tin–lead soldering material, the brass hook-and-eye closures were hand-made from drawn brass wire, and manufactured from commercial drawn brass bars by a cold-working process. The lead isotope analyses suggest different provenances of the raw materials used for making the brass objects, thus the different origins of the ores may hint that the brass wire and sheet were imported to the workshops in which the objects were manufactured. - Highlights: • Brass cases and hook-and-eye closures were retrieved from the Akko 1 shipwreck. • Both types of objects were made of binary copper–zinc alloy (about 30 wt.% zinc). • The cases were hand-made from rolled sheets and joined by tin–lead soldering. • Hook-and-eye closures were made from drawn brass wire manufactured by cold-working. • Lead isotope analyses suggest that the origins of the raw material were diverse.« less

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

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

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

Gulson, Brian; Mizon, Karen; Korsch, Michael

2006-01-15

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

Stable Isotopes of C and N Reveal Habitat Dependent Dietary Overlap between Native and Introduced Turtles Pseudemys rubriventris and Trachemys scripta

PubMed Central

Pearson, Steven H.; Avery, Harold W.; Kilham, Susan S.; Velinsky, David J.; Spotila, James R.

2013-01-01

Habitat degradation and species introductions are two of the leading causes of species declines on a global scale. Invasive species negatively impact native species through predation and competition for limited resources. The impacts of invasive species may be increased in habitats where habitat degradation is higher due to reductions of prey abundance and distribution. Using stable isotope analyses and extensive measurements of resource availability we determined how resource availability impacts the long term carbon and nitrogen assimilation of the invasive red-eared slider turtle (Trachemys scripta elegans) and a native, threatened species, the red-bellied turtle (Pseudemys rubriventris) at two different freshwater wetland complexes in Pennsylvania, USA. At a larger wetland complex with greater vegetative species richness and diversity, our stable isotope analyses showed dietary niche partitioning between species, whereas analyses from a smaller wetland complex with lower vegetative species richness and diversity showed significant dietary niche overlap. Determining the potential for competition between these two turtle species is important to understanding the ecological impacts of red-eared slider turtles in wetland habitats. In smaller wetlands with increased potential for competition between native turtles and invasive red-eared slider turtles we expect that when shared resources become limited, red-eared slider turtles will negatively impact native turtle species leading to long term population declines. Protection of intact wetland complexes and the reduction of introduced species populations are paramount to preserving populations of native species. PMID:23675437

Stable isotopes of C and N reveal habitat dependent dietary overlap between native and introduced turtles Pseudemys rubriventris and Trachemys scripta.

PubMed

Pearson, Steven H; Avery, Harold W; Kilham, Susan S; Velinsky, David J; Spotila, James R

2013-01-01

Habitat degradation and species introductions are two of the leading causes of species declines on a global scale. Invasive species negatively impact native species through predation and competition for limited resources. The impacts of invasive species may be increased in habitats where habitat degradation is higher due to reductions of prey abundance and distribution. Using stable isotope analyses and extensive measurements of resource availability we determined how resource availability impacts the long term carbon and nitrogen assimilation of the invasive red-eared slider turtle (Trachemys scripta elegans) and a native, threatened species, the red-bellied turtle (Pseudemys rubriventris) at two different freshwater wetland complexes in Pennsylvania, USA. At a larger wetland complex with greater vegetative species richness and diversity, our stable isotope analyses showed dietary niche partitioning between species, whereas analyses from a smaller wetland complex with lower vegetative species richness and diversity showed significant dietary niche overlap. Determining the potential for competition between these two turtle species is important to understanding the ecological impacts of red-eared slider turtles in wetland habitats. In smaller wetlands with increased potential for competition between native turtles and invasive red-eared slider turtles we expect that when shared resources become limited, red-eared slider turtles will negatively impact native turtle species leading to long term population declines. Protection of intact wetland complexes and the reduction of introduced species populations are paramount to preserving populations of native species.

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.

Evidence for Patterns of Selective Urban Migration in the Greater Indus Valley (2600-1900 BC): A Lead and Strontium Isotope Mortuary Analysis

PubMed Central

Valentine, Benjamin; Kamenov, George D.; Kenoyer, Jonathan Mark; Shinde, Vasant; Mushrif-Tripathy, Veena; Otarola-Castillo, Erik; Krigbaum, John

2015-01-01

Just as modern nation-states struggle to manage the cultural and economic impacts of migration, ancient civilizations dealt with similar external pressures and set policies to regulate people’s movements. In one of the earliest urban societies, the Indus Civilization, mechanisms linking city populations to hinterland groups remain enigmatic in the absence of written documents. However, isotopic data from human tooth enamel associated with Harappa Phase (2600-1900 BC) cemetery burials at Harappa (Pakistan) and Farmana (India) provide individual biogeochemical life histories of migration. Strontium and lead isotope ratios allow us to reinterpret the Indus tradition of cemetery inhumation as part of a specific and highly regulated institution of migration. Intra-individual isotopic shifts are consistent with immigration from resource-rich hinterlands during childhood. Furthermore, mortuary populations formed over hundreds of years and composed almost entirely of first-generation immigrants suggest that inhumation was the final step in a process linking certain urban Indus communities to diverse hinterland groups. Additional multi disciplinary analyses are warranted to confirm inferred patterns of Indus mobility, but the available isotopic data suggest that efforts to classify and regulate human movement in the ancient Indus region likely helped structure socioeconomic integration across an ethnically diverse landscape. PMID:25923705

Evidence for Patterns of Selective Urban Migration in the Greater Indus Valley (2600-1900 BC): A Lead and Strontium Isotope Mortuary Analysis.

PubMed

Valentine, Benjamin; Kamenov, George D; Kenoyer, Jonathan Mark; Shinde, Vasant; Mushrif-Tripathy, Veena; Otarola-Castillo, Erik; Krigbaum, John

2015-01-01

Just as modern nation-states struggle to manage the cultural and economic impacts of migration, ancient civilizations dealt with similar external pressures and set policies to regulate people's movements. In one of the earliest urban societies, the Indus Civilization, mechanisms linking city populations to hinterland groups remain enigmatic in the absence of written documents. However, isotopic data from human tooth enamel associated with Harappa Phase (2600-1900 BC) cemetery burials at Harappa (Pakistan) and Farmana (India) provide individual biogeochemical life histories of migration. Strontium and lead isotope ratios allow us to reinterpret the Indus tradition of cemetery inhumation as part of a specific and highly regulated institution of migration. Intra-individual isotopic shifts are consistent with immigration from resource-rich hinterlands during childhood. Furthermore, mortuary populations formed over hundreds of years and composed almost entirely of first-generation immigrants suggest that inhumation was the final step in a process linking certain urban Indus communities to diverse hinterland groups. Additional multi disciplinary analyses are warranted to confirm inferred patterns of Indus mobility, but the available isotopic data suggest that efforts to classify and regulate human movement in the ancient Indus region likely helped structure socioeconomic integration across an ethnically diverse landscape.

Determination of lead, cadmium, indium, thallium and silver in ancient ices from Antarctica by isotope dilution-thermal ionization mass spectrometry

USGS Publications Warehouse

Matsumoto, A.; Hinkley, T.K.

1997-01-01

The concentrations of five chalcophile elements (Pb, Cd, In, Tl and Ag) and the lead isotope rarios in ancient ices from the Taylor Dome near coastal Antarctica, have been determined by the isotope dilutionthermal ionization mass spectrometry (ID-TIMS), with ultra-clean laboratory techniques. The samples were selected from segments of cores, one of which included a visible ash layer. Electric conductivity measurement (ECM) or dielectric properties (DEP) gave distinctive sharp peaks for some of the samples c hosen. Exterior portions of the sample segments were trimmed away by methods described here. Samples w ere evaporated to dryness and later separated into fractions for the five elements using an HBr-HNO3 a nion exchange column method. The concentrations are in the range 2.62-36.7 pg Pb/g of ice, 0.413-2.83 pg Cd/g, 0.081-0.34 pg In/g, 0.096-2.8 pg Tl/g and 0.15-0.84 pg Ag/g. respectively. The dispersions in duplicate analyses are about ??1% for lead and cadmium, ??2% for indium. ??4% for thallium and ??6% for silver, respectively. The concentrations of lead obtained are commonly higher than those in the present-day Antarctic surface snows, but the isotope ratios are distinctively higher than those of the present-day snows and close to those of the other ancient ice collected from a different Antarctic area.

Precise and accurate in situ Pb-Pb dating of apatite, monazite, and sphene by laser ablation multiple-collector ICP-MS

NASA Astrophysics Data System (ADS)

Willigers, B. J. A.; Baker, J. A.; Krogstad, E. J.; Peate, D. W.

2002-03-01

To evaluate in situ Pb dating by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), we analysed apatite, sphene, and monazite from Paleoproterozoic metamorphic rocks from West Greenland. Pb isotope ratios were also determined in the National Institute of Standards and Technology (NIST) 610 glass standard and were corrected for mass fractionation by reference to the measured thallium isotope ratio. The NIST 610 glass was used to monitor Pb isotope mass fractionation in the low Tl/Pb accessory minerals. Replicate analyses of the glass (1 to 2 min) yielded ratios with an external reproducibility comparable to conventional analyses of standard reference material 981 by thermal ionisation mass spectrometry (TIMS). Mineral grains were generally analysed with a 100-μm laser beam, although some monazite crystals were analysed at smaller spot sizes (10 and 25 μm). The common Pb isotope ratios required for age calculations were either measured on coexisting plagioclase by LA-MC-ICP-MS or could be ignored, as individual crystals exhibit sufficient Pb isotopic heterogeneity to perform isochron calculations on replicate analyses of single crystals. Mean mineral ages with the 204Pb ion beam measured in the multiplier were as follows: apatite, 1715 ± 23 m.y.; sphene, 1789 ± 11 m.y.; and monazite, 1783 to 1888 m.y., with relative uncertainties on individual monazite ages of <0.2% but highly reproducible age determinations on single monazite crystals (≪1%). Isochron ages calculated from several mineral analyses without assumption of common Pb also yield precise age determinations. Apatite and monazite Pb ages determined by in situ Pb isotope analysis are identical to those determined by conventional TIMS analysis of bulk mineral separates, and the analytical uncertainties of these short laser analyses with no prior mechanical or chemical separation are comparable to those obtained by TIMS. Detailed examination of the sphene in situ age data does, however, show a small discrepancy between the LA-MC-ICP-MS and TIMS ages (˜1% younger). High-resolution mass scans of the sphene during ablation clearly showed several small and as yet unidentified isobaric interferences that overlap with the 207Pb peak at the resolution conditions for measurement of isotope ratios. These might account for the age discrepancy between the LA-MC-ICP-MS and TIMS sphene ages. LA-MC-ICP-MS is a rapid, accurate, and precise method for in situ determination of Pb isotope ratios that can be used for geochronological studies in a manner similar to an ion microprobe, albeit currently at a somewhat degraded spatial resolution. Further modifications to the LA-MC-ICP-MS system, such as improved sensitivity, ion transmission, and LA methodology, may lead to this type of instrument becoming the method of choice for many types of in situ Pb isotope dating.

Minimal incorporation of Deepwater Horizon oil by estuarine filter feeders.

PubMed

Fry, Brian; Anderson, Laurie C

2014-03-15

Natural abundance carbon isotope analyses are sensitive tracers for fates and use of oil in aquatic environments. Use of oil carbon in estuarine food webs should lead to isotope values approaching those of oil itself, -27‰ for stable carbon isotopes reflecting oil origins and -1000‰ for carbon-14 reflecting oil age. To test for transfer of oil from the 2010 Deepwater Horizon spill into estuarine food webs, filter-feeding barnacles (Balanus sp.) and marsh mussels (Geukensia demissa) were collected from Louisiana estuaries near the site of the oil spill. Carbon-14 analyses of these animals from open waters and oiled marshes showed that oil use was <1% and near detection limits estimated at 0.3% oil incorporation. Respiration studies showed no evidence for enhanced microbial activity in bay waters. Results are consistent with low dietary impacts of oil for filter feeders and little overall impact on respiration in the productive Louisiana estuarine systems. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

Record of Anthropocene pollution sources of lead in disturbed peatlands from Southern Poland

NASA Astrophysics Data System (ADS)

Fiałkiewicz-Kozieł, Barbara; De Vleeschouwer, François; Mattielli, Nadine; Fagel, Nathalie; Palowski, Bernard; Pazdur, Anna; Smieja-Król, Beata

2018-04-01

The importance of human impacts on Earth has led to the proposal of a new geologic epoch called the Anthropocene. However markers, recognizable in all records, are required to define this period. Here we combine elemental geochemistry with stable lead (Pb) isotopes and mineralogical analyses to decipher the sources of lead in two exploited ombrotrophic peat bogs (Puścizna Mała and Puścizna Krauszowska) from Southern Poland. The most disturbed parts of the cores, distinguished using bulk density and age-depth models (22-45 cm in PM and 22-46 cm in PK), were excluded from the interpretation. The two studied cores record ca. 2000 years of variations in lead accumulation rates and isotopic compositions. In the lowest part of the cores (2nd to 4th century AD for Puścizna Mała and 2nd century BC to 2nd century AD for Puścizna Krauszowska), the 206Pb/207Pb ratios (1.188) are consistent with natural supplies from the erosion of the nearby Tatra Mountains. From the 9th to the 19th century AD, 206Pb/207Pb ratios (1.176-1.179) are similar to the signatures obtained from Polish galena ores. The highest Pb accumulation rates are found around 1950 AD and reflect the primary influence of bituminous coal combustion together with the secondary influence of leaded gasoline. This result agrees with the occurrence and abundance of spheroidal aluminosilicates, an unambiguous marker of human industrial activity and coal burning as well as with the acceleration of Zn, Cd and Fe accumulation rate. Our results provide evidence that similar geochemical patterns exist in both analysed cores despite differences in the history of peatland exploitation. Therefore, given that extra care is taken to identify the disturbed peat layers, exploited peatlands can be used to record past changes in lead isotopic signature during the Anthropocene.

High risk of lead contamination for scavengers in an area with high moose hunting success.

PubMed

Legagneux, Pierre; Suffice, Pauline; Messier, Jean-Sébastien; Lelievre, Frédérick; Tremblay, Junior A; Maisonneuve, Charles; Saint-Louis, Richard; Bêty, Joël

2014-01-01

Top predators and scavengers are vulnerable to pollutants, particularly those accumulated along the food chain. Lead accumulation can induce severe disorders and alter survival both in mammals (including humans) and in birds. A potential source of lead poisoning in wild animals, and especially in scavengers, results from the consumption of ammunition residues in the tissues of big game killed by hunters. For two consecutive years we quantified the level lead exposure in individuals of a sentinel scavenger species, the common raven (Corvus corax), captured during the moose (Alces alces) hunting season in eastern Quebec, Canada. The source of the lead contamination was also determined using stable isotope analyses. Finally, we identified the different scavenger species that could potentially be exposed to lead by installing automatic cameras targeting moose gut piles. Blood lead concentration in ravens increased over time, indicating lead accumulation over the moose-hunting season. Using a contamination threshold of 100 µg x L(-1), more than 50% of individuals were lead-contaminated during the moose hunting period. Lead concentration was twice as high in one year compared to the other, matching the number of rifle-shot moose in the area. Non-contaminated birds exhibited no ammunition isotope signatures. The isotope signature of the lead detected in contaminated ravens tended towards the signature from lead ammunition. We also found that black bears (Ursus americanus), golden eagles and bald eagles (Aquila chrysaetos and Haliaeetus leucocephalus, two species of conservation concern) scavenged heavily on moose viscera left by hunters. Our unequivocal results agree with other studies and further motivate the use of non-toxic ammunition for big game hunting.

High Risk of Lead Contamination for Scavengers in an Area with High Moose Hunting Success

PubMed Central

Legagneux, Pierre; Suffice, Pauline; Messier, Jean-Sébastien; Lelievre, Frédérick; Tremblay, Junior A.; Maisonneuve, Charles; Saint-Louis, Richard; Bêty, Joël

2014-01-01

Top predators and scavengers are vulnerable to pollutants, particularly those accumulated along the food chain. Lead accumulation can induce severe disorders and alter survival both in mammals (including humans) and in birds. A potential source of lead poisoning in wild animals, and especially in scavengers, results from the consumption of ammunition residues in the tissues of big game killed by hunters. For two consecutive years we quantified the level lead exposure in individuals of a sentinel scavenger species, the common raven (Corvus corax), captured during the moose (Alces alces) hunting season in eastern Quebec, Canada. The source of the lead contamination was also determined using stable isotope analyses. Finally, we identified the different scavenger species that could potentially be exposed to lead by installing automatic cameras targeting moose gut piles. Blood lead concentration in ravens increased over time, indicating lead accumulation over the moose-hunting season. Using a contamination threshold of 100 µg.L−1, more than 50% of individuals were lead-contaminated during the moose hunting period. Lead concentration was twice as high in one year compared to the other, matching the number of rifle-shot moose in the area. Non-contaminated birds exhibited no ammunition isotope signatures. The isotope signature of the lead detected in contaminated ravens tended towards the signature from lead ammunition. We also found that black bears (Ursus americanus), golden eagles and bald eagles (Aquila chrysaetos and Haliaeetus leucocephalus, two species of conservation concern) scavenged heavily on moose viscera left by hunters. Our unequivocal results agree with other studies and further motivate the use of non-toxic ammunition for big game hunting. PMID:25389754

Hydrogen and Oxygen Stable Isotope Fractionation in Body Fluid Compartments of Dairy Cattle According to Season, Farm, Breed, and Reproductive Stage

PubMed Central

Abeni, Fabio; Petrera, Francesca; Capelletti, Maurizio; Dal Prà, Aldo; Bontempo, Luana; Tonon, Agostino; Camin, Federica

2015-01-01

Environmental temperature affects water turnover and isotope fractionation by causing water evaporation from the body in mammals. This may lead to rearrangement of the water stable isotope equilibrium in body fluids. We propose an approach to detect possible variations in the isotope ratio in different body fluids on the basis of different homoeothermic adaptations in varying reproductive stages. Three different reproductive stages (pregnant heifer, primiparous lactating cow, and pluriparous lactating cow) of two dairy cattle breeds (Italian Friesian and Modenese) were studied in winter and summer. Blood plasma, urine, faecal water, and milk were sampled and the isotope ratios of H (2H/1H) and O (18O/16O) were determined. Deuterium excess and isotope-fractionation factors were calculated for each passage from plasma to faeces, urine and milk. The effects of the season, reproductive stages and breed on δ 2H and δ 18O were significant in all the fluids, with few exceptions. Deuterium excess was affected by season in all the analysed fluids. The correlations between water isotope measurements in bovine body fluids ranged between 0.6936 (urine-milk) and 0.7848 (urine-plasma) for δ 2H, and between 0.8705 (urine-milk) and 0.9602 (plasma-milk) for δ 18O. The increase in both isotopic δ values in all body fluids during summer is representative of a condition in which fractionation took place as a consequence of a different ratio between ingested and excreted water, which leads to an increased presence of the heavy isotopes. The different body water turnover between adult lactating cattle and non-lactating heifers was confirmed by the higher isotopic δ for the latter, with a shift in the isotopic equilibrium towards values more distant from those of drinking water. PMID:25996911

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

NASA Astrophysics Data System (ADS)

Felix Villar, Omar I.

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

The Neoarchaean surficial sulphur cycle: An alternative hypothesis based on analogies with 20th-century atmospheric lead.

PubMed

Gallagher, M; Whitehouse, M J; Kamber, B S

2017-05-01

We revisit the S-isotope systematics of sedimentary pyrite in a shaly limestone from the ca. 2.52 Ga Gamohaan Formation, Upper Campbellrand Subgroup, Transvaal, South Africa. The analysed rock is interpreted to have been deposited in a water depth of ca. 50-100 m, in a restricted sub-basin on a drowning platform. A previous study discovered that the pyrites define a nonzero intercept δ 34 S V - CDT -Δ 33 S data array. The present study carried out further quadruple S-isotope analyses of pyrite, confirming and expanding the linear δ 34 S V - CDT -Δ 33 S array with an δ 34 S zero intercept at ∆ 33 S ca. +5. This was previously interpreted to indicate mixing of unrelated S-sources in the sediment environment, involving a combination of recycled sulphur from sulphides that had originally formed by sulphate-reducing bacteria, along with elemental sulphur. Here, we advance an alternative explanation based on the recognition that the Archaean seawater sulphate concentration was likely very low, implying that the Archaean ocean could have been poorly mixed with respect to sulphur. Thus, modern oceanic sulphur systematics provide limited insight into the Archaean sulphur cycle. Instead, we propose that the 20th-century atmospheric lead event may be a useful analogue. Similar to industrial lead, the main oceanic input of Archaean sulphur was through atmospheric raindown, with individual giant point sources capable of temporally dominating atmospheric input. Local atmospheric S-isotope signals, of no global significance, could thus have been transmitted into the localised sediment record. Thus, the nonzero intercept δ 34 S V - CDT -Δ 33 S data array may alternatively represent a very localised S-isotope signature in the Neoarchaean surface environment. Fallout from local volcanic eruptions could imprint recycled MIF-S signals into pyrite of restricted depositional environments, thereby avoiding attenuation of the signal in the subdued, averaged global open ocean sulphur pool. Thus, the superposition of extreme local S-isotope signals offers an alternative explanation for the large Neoarchaean MIF-S excursions and asymmetry of the Δ 33 S rock record. © 2017 John Wiley & Sons Ltd.

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

A Bat's-Eye View of Holocene Climate Change in the Southwest: Resolving Ambiguities in Cave Isotopic Records

NASA Astrophysics Data System (ADS)

Cole, J. E.; Truebe, S. A.; Harrington, M. D.; Woodhead, J. D.; Overpeck, J. T.; Hlohowskyj, S.; Henderson, G. M.

2015-12-01

In dry environments, speleothems provide an outstanding archive of information on past climate change, particularly since lakes are typically absent or intermittent. Speleothem stable isotopes are widely used for climate reconstruction, but the isotope-climate relationship is complex in arid-region precipitation, and within-cave processes further complicate climate interpretations. Our isotope results from 3 southeastern Arizona caves, spanning the past 3.5-12 kyr, collectively indicate a weakening monsoon from 7kyr to present. These records exhibit substantial multidecadal-multicentury variability that is sometimes shared, and sometimes independent among caves. Strategies to overcome ambiguities in isotope records include long-term monitoring of cave dripwaters, multi-site comparisons, and multiproxy measurements. Monthly dripwater measurements from two caves spanning several years highlight substantial seasonal biases that create distinct differences in the climate sensitivity of individual cave records. These biases can lead to lack of correlation between records, but also creates opportunities for seasonally specific moisture reconstructions. New preliminary analyses suggest that elemental data can help to unravel the multivariate signal contained in speleothem oxygen isotope records.

A Noninvasive Isotopic Approach to Estimate the Bone Lead Contribution to Blood in Children: Implications for Assessing the Efficacy of Lead Abatement

PubMed Central

Gwiazda, Roberto; Campbell, Carla; Smith, Donald

2005-01-01

Lead hazard control measures to reduce children’s exposure to household lead sources often result in only limited reductions in blood lead levels. This may be due to incomplete remediation of lead sources and/or to the remobilization of lead stores from bone, which may act as an endogenous lead source that buffers reductions in blood lead levels. Here we present a noninvasive isotopic approach to estimate the magnitude of the bone lead contribution to blood in children following household lead remediation. In this approach, lead isotopic ratios of a child’s blood and 5-day fecal samples are determined before and after a household intervention aimed at reducing the child’s lead intake. The bone lead contribution to blood is estimated from a system of mass balance equations of lead concentrations and isotopic compositions in blood at the different times of sample collection. The utility of this method is illustrated with three cases of children with blood lead levels in the range of 18–29 μg/dL. In all three cases, the release of lead from bone supported a substantial fraction of the measured blood lead level postintervention, up to 96% in one case. In general, the lead isotopic compositions of feces matched or were within the range of the lead isotopic compositions of the household dusts with lead loadings exceeding U.S. Environmental Protection Agency action levels. This isotopic agreement underscores the utility of lead isotopic measurements of feces to identify household sources of lead exposure. Results from this limited number of cases support the hypothesis that the release of bone lead into blood may substantially buffer the decrease in blood lead levels expected from the reduction in lead intake. PMID:15626656

Chemical analyses of water samples from the Picher mining area, northeast Oklahoma and southeast Kansas

USGS Publications Warehouse

Parkhurst, David L.

1987-01-01

Chemical analyses are presented for 169 water samples from Tar Creek drainage and the Picher lead-zinc mining area of northeast Oklahoma and southeast Kansas. Water samples were taken from November 1983 through February 1986 from the abandoned mines, from points of mine-water discharge, and from surface-water locations upstream and downstream from mine discharge area. The pH, temperature, alkalinity, dissolved oxygen, and specific conductance were measured in the field. Laboratory analyses routinely included the major ions plus aluminum, cadmium, copper, iron, lead, manganese, nickel, and zinc. Non-routine analyses of dissolved gases and tritium are presented. Stable carbon-isotope ratios for 11 mine-water samples and three carbonate-rock samples are reported. Miscellaneous stream-discharge measurements made at the time of sampling or taken from gaging-station records are included in the report.

Multivariate statistical and lead isotopic analyses approach to identify heavy metal sources in topsoil from the industrial zone of Beijing Capital Iron and Steel Factory.

PubMed

Zhu, Guangxu; Guo, Qingjun; Xiao, Huayun; Chen, Tongbin; Yang, Jun

2017-06-01

Heavy metals are considered toxic to humans and ecosystems. In the present study, heavy metal concentration in soil was investigated using the single pollution index (PIi), the integrated Nemerow pollution index (PIN), and the geoaccumulation index (Igeo) to determine metal accumulation and its pollution status at the abandoned site of the Capital Iron and Steel Factory in Beijing and its surrounding area. Multivariate statistical (principal component analysis and correlation analysis), geostatistical analysis (ArcGIS tool), combined with stable Pb isotopic ratios, were applied to explore the characteristics of heavy metal pollution and the possible sources of pollutants. The results indicated that heavy metal elements show different degrees of accumulation in the study area, the observed trend of the enrichment factors, and the geoaccumulation index was Hg > Cd > Zn > Cr > Pb > Cu ≈ As > Ni. Hg, Cd, Zn, and Cr were the dominant elements that influenced soil quality in the study area. The Nemerow index method indicated that all of the heavy metals caused serious pollution except Ni. Multivariate statistical analysis indicated that Cd, Zn, Cu, and Pb show obvious correlation and have higher loads on the same principal component, suggesting that they had the same sources, which are related to industrial activities and vehicle emissions. The spatial distribution maps based on ordinary kriging showed that high concentrations of heavy metals were located in the local factory area and in the southeast-northwest part of the study region, corresponding with the predominant wind directions. Analyses of lead isotopes confirmed that Pb in the study soils is predominantly derived from three Pb sources: dust generated during steel production, coal combustion, and the natural background. Moreover, the ternary mixture model based on lead isotope analysis indicates that lead in the study soils originates mainly from anthropogenic sources, which contribute much more than the natural sources. Our study could not only reveal the overall situation of heavy metal contamination, but also identify the specific pollution sources.

All Roads Lead to Rome: Exploring Human Migration to the Eternal City through Biochemistry of Skeletons from Two Imperial-Era Cemeteries (1st-3rd c AD)

PubMed Central

Killgrove, Kristina; Montgomery, Janet

2016-01-01

Migration within the Roman Empire occurred at multiple scales and was engaged in both voluntarily and involuntarily. Because of the lengthy tradition of classical studies, bioarchaeological analyses must be fully contextualized within the bounds of history, material culture, and epigraphy. In order to assess migration to Rome within an updated contextual framework, strontium isotope analysis was performed on 105 individuals from two cemeteries associated with Imperial Rome—Casal Bertone and Castellaccio Europarco—and oxygen and carbon isotope analyses were performed on a subset of 55 individuals. Statistical analysis and comparisons with expected local ranges found several outliers who likely immigrated to Rome from elsewhere. Demographics of the immigrants show men and children migrated, and a comparison of carbon isotopes from teeth and bone samples suggests the immigrants may have significantly changed their diet. These data represent the first physical evidence of individual migrants to Imperial Rome. This case study demonstrates the importance of employing bioarchaeology to generate a deeper understanding of a complex ancient urban center. PMID:26863610

All Roads Lead to Rome: Exploring Human Migration to the Eternal City through Biochemistry of Skeletons from Two Imperial-Era Cemeteries (1st-3rd c AD).

PubMed

Killgrove, Kristina; Montgomery, Janet

2016-01-01

Migration within the Roman Empire occurred at multiple scales and was engaged in both voluntarily and involuntarily. Because of the lengthy tradition of classical studies, bioarchaeological analyses must be fully contextualized within the bounds of history, material culture, and epigraphy. In order to assess migration to Rome within an updated contextual framework, strontium isotope analysis was performed on 105 individuals from two cemeteries associated with Imperial Rome-Casal Bertone and Castellaccio Europarco-and oxygen and carbon isotope analyses were performed on a subset of 55 individuals. Statistical analysis and comparisons with expected local ranges found several outliers who likely immigrated to Rome from elsewhere. Demographics of the immigrants show men and children migrated, and a comparison of carbon isotopes from teeth and bone samples suggests the immigrants may have significantly changed their diet. These data represent the first physical evidence of individual migrants to Imperial Rome. This case study demonstrates the importance of employing bioarchaeology to generate a deeper understanding of a complex ancient urban center.

Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry

NASA Technical Reports Server (NTRS)

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

1995-01-01

Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry.

PubMed

Merritt, D A; Freeman, K H; Ricci, M P; Studley, S A; Hayes, J M

1995-07-15

Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

Authenticity of Benin metalworks evaluated by inductively coupled plasma mass spectrometry and lead isotope analyses

NASA Astrophysics Data System (ADS)

Fabbri, E.; Soffritti, C.; Merlin, M.; Vaccaro, C.; Garagnani, G. L.

2017-05-01

Two metal plaques and a cock statuette belonging to a private collection and stylistically consistent with the Royal Art of Benin (Nigeria) were investigated in order to verify their authenticity. The characterization of alloys and patinas were carried out by inductively coupled plasma mass spectrometry, optical microscopy, scanning electron microscopy and energy dispersion spectroscopy, and X-Ray diffraction spectrometry. Furthermore, thermal ionization mass spectrometry was used to assess the abundances of lead isotopes and to attempt a dating by the measurement of 210Pb/204Pb ratio. The results showed that all three artefacts were mainly composed of low lead-brass alloys, with relatively high concentrations of zinc, antimony, cadmium and aluminum in the solid copper solution. Microstructures were mostly dendritic, typical of as-cast brasses, and characterized by recrystallized non-homogeneous twinned grains in areas corresponding to surface decorations, probably due to multiple hammering steps followed by partial annealing treatments. The matrix was composed of a cored α-Cu solid solution together with non-metallic inclusions, lead globules and Sn-rich precipitates in interdendritic spaces. On the surface of all metalworks, both copper and zinc oxides, a non-continuous layer of sulphur-containing contaminants and chloride-containing compounds, were identified. The lead isotope results were consistent with brasses produced shortly before or after 1900 CE. Overall, the data obtained by different techniques supported the hypothesis that the three artefacts were not authentic.

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

Constraining recent lead pollution sources in the North Pacific using ice core stable lead isotopes

NASA Astrophysics Data System (ADS)

Kreutz, K. J.; Osterberg, E. C.; Gross, B.; Handley, M.; Wake, C. P.; Yalcin, K.

2009-12-01

Trends and sources of lead aerosol pollution in the North Pacific boundary layer from 1970-2001 are investigated using a high-resolution ice core record recovered from Eclipse Icefield (3017 masl; St. Elias Mountains, Canada). Average Pb concentrations in the ice core are enriched 31.8 times above crustal values based on ratios with five crustal reference elements (La, Ce, Pr, Al and Ti), indicating that >90% of the Pb deposited is anthropogenic. Isotopic analyses (208Pb/207Pb and 206Pb/207Pb) confirm that the Pb deposited at Eclipse Icefield is predominantly anthropogenic. Annually averaged Pb concentrations range from 25.6 ng/l to 96.7 ng/l (67.6 ng/l mean) and show no long term trend for the 1970-2001 period, contrary to other ice core records from the North Atlantic and the North Pacific. The stable Pb isotope ratio (208Pb/207Pb and 206Pb/207Pb) field indicates that recent Eclipse Icefield Pb pollution represents a variable mixture of North American, Central Eurasian and Asian (Chinese and Japanese) emissions transported across the Pacific basin, with Chinese coal combustion likely being the primary source. Increasing 208Pb/207Pb and 206Pb/207Pb ratios from the 1970’s through 2001 reflect the progressive East Asian industrialization concurrent with a decrease in Eurasian Pb emissions. We compare Pb isotope results from the Eclipse Icefield to data recently acquired from Denali National Park, where snowpit samples were collected from the Kahiltna Pass region (3048 masl). Pb isotope data from both sites are used to evaluate the relative importance of Asian emissions at similar altitudes yet different latitudes.

Mapping the spatio-temporal risk of lead exposure in apex species for more effective mitigation

PubMed Central

Mateo-Tomás, Patricia; Olea, Pedro P.; Jiménez-Moreno, María; Camarero, Pablo R.; Sánchez-Barbudo, Inés S.; Rodríguez Martín-Doimeadios, Rosa C.; Mateo, Rafael

2016-01-01

Effective mitigation of the risks posed by environmental contaminants for ecosystem integrity and human health requires knowing their sources and spatio-temporal distribution. We analysed the exposure to lead (Pb) in griffon vulture Gyps fulvus—an apex species valuable as biomonitoring sentinel. We determined vultures' lead exposure and its main sources by combining isotope signatures and modelling analyses of 691 bird blood samples collected over 5 years. We made yearlong spatially explicit predictions of the species risk of lead exposure. Our results highlight elevated lead exposure of griffon vultures (i.e. 44.9% of the studied population, approximately 15% of the European, showed lead blood levels more than 200 ng ml−1) partly owing to environmental lead (e.g. geological sources). These exposures to environmental lead of geological sources increased in those vultures exposed to point sources (e.g. lead-based ammunition). These spatial models and pollutant risk maps are powerful tools that identify areas of wildlife exposure to potentially harmful sources of lead that could affect ecosystem and human health. PMID:27466455

Quality assurance and quality control in light stable isotope laboratories: A case study of Rio Grande, Texas, water samples

USGS Publications Warehouse

Coplen, T.B.; Qi, H.

2009-01-01

New isotope laboratories can achieve the goal of reporting the same isotopic composition within analytical uncertainty for the same material analysed decades apart by (1) writing their own acceptance testing procedures and putting them into their mass spectrometric or laser-based isotope-ratio equipment procurement contract, (2) requiring a manufacturer to demonstrate acceptable performance using all sample ports provided with the instrumentation, (3) for each medium to be analysed, prepare two local reference materials substantially different in isotopic composition to encompass the range in isotopic composition expected in the laboratory and calibrated them with isotopic reference materials available from the International Atomic Energy Agency (IAEA) or the US National Institute of Standards and Technology (NIST), (4) using the optimum storage containers (for water samples, sealing in glass ampoules that are sterilised after sealing is satisfactory), (5) interspersing among sample unknowns local laboratory isotopic reference materials daily (internationally distributed isotopic reference materials can be ordered at three-year intervals, and can be used for elemental analyser analyses and other analyses that consume less than 1 mg of material) - this process applies to H, C, N, O, and S isotope ratios, (6) calculating isotopic compositions of unknowns by normalising isotopic data to that of local reference materials, which have been calibrated to internationally distributed isotopic reference materials, (7) reporting results on scales normalised to internationally distributed isotopic reference materials (where they are available) and providing to sample submitters the isotopic compositions of internationally distributed isotopic reference materials of the same substance had they been analysed with unknowns, (8) providing an audit trail in the laboratory for analytical results - this trail commonly will be in electronic format and might include a laboratory information management system, (9) making at regular intervals a complete backup of laboratory analytical data (both of samples logged into the laboratory and of mass spectrometric analyses), being sure to store one copy of this backup offsite, and (10) participating in interlaboratory comparison exercises sponsored by the IAEA and other agencies at regular intervals. ?? Taylor & Francis.

Origin of the mysterious Yin-Shang bronzes in China indicated by lead isotopes.

PubMed

Sun, Wei-dong; Zhang, Li-peng; Guo, Jia; Li, Cong-ying; Jiang, Yu-hang; Zartman, Robert E; Zhang, Zhao-feng

2016-03-18

Fine Yin-Shang bronzes containing lead with puzzlingly highly radiogenic isotopic compositions appeared suddenly in the alluvial plain of the Yellow River around 1400 BC. The Tongkuangyu copper deposit in central China is known to have lead isotopic compositions even more radiogenic and scattered than those of the Yin-Shang bronzes. Most of the Yin-Shang bronzes are tin-copper alloys with high lead contents. The low lead and tin concentrations, together with the less radiogenic lead isotopes of bronzes in an ancient smelting site nearby, however, exclude Tongkuangyu as the sole supplier of the Yin-Shang bronzes. Interestingly, tin ingots/prills and bronzes found in Africa also have highly radiogenic lead isotopes, but it remains mysterious as to how such African bronzes may have been transported to China. Nevertheless, these African bronzes are the only bronzes outside China so far reported that have lead isotopes similar to those of the Yin-Shang bronzes. All these radiogenic lead isotopes plot along ~2.0-2.5 Ga isochron lines, implying that deposits around Archean cratons are the most likely candidates for the sources. African cratons along the Nile and even micro-cratons in the Sahara desert may have similar lead signatures. These places were probably accessible by ancient civilizations, and thus are the most favorable suppliers of the bronzes.

Rapid enhancement of chemical weathering recorded by extremely light seawater lithium isotopes at the Permian–Triassic boundary

PubMed Central

Sun, He; Xiao, Yilin; Zhang, Guijie; Casey, John F.; Shen, Yanan

2018-01-01

Lithium (Li) isotope analyses of sedimentary rocks from the Meishan section in South China reveal extremely light seawater Li isotopic signatures at the Permian–Triassic boundary (PTB), which coincide with the most severe mass extinction in the history of animal life. Using a dynamic seawater lithium box model, we show that the light seawater Li isotopic signatures can be best explained by a significant influx of riverine [Li] with light δ7Li to the ocean realm. The seawater Li isotope excursion started ≥300 Ky before and persisted up to the main extinction event, which is consistent with the eruption time of the Siberian Traps. The eruption of the Siberian Traps exposed an enormous amount of fresh basalt and triggered CO2 release, rapid global warming, and acid rains, which in turn led to a rapid enhancement of continental weathering. The enhanced continental weathering delivered excessive nutrients to the oceans that could lead to marine eutrophication, anoxia, acidification, and ecological perturbation, ultimately resulting in the end-Permian mass extinction. PMID:29581278

Rapid enhancement of chemical weathering recorded by extremely light seawater lithium isotopes at the Permian-Triassic boundary

NASA Astrophysics Data System (ADS)

Sun, He; Xiao, Yilin; Gao, Yongjun; Zhang, Guijie; Casey, John F.; Shen, Yanan

2018-04-01

Lithium (Li) isotope analyses of sedimentary rocks from the Meishan section in South China reveal extremely light seawater Li isotopic signatures at the Permian–Triassic boundary (PTB), which coincide with the most severe mass extinction in the history of animal life. Using a dynamic seawater lithium box model, we show that the light seawater Li isotopic signatures can be best explained by a significant influx of riverine [Li] with light δ7Li to the ocean realm. The seawater Li isotope excursion started ≥300 Ky before and persisted up to the main extinction event, which is consistent with the eruption time of the Siberian Traps. The eruption of the Siberian Traps exposed an enormous amount of fresh basalt and triggered CO2 release, rapid global warming, and acid rains, which in turn led to a rapid enhancement of continental weathering. The enhanced continental weathering delivered excessive nutrients to the oceans that could lead to marine eutrophication, anoxia, acidification, and ecological perturbation, ultimately resulting in the end-Permian mass extinction.

Modification degrees at specific sites on heparan sulphate: an approach to measure chemical modifications on biological molecules with stable isotope labelling

PubMed Central

Wu, Zhengliang L.; Lech, Miroslaw

2005-01-01

Chemical modification of biological molecules is a general mechanism for cellular regulation. A quantitative approach has been developed to measure the extent of modification on HS (heparan sulphates). Sulphation on HS by sulphotransferases leads to variable sulphation levels, which allows cells to tune their affinities to various extracellular proteins, including growth factors. With stable isotope labelling and HPLC-coupled MS, modification degrees at various O-sulphation sites could be determined. A bovine kidney HS sample was first saturated in vitro with 34S by an OST (O-sulphotransferase), then digested with nitrous acid and analysed with HPLC-coupled MS. The 34S-labelled oligosaccharides were identified based on their unique isotope clusters. The modification degrees at the sulphotransferase recognition sites were obtained by calculating the intensities of isotopic peaks in the isotope clusters. The modification degrees at 3-OST-1 and 6-OST-1 sites were examined in detail. This approach can also be used to study other types of chemical modifications on biological molecules. PMID:15743272

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

NASA Astrophysics Data System (ADS)

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

2000-03-01

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

Hydrogen, Oxygen and Silicon Isotope Systematics of Groundwater-Magma Interaction in Icelandic Hydrothermal Systems

NASA Astrophysics Data System (ADS)

Kleine, B. I.; Stefansson, A.; Halldorsson, S. A.; Martin, W.; Barnes, J.; Jónasson, K.; Franzson, H.

2016-12-01

Magma often encounters groundwater (meteoric or seawater derived) when intruded into the crust. Magma-groundwater interactions result in the formation of hydrothermal fluids which can lead to contact metamorphism and elemental transport in the country rock. In fact, magma-hydrothermal fluid interaction (rather than magma-magmatic fluid interaction) may lead to classic contact metamorphic reactions. In order to explore the importance of hydrothermal fluid during contact metamorphism we use stable isotopes (δD, δ18O, δ30Si) from both active and extinct magma chambers and hydrothermal systems from across Iceland. Quartz grains from various hydrothermal systems, from crustal xenoliths from the Askja central volcano and from the Hafnarfjall pluton, as well as quartz grains associated with low-T zeolites were analysed for δ18O and δ30Si in-situ using SIMS. Whole rock material of these samples was analysed for δD values using a TCEA coupled to an IRMS. Our results indicate that low-T quartz (<150°C) are dominated by negative δ30Si values whereas positive δ30Si values prevail in quartz precipitated at higher T (>300°C). Combining the results from the analyses of δ18O and δD allows further division of samples into (i) seawater and/or rock dominated and (ii) meteoric water dominated hydrothermal systems. In order to isolate the effects of fluid-rock interaction, fluid source and formation temperature at the magma-groundwater contact, δD, δ18O and δ30Si values of rocks and fluids were modeled using the PHREEQC software. Comparison of analytical and model results shows that the isotopic compositions are influenced by multiple processes. In some cases, groundwater penetrates the contact zone and causes alteration at >400°C by groundwater-magma heat interaction. Other cases document "baked" contact zones without groundwater. Our analyses and modeling demonstrates that groundwater flow and permeability are crucial in setting the style of contact metamorphism around high T intrusions.

Ore genesis of the Wusihe carbonate-hosted Zn-Pb deposit in the Dadu River Valley district, Yangtze Block, SW China: evidence from ore geology, S-Pb isotopes, and sphalerite Rb-Sr dating

NASA Astrophysics Data System (ADS)

Xiong, Suo-Fei; Gong, Yong-Jun; Jiang, Shao-Yong; Zhang, Xiao-Jing; Li, Qian; Zeng, Guo-Ping

2018-01-01

The Wusihe carbonate-hosted Zn-Pb deposit (3.7 Mt. Zn + Pb at a grade of 8.6% Zn and 2.0% Pb) is the largest deposit in the Dadu River Valley district of the Sichuan-Yunnan-Guizhou metallogenic province of southwest China. Three types of orebodies occur: (1) stratiform, banded and lamellar, within dolomite of the Neoproterozoic Dengying Formation; (2) vein type; and (3) breccia type. Four stages of mineralization are distinguished: (i) pyrite stage, (ii) pyrite-pyrrhotite-galena-sphalerite-bitumen stage, (iii) sphalerite-galena stage, and (iv) bitumen-calcite stage. Sphalerite and galena from stages II and III show δ34S ranges from +7.1 to +9.7‰ and +9.1 to +13.1‰, respectively. High-precision in situ lead isotope analyses of sulfides show 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb ratios of 37.938 to 38.336, 15.579 to 15.682, and 17.951 to 18.195, respectively, which suggest a mixing of lead from the basement and the host rocks. Rb-Sr isotope analyses for six sphalerite samples of stage II yielded an isochron age of 411 ± 10 Ma (MSWD = 1.4). Combining all available ore geology and geochemical data, together with fluid inclusion data reported previously, we suggest that the Wusihe deposit is a Mississippi Valley-type (MVT) deposit.

Geochemical and Pb isotopic characterization of soil, groundwater, human hair, and corn samples from the Domizio Flegreo and Agro Aversano area (Campania region, Italy)

USGS Publications Warehouse

Rezza, Carmela; Albanese, Stefano; Ayuso, Robert A.; Lima, Annamaria; Sorvari, Jaana; De Vivo, Benedetto

2018-01-01

A geochemical survey was carried out to investigate metal contamination in the Domizio Littoral and Agro Aversano area (Southern Italy) by means of soil, groundwater, human hair and corn samples. Pb isotope ratios were also determined to identify the sources of metals. Specifically, the investigation focused on topsoils (n = 1064), groundwater (n = 26), 25 human hair (n = 24) and corn samples (n = 13). Topsoils have been sampled and analysed in a previous study for 53 elements (including potentially harmful ones), and determined by ICP-MS after dissolving with aqua regia. Groundwater was analysed for 72 elements by ICP-MS and by ICP-ES. Samples of human hair were prepared and analysed for 16 elements by ICP-MS. Dried corn collected at several farms were also analysed for 53 elements by ICP-MS. The isotopic ratios of 206Pb/207Pb and 208Pb/207Pb in selected topsoil (n = 24), groundwater (n = 9), human hair (n = 9) and corn (n = 4) samples were analysed from both eluates and residues to investigate possible anthropogenic contamination and geogenic contributions. All data were processed and mapped by ArcGis software to produce interpolated maps and contamination factor maps of potentially harmful elements, in accordance with Italian Environmental Law (Legislative Decree 152/06). Results show that soil sampling sites are characterized by As, Cd, Co, Cr, Cu, Hg, Pb, Se, and Zn contents exceeding the action limits established for residential land use (RAL) and, in some cases, also the action limits for industrial land use (IAL) as established by Legislative Decree 152/06. A map of contamination factors and a map showing the degrees of contamination indicate that the areas in the municipalities of Acerra, Casoria and Giugliano have been affected by considerable anthropogenic-related pollution. To interpret the isotopic data and roughly estimate proportion of Pb from an anthropogenic source we broadly defined possible natural and anthropogenic Pb end-member fields based on literature data. For example, we summarized data for Vesuvius and Campi Flegrei volcanic rocks, gasoline, and aerosol deposits.Lead isotope data show mixing between geogenic and anthropogenic sources. Topsoil, groundwater, human hair and corn samples show a greater contribution from geogenic sources like the Yellow Tuff (from Campi Flegrei) and volcanic rocks from Mt. Vesuvius. Aerosols, fly ash and gasoline (anthropogenic sources) have also been contributors. In detail, 46% of the topsoil residues, 96% of topsoil leachates, 88% of groundwater, 90% of human hair, and 25% of corn samples indicate that > 50% percent of the lead in this area can be ascribed to anthropogenic activity.

Wild rabbit host and some parasites show trophic-level relationships for delta 13C and delta 15N: a first report.

PubMed

Boag, B; Neilson, R; Robinson, D; Scrimgeour, C M; Handley, L L

1998-01-01

We report the first isotopic study of an animal host-parasite system. Parasitic, intestinal nematodes, Graphidium strigosum and Passalurus ambiguus, were 15N-enriched relative to their host, the European rabbit Oryctolagus cuniculus, while parasitic cestodes, Cittataenia denticulata and Mosgovoyia pectinata, were 15N-depleted, suggesting different trophic relationships. Host embryos were more similar in their delta 13C and delta 15N values to maternal muscle than were any of the parasites. Coprophagy, the direct recycling of food by the rabbit eating its own faeces, did not lead to isotopic differences between stomach contents and faeces, suggesting that the major point for isotopic discrimination in lagomorph nitrogen metabolism is in the animal rather than in the gut. We conclude that bulk delta 13C and delta 15N can reveal valuable new information about host-parasite relationships, and these could be explored further at the biochemical level using compound-specific isotopic analyses.

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

NASA Astrophysics Data System (ADS)

Suzuki, K.; Takamasa, A.

2017-12-01

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

Theoretical estimates of supernova-neutrino cross sections for the stable even-even lead isotopes: Charged-current reactions

NASA Astrophysics Data System (ADS)

Almosly, W.; Carlsson, B. G.; Suhonen, J.; Toivanen, J.; Ydrefors, E.

2016-10-01

A detailed study of the charged-current supernova electron neutrino and electron antineutrino scattering off the stable even-mass lead isotopes A =204 , 206, and 208 is reported in this work. The proton-neutron quasiparticle random-phase approximation (pnQRPA) is adopted to construct the nuclear final and initial states. Three different Skyrme interactions are tested for their isospin and spin-isospin properties and then applied to produce (anti)neutrino-nucleus scattering cross sections for (anti)neutrino energies below 80 MeV. Realistic estimates of the nuclear responses to supernova (anti)neutrinos are computed by folding the computed cross sections with a two-parameter Fermi-Dirac distribution of the electron (anti)neutrino energies. The computed cross sections are compared with earlier calculations and the analyses are extended to take into account the effects coming from the neutrino oscillations.

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

USGS Publications Warehouse

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

2018-01-01

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

Origin of the mysterious Yin-Shang bronzes in China indicated by lead isotopes

PubMed Central

Sun, Wei-dong; Zhang, Li-peng; Guo, Jia; Li, Cong-ying; Jiang, Yu-hang; Zartman, Robert E.; Zhang, Zhao-feng

2016-01-01

Fine Yin-Shang bronzes containing lead with puzzlingly highly radiogenic isotopic compositions appeared suddenly in the alluvial plain of the Yellow River around 1400 BC. The Tongkuangyu copper deposit in central China is known to have lead isotopic compositions even more radiogenic and scattered than those of the Yin-Shang bronzes. Most of the Yin-Shang bronzes are tin-copper alloys with high lead contents. The low lead and tin concentrations, together with the less radiogenic lead isotopes of bronzes in an ancient smelting site nearby, however, exclude Tongkuangyu as the sole supplier of the Yin-Shang bronzes. Interestingly, tin ingots/prills and bronzes found in Africa also have highly radiogenic lead isotopes, but it remains mysterious as to how such African bronzes may have been transported to China. Nevertheless, these African bronzes are the only bronzes outside China so far reported that have lead isotopes similar to those of the Yin-Shang bronzes. All these radiogenic lead isotopes plot along ~2.0–2.5 Ga isochron lines, implying that deposits around Archean cratons are the most likely candidates for the sources. African cratons along the Nile and even micro-cratons in the Sahara desert may have similar lead signatures. These places were probably accessible by ancient civilizations, and thus are the most favorable suppliers of the bronzes. PMID:26988425

Micro-scale novel stable isotope fractionation during weathering disclosed by femtosecond laser ablation

NASA Astrophysics Data System (ADS)

Schuessler, J. A.; von Blanckenburg, F.

2012-12-01

The stable isotope fractionation of metals and metalloids during chemical weathering and alteration of rocks at low temperature is a topic receiving increasing scientific attention. For these systems, weathering of primary minerals leads to selective partitioning of isotopes between the secondary minerals formed from them, and the dissolved phase of soil or river water. While the isotopic signatures of these processes have been mapped-out at the catchment or the soil scale, the actual isotopic fractionation is occurring at the mineral scale. To identify the processes underlying such micro-scale fractionation, the development of micro-analytical tools allows to investigate mechanisms of isotope fractionation in-situ, in combination with textural information of weathering reactions. We have developed a second-generation UV femtosecond (fs) laser system at GFZ Potsdam. The advantage of UV-fs laser ablation is the reduction of laser-induced isotopic and elemental fractionation by avoiding 'thermal effects' during ablation, such that accurate isotope ratios can be measured by standard-sample-standard bracketing using laser ablation multicollector ICP-MS; where the matrix of the bracketing standard does not need to match that of the sample [1]. Our system consists of the latest generation femtosecond solid-state laser (Newport Spectra Physics Solstice), producing an ultra short pulse width of about 100 femtoseconds at a wavelength of 196 nm. The system is combined with a custom-build computer-controlled sample stage and allows fully automated isotope analyses through synchronised operation of the laser with the Neptune MC-ICP-MS. To assess precision and accuracy of our laser ablation method, we analysed various geological reference materials. We obtained δ30Si values of -0.31 ± 0.23 (2SD, n = 13) for basalt glass BHVO-2G, and -1.25 ± 0.21 (2SD, n = 27) for pure Si IRMM17 when bracketed against NBS-28 quartz. δ56Fe and δ26Mg values obtained from non-matrix matched standard-sample-bracketing laser ablation analyses on sulfides, oxides and silicates agree within 0.15 permil to measurements done by solution MC-ICP-MS after chromatographic matrix separation. With our laser ablation method all compartments of the weathering zone can be analysed with minimal sample preparation [2]. In a first application, we investigate Si isotope fractionation during deep (10 m) core stone weathering, where crystalline rock is altered, producing secondary clay minerals along 20 micrometer wide (biogenic?) alteration textures. While unweathered centers of plagioclase grains show a homogenous Si isotope composition of δ30Si = -0.20 ± 0.17 permil (2SD, n=12), the secondary weathering products found in fissures within and between plagioclase grains consistently show negative δ30Si values - as low as -1.13 permil. Comparison with isotope studies at the soil and catchment scale suggests that the isotopic weathering signatures found in dissolved and particulate Si in rivers can be traced to processes operating at the micro scale. [1] Horn & von Blanckenburg, Spectrochimica Acta B. 62, 2007 [2] Steinhoefel et al., Chem. Geol. 286, 2011

A Reassessment of the Precision of Carbonate Clumped Isotope Measurements: Implications for Calibrations and Paleoclimate Reconstructions

NASA Astrophysics Data System (ADS)

Fernandez, Alvaro; Müller, Inigo A.; Rodríguez-Sanz, Laura; van Dijk, Joep; Looser, Nathan; Bernasconi, Stefano M.

2017-12-01

Carbonate clumped isotopes offer a potentially transformational tool to interpret Earth's history, but the proxy is still limited by poor interlaboratory reproducibility. Here, we focus on the uncertainties that result from the analysis of only a few replicate measurements to understand the extent to which unconstrained errors affect calibration relationships and paleoclimate reconstructions. We find that highly precise data can be routinely obtained with multiple replicate analyses, but this is not always done in many laboratories. For instance, using published estimates of external reproducibilities we find that typical clumped isotope measurements (three replicate analyses) have margins of error at the 95% confidence level (CL) that are too large for many applications. These errors, however, can be systematically reduced with more replicate measurements. Second, using a Monte Carlo-type simulation we demonstrate that the degree of disagreement on published calibration slopes is about what we should expect considering the precision of Δ47 data, the number of samples and replicate analyses, and the temperature range covered in published calibrations. Finally, we show that the way errors are typically reported in clumped isotope data can be problematic and lead to the impression that data are more precise than warranted. We recommend that uncertainties in Δ47 data should no longer be reported as the standard error of a few replicate measurements. Instead, uncertainties should be reported as margins of error at a specified confidence level (e.g., 68% or 95% CL). These error bars are a more realistic indication of the reliability of a measurement.

The lead isotopic age of the Earth can be explained by core formation alone.

PubMed

Wood, Bernard J; Halliday, Alex N

2010-06-10

The meaning of the age of the Earth defined by lead isotopes has long been unclear. Recently it has been proposed that the age of the Earth deduced from lead isotopes reflects volatile loss to space at the time of the Moon-forming giant impact rather than partitioning into metallic liquids during protracted core formation. Here we show that lead partitioning into liquid iron depends strongly on carbon content and that, given a content of approximately 0.2% carbon, experimental and isotopic data both provide evidence of strong partitioning of lead into the core throughout the Earth's accretion. Earlier conclusions that lead is weakly partitioned into iron arose from the use of carbon-saturated (about 5% C) iron alloys. The lead isotopic age of the Earth is therefore consistent with partitioning into the core and with no significant late losses of moderately volatile elements to space during the giant impact.

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

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

Intraspecific carbon and nitrogen isotopic variability in foxtail millet (Setaria italica).

PubMed

Lightfoot, Emma; Przelomska, Natalia; Craven, Martha; O Connell, Tamsin C; He, Lu; Hunt, Harriet V; Jones, Martin K

2016-07-15

Isotopic palaeodietary studies generally focus on bone collagen from human and/or animal remains. While plant remains are rarely analysed, it is known that plant isotope values can vary as a result of numerous factors, including soil conditions, the environment and type of plant. The millets were important food crops in prehistoric Eurasia, yet little is known about the isotopic differences within millet species. Here we compare the stable isotope ratios within and between Setaria italica plants grown in a controlled environment chamber. Using homogenised samples, we compare carbon isotope ratios of leaves and grains, and nitrogen isotope ratios of grains, from 29 accessions of Setaria italica. We find significant isotopic variability within single leaves and panicles, and between leaves and panicles within the same plant, which must be considered when undertaking plant isotope studies. We find that the leaves and grains from the different accessions have a ca 2‰ range in δ(13) C values, while the nitrogen isotope values in the grains have a ca 6‰ range. We also find an average offset of 0.9‰ between leaves and grains in their δ(13) C values. The variation found is large enough to have archaeological implications and within- and between-plant isotope variability should be considered in isotope studies. The range in δ(15) N values is particularly significant as it is larger than the typical values quoted for a trophic level enrichment, and as such may lead to erroneous interpretations of the amount of animal protein in human or animal diets. It is therefore necessary to account for the variability in plant stable isotope values during palaeodietary reconstructions. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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.

Trophic overlap between native and invasive stream crayfish

USGS Publications Warehouse

Magoulick, Daniel D.; Piercey, Glenn L.

2016-01-01

We examined trophic dynamics of a stream food web where invasive Orconectes neglectus appear to be displacing native O. eupunctus in the Spring River drainage of the Ozark Highlands, Missouri and Arkansas, USA. We collected crayfish species and possible food sources seasonally from a site of sympatry on the South Fork Spring River. We determined diet overlap and potential for competition between O. eupunctus and O. neglectus, and investigated seasonal variation using carbon and nitrogen stable isotope analyses and gut content analyses. Gut content analysis showed both species of crayfish consumed mainly detritus during summer and spring, with other prey categories varying by species and season. Stable isotope analysis showed that O. eupunctus and O. neglectus relied on invertebrates as a major energy and nutrient source throughout summer, autumn, and spring, and the two species showed differences in their stable isotope signatures during spring and summer, but not autumn. Given the trophic overlap between O. eupunctus and O. neglectus, there is a potential for the two species to compete for food and to be ecologically redundant. Ecological redundancy can lead to reduced effects on ecosystem function post-invasion, and therefore examining ecological redundancy of potential invaders should be a conservation priority.

Lead (Pb) Isotope Baselines for Studies of Ancient Human Migration and Trade in the Maya Region.

PubMed

Sharpe, Ashley E; Kamenov, George D; Gilli, Adrian; Hodell, David A; Emery, Kitty F; Brenner, Mark; Krigbaum, John

2016-01-01

We examined the potential use of lead (Pb) isotopes to source archaeological materials from the Maya region of Mesoamerica. The main objectives were to determine if: 1) geologic terrains throughout the Maya area exhibit distinct lead isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb), and 2) a combination of lead and strontium ratios can enhance sourcing procedures in the Mesoamerica region. We analyzed 60 rock samples for lead isotope ratios and a representative subset of samples for lead, uranium, and thorium concentrations across the Maya region, including the Northern Lowlands of the Mexican Yucatan Peninsula, the Southern Lowlands of Guatemala and Belize, the Volcanic Highlands, the Belizean Maya Mountains, and the Metamorphic Province/Motagua Valley. Although there is some overlap within certain sub-regions, particularly the geologically diverse Metamorphic Province, lead isotopes can be used to distinguish between the Northern Lowlands, the Southern Lowlands, and the Volcanic Highlands. The distinct lead isotope ratios in the sub-regions are related to the geology of the Maya area, exhibiting a general trend in the lowlands of geologically younger rocks in the north to older rocks in the south, and Cenozoic volcanic rocks in the southern highlands. Combined with other sourcing techniques such as strontium (87Sr/86Sr) and oxygen (δ18O), a regional baseline for lead isotope ratios can contribute to the development of lead isoscapes in the Maya area, and may help to distinguish among geographic sub-regions at a finer scale than has been previously possible. These isotope baselines will provide archaeologists with an additional tool to track the origin and movement of ancient humans and artifacts across this important region.

Lead (Pb) Isotope Baselines for Studies of Ancient Human Migration and Trade in the Maya Region

PubMed Central

Kamenov, George D.; Gilli, Adrian; Hodell, David A.; Emery, Kitty F.; Brenner, Mark; Krigbaum, John

2016-01-01

We examined the potential use of lead (Pb) isotopes to source archaeological materials from the Maya region of Mesoamerica. The main objectives were to determine if: 1) geologic terrains throughout the Maya area exhibit distinct lead isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb), and 2) a combination of lead and strontium ratios can enhance sourcing procedures in the Mesoamerica region. We analyzed 60 rock samples for lead isotope ratios and a representative subset of samples for lead, uranium, and thorium concentrations across the Maya region, including the Northern Lowlands of the Mexican Yucatan Peninsula, the Southern Lowlands of Guatemala and Belize, the Volcanic Highlands, the Belizean Maya Mountains, and the Metamorphic Province/Motagua Valley. Although there is some overlap within certain sub-regions, particularly the geologically diverse Metamorphic Province, lead isotopes can be used to distinguish between the Northern Lowlands, the Southern Lowlands, and the Volcanic Highlands. The distinct lead isotope ratios in the sub-regions are related to the geology of the Maya area, exhibiting a general trend in the lowlands of geologically younger rocks in the north to older rocks in the south, and Cenozoic volcanic rocks in the southern highlands. Combined with other sourcing techniques such as strontium (87Sr/86Sr) and oxygen (δ18O), a regional baseline for lead isotope ratios can contribute to the development of lead isoscapes in the Maya area, and may help to distinguish among geographic sub-regions at a finer scale than has been previously possible. These isotope baselines will provide archaeologists with an additional tool to track the origin and movement of ancient humans and artifacts across this important region. PMID:27806065

Uranium-lead Isotope Evidence in the Shelyabinsk LL5 Chondrite Meteorite for Ancient and Recent Thermal Events

NASA Technical Reports Server (NTRS)

Lapen, T. J.; Kring, D. A.; Zolensky, M. E.; Andreasen, R.; Righter, M.; Swindle, T. D.; Beard, S. P.; Swindle, T. D.

2014-01-01

The impact histories on chondrite parent bodies can be deduced from thermochronologic analyses of materials and isotope systems with distinct apparent closure temperatures. It is especially critical to better understand the geological histories and physical properties of potenally hazardous near-Earth asteroids. Chelyabinsk is an LL5 chondrite meteorite that was dispersed over a wide area tens of kilometers south of the town of Chelyabinsk, Russia by an explosion at an altitude of 27 km at 3:22 UT on 15 Feb 2013 [1,2]. The explosion resulted in significant damage to surrounding areas and over 1500 injuries along with meteorite fragments being spread over a wide area [1].

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

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

USGS Publications Warehouse

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

2000-01-01

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

Lead isotope determinations from sulfide mineral occurrences--Russian Far East

USGS Publications Warehouse

Church, Stan E.; Goryachev, Nikolai A.; Shpikerman, Vladimir I.

2013-01-01

The lead isotope database for sulfide deposits and occurrences in the Russian Far East was funded by the Mineral Resources Program, U.S. Geological Survey (USGS) in conjunction with the collaborative studies of mineral resources by the Russian Academy of Sciences and the U. S. Geological Survey (Nokleberg and others, 1996). Comparisons of these data with similar lead isotope data from Alaska published in Church, Delevaux, and others (1987) and Gaccetta and Church (1989) provide a basis for the following three-fold project objectives: 1. To utilize lead isotope signatures, in conjunction with regional mapping, to assess the relative ages and to categorize the types of mineral deposits studied, 2. To relate the lead isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and 3. To use the lead isotope data to correlate lithotectonic terranes within the northern Cordillera (Alaska, Yukon Territories and British Columbia in Canada, and the western Cordillera of the United States). The report by Church, Gray, and others (1987) shows how this fingerprinting methodology can be applied to trace the offset of lithotectonic (or lithostratigraphic as labeled by some authors) terranes.The lead isotope data presented in table 1 represent the work completed on sulfide mineral deposits located in the Russian Far East from 1993 to 1995, when this study was terminated due to lack of funding. The lead isotope data are reported here for use by investigators who may find them of value in mineral exploration. No attempt is made to summarize the voluminous literature on these mineral deposits.

Elevated Blood Lead Levels in Infants and Mothers in Benin and Potential Sources of Exposure

PubMed Central

Bodeau-Livinec, Florence; Glorennec, Philippe; Cot, Michel; Dumas, Pierre; Durand, Séverine; Massougbodji, Achille; Ayotte, Pierre; Le Bot, Barbara

2016-01-01

Lead in childhood is well known to be associated with poor neurodevelopment. As part of a study on maternal anemia and offspring neurodevelopment, we analyzed blood lead level (BLL) with no prior knowledge of lead exposure in 225 mothers and 685 offspring 1 to 2 years old from Allada, a semi-rural area in Benin, sub-Saharan Africa, between May 2011 and May 2013. Blood samples were analyzed by inductively coupled plasma mass spectrometry. Environmental assessments in households and isotopic ratio measurements were performed for eight children with BLL > 100 µg/L. High lead levels (BLL > 50 µg/L) were found in 44% of mothers and 58% of children. The median BLL was 55.1 (interquartile range 39.2–85.0) and 46.6 (36.5–60.1) µg/L, respectively. Maternal BLL was associated with offspring’s consumption of piped water and animals killed by ammunition. Children’s BLL was associated with presence of paint chips in the house and consumption of animals killed by ammunition. In this population, with 98% of children still breastfed, children’s BLL was highly associated with maternal BLL on multivariate analyses. Environmental measures and isotopic ratios supported these findings. Offspring may be highly exposed to lead in utero and probably via breastfeeding in addition to lead paint exposure. PMID:26978384

Lead (Pb) isotopic fingerprinting and its applications in lead pollution studies in China: a review.

PubMed

Cheng, Hefa; Hu, Yuanan

2010-05-01

As the most widely scattered toxic metal in the world, the sources of lead (Pb) observed in contamination investigation are often difficult to identify. This review presents an overview of the principles, analysis, and applications of Pb isotopic fingerprinting in tracing the origins and transport pathways of Pb in the environment. It also summarizes the history and current status of lead pollution in China, and illustrates the power of Pb isotopic fingerprinting with examples of its recent applications in investigating the effectiveness of leaded gasoline phase-out on atmospheric lead pollution, and the sources of Pb found in various environmental media (plants, sediments, and aquatic organisms) in China. The limitations of Pb isotopic fingerprinting technique are discussed and a perspective on its development is also presented. Further methodological developments and more widespread instrument availability are expected to make isotopic fingerprinting one of the key tools in lead pollution investigation. Copyright 2009 Elsevier Ltd. All rights reserved.

Methane Emissions in the London Region: Deciphering Regional Sources with Mobile Measurements

NASA Astrophysics Data System (ADS)

Zazzeri, G.; Lowry, D.; Fisher, R. E.; France, J. L.; Lanoisellé, M.; Bjorkegren, A.; Nisbet, E. G.

2014-12-01

Methane stable isotope analysis, coupled with mole fraction measurement, has been used to link isotopic signature to methane emissions from the leading methane sources in the London region, such as landfills and gas leaks. A mobile Picarro G2301 CRDS analyser was installed in a vehicle, together with an anemometer and a Hemisphere GPS receiver, to measure atmospheric methane mole fractions and their relative location. When methane plumes were located and intercepted, air samples were collected in Tedlar bags, for δ13C-CH4 isotopic analysis by CF-GC-IRMS (Continous Flow-Gas Chromatography-Isotopic Ratio Mass Spectroscopy). This method provides high precision isotopic values, determining δ13C-CH4 to ±0.05 per mil. The bulk signature of the methane plume into the atmosphere from the whole source area was obtained by Keeling plot analysis, and a δ13C-CH4 signature, with the relative uncertainty, allocated to each methane source investigated. The averaged δ13C-CH4 signature for landfill sites around the London region is - 58 ± 3 ‰, whereas the δ13C-CH4 signature for gas leaks is fairly constant at -36 ± 2 ‰, a value characteristic of North Sea supply. The Picarro G2301 analyser was installed also on the roof of King's College London, located in the centre of the city, and connected to an air inlet located 7 meters above roof height. An auto-sampler was connected to the same air inlet and launched remotely when a high nocturnal build up was expected, allowing up to twenty air bags to be collected for methane isotopic analysis over a 24 hour period. The main source contributing to overnight methane build up in central London is fugitive gas, in agreement with inventories. From the isotopic characterisation of urban methane sources and the source mix in London, the contribution to the urban methane budget and the local distribution of the methane sources given in inventories can be validated.

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

USGS Publications Warehouse

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

2003-01-01

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

Multiple tree-ring isotopes as environmental indicators of diffuse atmospheric pollution in a peri-urban area

NASA Astrophysics Data System (ADS)

Doucet, A.; Savard, M. M.; Bégin, C.; Ouarda, T. B.; Marion, J.

2010-12-01

The combined analyses of tree-ring δ13C, δ18O, δ15N, 206Pb/207Pb, 206Pb/204Pb and 206Pb/208Pb isotope ratios of three red spruce specimens from the Tantaré ecological reserve located 40 km northwest of Québec City (Canada) were studied with the aim of reconstructing environmental conditions and unravel past air-quality changes of the 1880-2007 period. To separate the tree-ring δ18O and δ13C patterns induced by natural conditions from those generated by anthropogenic perturbations, a linear regression was applied between the most explicative meteorological parameters and the isotopic series for the period of low pollution (1880 to 1909). The model equations were then applied to the most recent part of the series (1910-2007) to verify if climatic conditions have remained the main driver of the tree-ring isotopic variations. The good fit between the modeled and measured δ18O series for the entire studied period suggests that the assimilation of oxygen by red spruce trees is not significantly affected by pollution stress near Québec City. However, the deviation between the measured and modeled δ13C values for the 1944-2007 period indicates that diffuse pollution affected carbon assimilation by the investigated trees. To independently validate if atmospheric pollution could have generated the deviation between the measured and the estimated δ13C values, a linear regression was applied between the portion of the residual δ13C values and atmospheric pollution (Canadian fossil fuel proxy from 1958 to 2000). The nice fit between the modeled δ13C values from the combination of the two regression analyses based on climate and emission proxy strongly supports the hypothesis that there is a natural and an anthropogenic portion in the δ13C variations of the studied specimens. The short-term variations of the red spruce δ15N series are correlated with the instrumentally measured amounts of provincial N emissions for the 1990 to 2006 period (longest measurements available). Additionally, the long-term decrease of the δ15N series after 1956 is linked to the low isotopic values of NOx emitted by car exhausts, as expressed by the provincial number of cars which reflect the amount of transport-related N deposition at the provincial scale. The 208Pb/206Pb and 204Pb/206Pb ratios as a function of 206Pb/207Pb of the 1880-1919 period reflect a mixture of natural lead from the mineral soil horizon and mainly anthropogenic lead from north-eastern American coal combustion. The lower Pb ratios of the 1920-1989 period correlate well with the introduction of leaded additives to gasoline characterized by lower ratios relative to coal combustion. Inferring the lead sources of the 1990-2008 period is not as straightforward because lead can potentially derive from three main sources: coal combustion, burnt recycled material and natural lead present in soils. Our results show the great potential of tree-ring stable isotopes to record pollution events in the context of peri-urban diffuse pollution, and to prolong the pollution history in regions where direct measurements of pollutants only covers a relatively short period.

Authenticity of carbon dioxide bubbles in French ciders through multiflow-isotope ratio mass spectrometry measurements.

PubMed

Gaillard, Laetitia; Guyon, Francois; Salagoïty, Marie-Hélène; Médina, Bernard

2013-12-01

A procedure to detect whether carbon dioxide was added to French ciders has been developed. For this purpose, an optimised and simplified method is proposed to determine (13)C/(12)C isotope ratio of carbon dioxide (δ(13)C) in ciders. Three critical steps were checked: (1) influence of atmospheric CO2 remaining in the loaded vial, (2) impact of helium flush, (3) sampling speed. This study showed that atmospheric CO2 does not impact the measurement, that helium flush can lead to isotopic fractionation and finally, that a fractionation occurs only 5h after bottle opening. The method, without any other preparation, consists in sampling 0.2 mL of cold (4 °C) cider in a vial that is passed in an ultrasonic bath for 10 min at room temperature to enhance cider de-carbonation. The headspace CO2 is then analysed using the link Multiflow®-isotope ratio mass spectrometer. Each year, a data bank is developed by fermenting authentic apples juices in order to control cider authenticity. Over a four year span (2008-2011), the CO2 produced during the fermentation step was studied. This set of 61 authentic ciders, from various French production areas, was used to determine a δ(13)C value range of -22.59±0.92‰ for authentic ciders CO2 bubbles. 75 commercial ciders were analysed with this method. Most of the samples analysed present a gas δ(13)C value in the expected range. Nevertheless, some ciders have δ(13)C values outside the 3σ limit, revealing carbonation by technical CO2. This practice is not allowed for organic, "Controlled Appellation of Origin" ciders and ciders specifying natural carbonation on the label. Copyright © 2013 Elsevier Ltd. All rights reserved.

Feather lead concentrations and (207)Pb/(206)Pb ratios reveal lead exposure history of California Condors (Gymnogyps californianus).

PubMed

Finkelstein, M E; George, D; Scherbinski, S; Gwiazda, R; Johnson, M; Burnett, J; Brandt, J; Lawrey, S; Pessier, A P; Clark, M; Wynne, J; Grantham, J; Smith, D R

2010-04-01

Lead poisoning is a primary factor impeding the survival and recovery of the critically endangered California Condor (Gymnogyps californianus). However, the frequency and magnitude of lead exposure in condors is not well-known in part because most blood lead monitoring occurs biannually, and biannual blood samples capture only approximately 10% of a bird's annual exposure history. We investigated the use of growing feathers from free-flying condors in California to establish a bird's lead exposure history. We show that lead concentration and stable lead isotopic composition analyses of sequential feather sections and concurrently collected blood samples provided a comprehensive history of lead exposure over the 2-4 month period of feather growth. Feather analyses identified exposure events not evident from blood monitoring efforts, and by fitting an empirically derived timeline to actively growing feathers, we were able to estimate the time frame for specific lead exposure events. Our results demonstrate the utility of using sequentially sampled feathers to reconstruct lead exposure history. Since exposure risk in individuals is one determinant of population health, our findings should increase the understanding of population-level effects from lead poisoning in condors; this information may also be helpful for other avian species potentially impacted by lead poisoning.

Feather lead concentrations and 207Pb/206Pb ratios reveal lead exposure history of California Condors (Gymnogyps californianus)

USGS Publications Warehouse

Finkelstein, M.E.; George, D.; Scherbinski, S.; Gwiazda, R.; Johnson, M.; Burnett, J.; Brandt, J.; Lawrey, S.; Pessier, Allan P.; Clark, M.R.; Wynne, J.; Grantham, And J.; Smith, D.R.

2010-01-01

Lead poisoning is a primary factor impeding the survival and recovery of the critically endangered California Condor (Gymnogyps californianus). However, the frequency and magnitude of lead exposure in condors is not well-known in part because most blood lead monitoring occurs biannually, and biannual blood samples capture only ∼10% of a bird’s annual exposure history. We investigated the use of growing feathers from free-flying condors in California to establish a bird’s lead exposure history. We show that lead concentration and stable lead isotopic composition analyses of sequential feather sections and concurrently collected blood samples provided a comprehensive history of lead exposure over the 2−4 month period of feather growth. Feather analyses identified exposure events not evident from blood monitoring efforts, and by fitting an empirically derived timeline to actively growing feathers, we were able to estimate the time frame for specific lead exposure events. Our results demonstrate the utility of using sequentially sampled feathers to reconstruct lead exposure history. Since exposure risk in individuals is one determinant of population health, our findings should increase the understanding of population-level effects from lead poisoning in condors; this information may also be helpful for other avian species potentially impacted by lead poisoning.

Diverse origins of Arctic and Subarctic methane point source emissions identified with multiply-substituted isotopologues

NASA Astrophysics Data System (ADS)

Douglas, P. M. J.; Stolper, D. A.; Smith, D. A.; Walter Anthony, K. M.; Paull, C. K.; Dallimore, S.; Wik, M.; Crill, P. M.; Winterdahl, M.; Eiler, J. M.; Sessions, A. L.

2016-09-01

Methane is a potent greenhouse gas, and there are concerns that its natural emissions from the Arctic could act as a substantial positive feedback to anthropogenic global warming. Determining the sources of methane emissions and the biogeochemical processes controlling them is important for understanding present and future Arctic contributions to atmospheric methane budgets. Here we apply measurements of multiply-substituted isotopologues, or clumped isotopes, of methane as a new tool to identify the origins of ebullitive fluxes in Alaska, Sweden and the Arctic Ocean. When methane forms in isotopic equilibrium, clumped isotope measurements indicate the formation temperature. In some microbial methane, however, non-equilibrium isotope effects, probably related to the kinetics of methanogenesis, lead to low clumped isotope values. We identify four categories of emissions in the studied samples: thermogenic methane, deep subsurface or marine microbial methane formed in isotopic equilibrium, freshwater microbial methane with non-equilibrium clumped isotope values, and mixtures of deep and shallow methane (i.e., combinations of the first three end members). Mixing between deep and shallow methane sources produces a non-linear variation in clumped isotope values with mixing proportion that provides new constraints for the formation environment of the mixing end-members. Analyses of microbial methane emitted from lakes, as well as a methanol-consuming methanogen pure culture, support the hypothesis that non-equilibrium clumped isotope values are controlled, in part, by kinetic isotope effects induced during enzymatic reactions involved in methanogenesis. Our results indicate that these kinetic isotope effects vary widely in microbial methane produced in Arctic lake sediments, with non-equilibrium Δ18 values spanning a range of more than 5‰.

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

USGS Publications Warehouse

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

1967-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Early formation of the Moon 4.51 billion years ago

PubMed Central

Barboni, Melanie; Boehnke, Patrick; Keller, Brenhin; Kohl, Issaku E.; Schoene, Blair; Young, Edward D.; McKeegan, Kevin D.

2017-01-01

Establishing the age of the Moon is critical to understanding solar system evolution and the formation of rocky planets, including Earth. However, despite its importance, the age of the Moon has never been accurately determined. We present uranium-lead dating of Apollo 14 zircon fragments that yield highly precise, concordant ages, demonstrating that they are robust against postcrystallization isotopic disturbances. Hafnium isotopic analyses of the same fragments show extremely low initial 176Hf/177Hf ratios corrected for cosmic ray exposure that are near the solar system initial value. Our data indicate differentiation of the lunar crust by 4.51 billion years, indicating the formation of the Moon within the first ~60 million years after the birth of the solar system. PMID:28097222

Trophic overlap between native and invasive stream crayfish

USGS Publications Warehouse

Magoulick, Daniel D.; Piercey, Glenn L.

2016-01-01

We examined trophic dynamics of a stream food web where invasive Orconectes neglectusappear to be displacing native O. eupunctus in the Spring River drainage of the Ozark Highlands, Missouri and Arkansas, USA. We collected crayfish species and possible food sources seasonally from a site of sympatry on the South Fork Spring River. We determined diet overlap and potential for competition between O. eupunctus and O. neglectus, and investigated seasonal variation using carbon and nitrogen stable isotope analyses and gut content analyses. Gut content analysis showed both species of crayfish consumed mainly detritus during summer and spring, with other prey categories varying by species and season. Stable isotope analysis showed that O. eupunctus and O. neglectus relied on invertebrates as a major energy and nutrient source throughout summer, autumn, and spring, and the two species showed differences in their stable isotope signatures during spring and summer, but not autumn. Given the trophic overlap between O. eupunctus and O. neglectus, there is a potential for the two species to compete for food and to be ecologically redundant. Ecological redundancy can lead to reduced effects on ecosystem function post-invasion, and therefore examining ecological redundancy of potential invaders should be a conservation priority.

Rome's urban history inferred from Pb-contaminated waters trapped in its ancient harbor basins.

PubMed

Delile, Hugo; Keenan-Jones, Duncan; Blichert-Toft, Janne; Goiran, Jean-Philippe; Arnaud-Godet, Florent; Albarède, Francis

2017-09-19

Heavy metals from urban runoff preserved in sedimentary deposits record long-term economic and industrial development via the expansion and contraction of a city's infrastructure. Lead concentrations and isotopic compositions measured in the sediments of the harbor of Ostia-Rome's first harbor-show that lead pipes used in the water supply networks of Rome and Ostia were the only source of radiogenic Pb, which, in geologically young central Italy, is the hallmark of urban pollution. High-resolution geochemical, isotopic, and 14 C analyses of a sedimentary core from Ostia harbor have allowed us to date the commissioning of Rome's lead pipe water distribution system to around the second century BC, considerably later than Rome's first aqueduct built in the late fourth century BC. Even more significantly, the isotopic record of Pb pollution proves to be an unparalleled proxy for tracking the urban development of ancient Rome over more than a millennium, providing a semiquantitative record of the water system's initial expansion, its later neglect, probably during the civil wars of the first century BC, and its peaking in extent during the relative stability of the early high Imperial period. This core record fills the gap in the system's history before the appearance of more detailed literary and inscriptional evidence from the late first century BC onward. It also preserves evidence of the changes in the dynamics of the Tiber River that accompanied the construction of Rome's artificial port, Portus , during the first and second centuries AD.

Deuterium isotope effects on 13C and 15N chemical shifts of intramolecularly hydrogen-bonded enaminocarbonyl derivatives of Meldrum’s and Tetronic acid

NASA Astrophysics Data System (ADS)

Ullah, Saif; Zhang, Wei; Hansen, Poul Erik

2010-07-01

Secondary deuterium isotope effects on 13C and 15N nuclear shieldings in a series of cyclic enamino-diesters and enamino-esters and acyclic enaminones and enamino-esters have been examined and analysed using NMR and DFT (B3LYP/6-31G(d,p)) methods. One-dimensional and two-dimensional NMR spectra of enaminocarbonyl and their deuterated analogues were recorded in CDCl 3 and CD 2Cl 2 at variable temperatures and assigned. 1JNH coupling constants for the derivatives of Meldrum's and tetronic acids reveal that they exist at the NH-form. It was demonstrated that deuterium isotope effects, for the hydrogen bonded compounds, due to the deuterium substitution at the nitrogen nucleus lead to large one-bond isotope effects at nitrogen, 1Δ 15N(D), and two-bond isotope effects on carbon nuclei, 2ΔC(ND), respectively. A linear correlations exist between 2ΔC(ND) and 1Δ 15N(D) whereas the correlation with δNH is divided into two. A good agreement between the experimentally observed 2ΔC(ND) and calculated dσ 13C/dR NH was obtained. A very good correlation between calculated NH bond lengths and observed NH chemical shifts is found. The observed isotope effects are shown to depend strongly on Resonance Assisted Hydrogen bonding.

High Precision Isotope Analyses Using Multi-Collector SIMS: Applications to Earth and Planetary Science.

NASA Astrophysics Data System (ADS)

Kita, N. T.; Ushikubo, T.; Valley, J. W.

2008-05-01

The CAMECA IMS-1280 large radius, multicollector ion microprobe at the Wisc-SIMS National Facility is capable of high accuracy and precision for in situ analysis of isotope ratios. With improved hardware stability and software capability, high precision isotope analyses are routinely performed, typically 5 min per spot. We have developed analytical protocols for stable isotope analyses of oxygen, carbon, Mg, Si and Sulfur using multi-collector Faraday Cups (MCFC) and achieved precision of 0.1-0.2 ‰ (1SD) from a typically 10μm spot analyses. A number of isotopically homogeneous mineral standards have been prepared and calibrated in order to certify the accuracy of analyses in the same level. When spatial resolution is critical, spot size is reduced down to sub- μm for δ 18O to obtain better than 0.5‰ (1SD) precision by using electron multiplier (EM) on multi-collection system. Multi-collection EM analysis is also applied at 10 ppm level to Li isotope ratios in zircon with precision better than 2‰ (1SD). A few applications will be presented. (1) Oxygen three isotope analyses of chondrules in ordinary chondrites revealed both mass dependent and mass independent oxygen isotope fractionations among chondrules as well as within individual chondrules. The results give constraints on the process of chondrule formation and origin of isotope reservoirs in the early solar system. (2) High precision 26Al-26Mg (half life of 0.73 Ma) chronology is applied to zoned melilite and anorthite from Ca, Al-rich inclusions (CAI) in Leoville meteorite, and a well-defined internal isochron is obtained. The results indicate the Al- Mg system was remained closed within 40ky of the crystallization of melilite and anorthite in this CAI. (3) Sub- μm spot analyses of δ18O in isotopically zoned zircon from high-grade metamorphism reveals a diffusion profile of ~6‰ over 2μm, indicating slow diffusion of oxygen in zircon. This result also implies that old Archean detrital zircons (> 4Ga) might preserve their primary oxygen isotopic records, which allows us to trace the geological processes of the early earth [1]. Lithium isotope analyses of pre- 4Ga zircon from Jack Hills show high Li abundance and low δ 7Li, indicating existence of highly weathered crustal material as early as 4.3Ga. In conclusion, these new techniques allow us to study small natural variations of stable isotopes at μm-scale that permit exciting and fundamental research where samples are small, precious, or zoned. [1] Page FZ et al. (2007) Am Min 92, 1772-1775.

Fish fins as non-lethal surrogates for muscle tissues in freshwater food web studies using stable isotopes.

PubMed

Hette Tronquart, Nicolas; Mazeas, Laurent; Reuilly-Manenti, Liana; Zahm, Amandine; Belliard, Jérôme

2012-07-30

Dorsal white muscle is the standard tissue analysed in fish trophic studies using stable isotope analyses. However, sampling white muscle often implies the sacrifice of fish. Thus, we examined whether the non-lethal sampling of fin tissue can substitute muscle sampling in food web studies. Analysing muscle and fin δ(15)N and δ(13)C values of 466 European freshwater fish (14 species) with an elemental analyser coupled with an isotope ratio mass spectrometer, we compared the isotope values of the two tissues. Correlations between fin and muscle isotope ratios were examined for all fish together and specifically for 12 species. We further proposed four methods of assessing muscle from fin isotope ratios and estimated the errors made using these muscle surrogates. Despite significant differences between isotope values of the two tissues, fin and muscle isotopic signals are strongly correlated. Muscle values, estimated with raw fin isotope ratios (1st method), induce an error of ca. 1‰ for both isotopes. In comparison, specific (2nd method) or general (3rd method) correlations provide meaningful corrections of fin isotope ratios (errors <0.6‰). On the other hand, relationships, established for Australian tropical fish, only give poor muscle estimates (errors >0.8‰). There is little chance that a global model can be created. However, the 2nd and 3rd methods of estimating muscle values from fin isotope ratios should provide an acceptable level of error for the studies of European freshwater food web. We thus recommend that future studies use fin tissue as a non-lethal surrogate for muscle. Copyright © 2012 John Wiley & Sons, Ltd.

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

USGS Publications Warehouse

Garnit, Hechmi; Bouhel, Salah; Barca, Donatella; Johnson, Craig A.; Chtara, Chaker

2012-01-01

The Sekarna Zn–Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn–Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation–inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000–20,000 ppm) and galena (12–189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80–130°C. The final ice melting temperatures range from −22°C to −11°C, which correspond to salinities of 15–24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (−11.2‰ to −9.3‰) and galena (−16‰ to −12.3‰). The δ34S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

NASA Astrophysics Data System (ADS)

Garnit, Hechmi; Bouhlel, Salah; Barca, Donatella; Johnson, Craig A.; Chtara, Chaker

2012-06-01

The Sekarna Zn-Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn-Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation-inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000-20,000 ppm) and galena (12-189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80-130°C. The final ice melting temperatures range from -22°C to -11°C, which correspond to salinities of 15-24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (-11.2‰ to -9.3‰) and galena (-16‰ to -12.3‰). The δ34S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.

New constraints on subduction inputs and volatile outputs along the Aleutian Arc

NASA Astrophysics Data System (ADS)

Lopez, T. M.; Fischer, T. P.; Plank, T. A.; Rizzo, A. L.; Rasmussen, D. J.; Cottrell, E.; Werner, C. A.; Kern, C.; Ilanko, T.; Buff, L.; Andrys, J.; Kelley, K. A.

2017-12-01

Volatile cycling drives volcanism in subduction zone settings. At arcs, volatiles can originate from the subducted slab, mantle wedge and/or crust. Each region has characteristic isotopic signatures, which can be used to fingerprint volatile provenance. We speculate that differences in subduction parameters, such as convergence angle, plate coupling and subducted sediment fluxes, may lead to differences in volatile provenance, which may in turn influence volcanic eruption style and frequency. Here we combine updated constraints on subduction inputs and volatile outputs to provide new insights into volatile cycling within the Aleutian Arc. The high proportion of organic carbon (80-100% to total carbon) in sediments subducting at the Aleutian trench stands out globally and predicts a light carbon isotopic composition of recycled volcanic fluids. We assess volatile outputs on volcanic timescales and along the arc by combining carbon (C), nitrogen (N) and helium (He) isotopic compositions of volcanic gases and new analyses of He and, where possible, C isotopes in olivine-hosted fluid inclusions. From our preliminary isotopic analyses of volcanic gases, we find a greater proportion of mantle-derived volatiles released from the Western segment of the Aleutian Arc (>40% mantle) compared with other volcanic arcs around the world (<30% mantle), where volatiles are sourced primarily from subducted or upper crustal carbonates. This trend may be due to the oblique convergence and low subducted sediment input in this region. The Aleutian Arc also exhibits among the lightest carbon isotope ratios of arcs worldwide (δ13C = -10 to -15‰), especially in the central part of the arc, where organic-bearing terrigneous sediment fills the trench and the convergence rate is high. New constraints on subduction inputs and outputs presented here will help discriminate between upper crustal and subducted carbon sources, and provide further insights into volatile cycling and subduction processes within the Aleutian Arc.

High congruence of isotope sewage signals in multiple marine taxa.

PubMed

Connolly, Rod M; Gorman, Daniel; Hindell, Jeremy S; Kildea, Timothy N; Schlacher, Thomas A

2013-06-15

Assessments of sewage pollution routinely employ stable nitrogen isotope analysis (δ(15)N) in biota, but multiple taxa are rarely used. This single species focus leads to underreporting of whether derived spatial N patterns are consistent. Here we test the question of 'reproducibility', incorporating 'taxonomic replication' in the measurement of δ(15)N gradients in algae, seagrasses, crabs and fish with distance from a sewage outfall on the Adelaide coast (southern Australia). Isotopic sewage signals were equally strong in all taxa and declined at the same rate. This congruence amongst taxa has not been reported previously. It implies that sewage-N propagates to fish via a tight spatial coupling between production and consumption processes, resulting from limited animal movement that closely preserves the spatial pollution imprint. In situations such as this where consumers mirror pollution signals of primary producers, analyses of higher trophic levels will capture a broader ambit of ecological effects. Copyright © 2013 Elsevier Ltd. All rights reserved.

Remobilisation of industrial lead depositions in ash during Australian wildfires.

PubMed

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

2017-12-01

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

Historical record of lead accumulation and source in the tidal flat of Haizhou Bay, Yellow Sea: Insights from lead isotopes.

PubMed

Zhang, Rui; Guan, Minglei; Shu, Yujie; Shen, Liya; Chen, Xixi; Zhang, Fan; Li, Tiegang

2016-05-15

In order to investigate the historical records of lead contamination and source in coastal region of Haizhou Bay, Yellow Sea, a sediment core was collected from tidal flat, dated by (210)Pb and (137)Cs. Lead and its stable isotopic ratios were determined. The profiles of enrichment factor (EF) and Pb isotope ratios showed increasing trend upward throughout the core, correlating closely with the experience of a rapid economic and industrial development of the catchment. According to Pb isotopic ratios, coal combustion emission mainly contributed to the Pb burden in sediments. Based on end-member model, coal combustion emission dominated anthropogenic Pb sources in recent decades contributing from 48% to 67% in sediment. And the contribution of leaded gasoline was lower than 20%. A stable increase of coal combustion source was found in sediment core, while the contribution of leaded gasoline had declined recently, with the phase-out of leaded gasoline in China. Copyright © 2016 Elsevier Ltd. All rights reserved.

Insights into Wilson's Warbler migration from analyses of hydrogen stable-isotope ratios

Treesearch

Jeffrey F. Kelly; Viorel Atudorei; Zachary D. Sharp; Deborah M. Finch

2002-01-01

Our ability to link the breeding locations of individual passerines to migration stopover sites and wintering locations is limited. Stable isotopes of hydrogen contained in bird feathers have recently shown potential in this regard. We measured hydrogen stable-isotope ratios (deltaD) of feathers from breeding, migrating, and wintering Wilson's Warblers. Analyses...

INTERLABORATORY COMPARISON OF MASS SPECTROMETRIC METHODS FOR LEAD ISOTOPES AND TRACE ELEMENTS IN NIST SRM 1400 BONE ASH

EPA Science Inventory

The results of an interlaboratory comparison are reported for he lead isotope composition and for trace element concentrations in NIST SRM 1400 Bone Ash obtained using quadrupole and magnetic-sector inductively coupled plasma mass spectrometry (ICP-MS) and (for the Pb isotopes on...

Geology and ore deposits of the Mahd Adh Dhahab District, Kingdom of Saudi Arabia

USGS Publications Warehouse

Luce, Robert W.; Bagdady, Abdulaziz; Roberts, Ralph Jackson

1976-01-01

The principal ore minerals are pyrite, chalcopyrite, sphalerite, galena, and minor tetrahedrite, argentite, and native gold and silver. The gold and silver occurs finely disseminated in the veins and in the altered selvages of the veins. Widespread potassic and propylitic alteration accompanied the ore-forming processes. Potassium feldspar was introduced during an early stage of vein formation. Isotopic analyses of lead in vein potassium feldspar and galena yield a model age of about 900-1050 million years with the possibility of the original lead source having been remobilized about 600 million years ago. Chlorite and carbonate are also prominent vein minerals.

Mass spectrometric measurements of the isotopic anatomies of molecules (Invited)

NASA Astrophysics Data System (ADS)

Eiler, J. M.; Krumwiede, D.; Schlueter, H.

2013-12-01

Site-specific and multiple isotopic substitutions in molecular structures potentially provide an extraordinarily rich set of constraints on their sources, conditions of formation, reaction and transport histories, and perhaps other issues. Examples include carbonate ';clumped isotope' thermometry, clumped isotope measurements of CO2, O2, and, recently, methane, ethane and N2O; site-specific 15N measurements in N2O and 13C and D analyses of fatty acids, sugars, cellulose, food products, and, recently, n-alkanes. Extension of the principles behind these tools to the very large number of isotopologues of complex molecules could potentially lead to new uses of isotope chemistry, similar to proteomics, metabolomics and genomics in their complexity and depth of detail (';isotomics'?). Several technologies are potentially useful for this field, including ';SNIF-NMR', gas source mass spectrometry and IR absorption spectroscopy. However, all well established methods have restrictive limits in the sizes of samples, types of analyzes, and the sorts of isotopologues that can be measured with useful precision. We will present an overview of several emerging instruments and techniques of high-resolution gas source mass spectrometry that may enable study of a large proportion of the isotopologues of a wide range of volatile and semi-volatile compounds, including many organics, with precisions and sample sizes suitable for a range of applications. A variety of isotopologues can be measured by combining information from the Thermo 253 Ultra (a new high resolution, multi-collector gas source mass spectrometer) and the Thermo DFS (a very high resolution single collector, but used here on a novel mode to achieve ~per mil precision ratio measurements), sometimes supplemented by conventional bulk isotopic measurements. It is possible to design methods in which no one of these sources of data meaningfully constrain abundances of specific isotopologues, but their combination fully and precisely constrains a large number. We have assembled a suite of instruments (including the prototype of the Ultra, and a modified version of the DFS that is capable of dual inlet analyses) that make it logistically straightforward to perform such multi-instrument analyses. Examples will be presented documenting the accuracy of these techniques for systems that are independently well known (e.g., isotopologues of methane), and the precision and internal consistency of results for larger, more complex molecules (e.g., a suite of singly and doubly substituted isotopologues of hexane and other moderate-molecular-weight organics).

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

USGS Publications Warehouse

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

2006-01-01

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

Stable Chlorine Isotopes and Elemental Chlorine by Thermal Ionization Mass Spectrometry and Ion Chromatography; Martian Meteorites, Carbonaceous Chondrites and Standard Rocks

NASA Technical Reports Server (NTRS)

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

2011-01-01

Recently significantly large mass fractionation of stable chlorine isotopes has been reported for terrestrial and lunar samples [1,2]. In addition, in view of possible early solar system processes [3] and also potential perchlorate-related fluid/microbial activities on the Martian surface [4,5], a large chlorine isotopic fractionation might be expected for some types of planetary materials. Due to analytical difficulties of isotopic and elemental analyses, however, current chlorine analyses for planetary materials are controversial among different laboratories, particularly between IRMS (gas source mass spectrometry) and TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1,6,7] for isotopic analyses, as well as between those doing pyrohydrolysis and other groups [i.e. 6,8]. Additional careful investigations of Cl isotope and elemental abundances are required to confirm real chlorine isotope and elemental variations for planetary materials. We have developed a TIMS technique combined with HF-leaching/ion chromatography at NASA JSC that is applicable to analysis of small amounts of meteoritic and planetary materials. We present here results for several standard rocks and meteorites, including Martian meteorites.

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

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

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

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

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

DOE PAGES

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

2016-04-25

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

Platinum stable isotopes in ferromanganese crust and nodules

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

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

NASA Astrophysics Data System (ADS)

Bonazza, Mattia; Meijide, Ana; Knohl, Alexander

2017-04-01

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

Rome’s urban history inferred from Pb-contaminated waters trapped in its ancient harbor basins

PubMed Central

Delile, Hugo; Keenan-Jones, Duncan; Goiran, Jean-Philippe; Arnaud-Godet, Florent; Albarède, Francis

2017-01-01

Heavy metals from urban runoff preserved in sedimentary deposits record long-term economic and industrial development via the expansion and contraction of a city’s infrastructure. Lead concentrations and isotopic compositions measured in the sediments of the harbor of Ostia—Rome’s first harbor—show that lead pipes used in the water supply networks of Rome and Ostia were the only source of radiogenic Pb, which, in geologically young central Italy, is the hallmark of urban pollution. High-resolution geochemical, isotopic, and 14C analyses of a sedimentary core from Ostia harbor have allowed us to date the commissioning of Rome’s lead pipe water distribution system to around the second century BC, considerably later than Rome’s first aqueduct built in the late fourth century BC. Even more significantly, the isotopic record of Pb pollution proves to be an unparalleled proxy for tracking the urban development of ancient Rome over more than a millennium, providing a semiquantitative record of the water system’s initial expansion, its later neglect, probably during the civil wars of the first century BC, and its peaking in extent during the relative stability of the early high Imperial period. This core record fills the gap in the system’s history before the appearance of more detailed literary and inscriptional evidence from the late first century BC onward. It also preserves evidence of the changes in the dynamics of the Tiber River that accompanied the construction of Rome’s artificial port, Portus, during the first and second centuries AD. PMID:28847928

Variable microstructural response of baddeleyite to shock metamorphism in young basaltic shergottite NWA 5298 and improved U-Pb dating of Solar System events

NASA Astrophysics Data System (ADS)

Darling, James R.; Moser, Desmond E.; Barker, Ivan R.; Tait, Kim T.; Chamberlain, Kevin R.; Schmitt, Axel K.; Hyde, Brendt C.

2016-06-01

The accurate dating of igneous and impact events is vital for the understanding of Solar System evolution, but has been hampered by limited knowledge of how shock metamorphism affects mineral and whole-rock isotopic systems used for geochronology. Baddeleyite (monoclinic ZrO2) is a refractory mineral chronometer of great potential to date these processes due to its widespread occurrence in achondrites and robust U-Pb isotopic systematics, but there is little understanding of shock-effects on this phase. Here we present new nano-structural measurements of baddeleyite grains in a thin-section of the highly-shocked basaltic shergottite Northwest Africa (NWA) 5298, using high-resolution electron backscattered diffraction (EBSD) and scanning transmission electron microscopy (STEM) techniques, to investigate shock-effects and their linkage with U-Pb isotopic disturbance that has previously been documented by in-situ U-Pb isotopic analyses. The shock-altered state of originally igneous baddeleyite grains is highly variable across the thin-section and often within single grains. Analyzed grains range from those that preserve primary (magmatic) twinning and trace-element zonation (baddeleyite shock Group 1), to quasi-amorphous ZrO2 (Group 2) and to recrystallized micro-granular domains of baddeleyite (Group 3). These groups correlate closely with measured U-Pb isotope compositions. Primary igneous features in Group 1 baddeleyites (n = 5) are retained in high shock impedance grain environments, and an average of these grains yields a revised late-Amazonian magmatic crystallization age of 175 ± 30 Ma for this shergottite. The youngest U-Pb dates occur from Group 3 recrystallized nano- to micro-granular baddeleyite grains, indicating that it is post-shock heating and new mineral growth that drives much of the isotopic disturbance, rather than just shock deformation and phase transitions. Our data demonstrate that a systematic multi-stage microstructural evolution in baddeleyite results from a single cycle of shock-loading, heating and cooling during transit to space, and that this leads to variable disturbance of the U-Pb isotope system. Furthermore, by linking in-situ U-Pb isotopic measurements with detailed micro- to nano-structural analyses, it is possible to resolve the timing of both endogenic crustal processes and impact events in highly-shocked planetary materials using baddeleyite. This opens up new opportunities to refine the timing of major events across the Solar System.

Lead isotopes in soils and groundwaters as tracers of the impact of human activities on the surface environment: The Domizio-Flegreo Littoral (Italy) case study

USGS Publications Warehouse

Grezzi, G.; Ayuso, R.A.; de Vivo, B.; Lima, A.; Albanese, S.

2011-01-01

The isotopic signature of geogenic and anthropogenic materials, in combination with concentration data for pollutants, can help trace the origin and the extent of contamination in the environment. This approach is particularly effective if naturally occurring and anthropogenically introduced metals have different isotopic ratios. Lead isotope analysis on soils from 7 profiles (1. m depth) and on groundwaters from 8 wells have been used to determine the impact of human activities on the surface environment of Domizio-Flegreo Littoral. Result obtained show that in sub-rural areas the isotopic composition of the samples collected along the soil profiles of Domizio-Flegreo Littoral is likely mostly controlled by the nature of the parent geologic material (natural) while in more urbanized areas (Giugliano) Pb isotopic composition in superficial soils is mostly influenced by anthropic sources such as motor vehicles. Lead isotopic ratios in groundwaters also show that the use of pesticides and, probably, the influence of aerosols and the presence of illegal waste disposal can influence water quality. ?? 2010 Elsevier B.V.

Letter Report: Stable Hydrogen and Oxygen Isotope Analysis of B-Complex Groundwater Samples

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

Lee, Brady D.; Moran, James J.; Nims, Megan K.

Report summarizing stable oxygen and hydrogen isotope analysis of two groundwater samples from the B-Complex. Results from analyses were compared to perched water and pore water analyses performed previously.

Characterizing the interaction of groundwater and surface water in the karst aquifer of Fangshan, Beijing (China)

NASA Astrophysics Data System (ADS)

Chu, Haibo; Wei, Jiahua; Wang, Rong; Xin, Baodong

2017-03-01

Correct understanding of groundwater/surface-water (GW-SW) interaction in karst systems is of greatest importance for managing the water resources. A typical karst region, Fangshan in northern China, was selected as a case study. Groundwater levels and hydrochemistry analyses, together with isotope data based on hydrogeological field investigations, were used to assess the GW-SW interaction. Chemistry data reveal that water type and the concentration of cations in the groundwater are consistent with those of the surface water. Stable isotope ratios of all samples are close to the local meteoric water line, and the 3H concentrations of surface water and groundwater samples are close to that of rainfall, so isotopes also confirm that karst groundwater is recharged by rainfall. Cross-correlation analysis reveals that rainfall leads to a rise in groundwater level with a lag time of 2 months and groundwater exploitation leads to a fall within 1 month. Spectral analysis also reveals that groundwater level, groundwater exploitation and rainfall have significantly similar response periods, indicating their possible inter-relationship. Furthermore, a multiple nonlinear regression model indicates that groundwater level can be negatively correlated with groundwater exploitation, and positively correlated with rainfall. The overall results revealed that groundwater level has a close correlation with groundwater exploitation and rainfall, and they are indicative of a close hydraulic connection and interaction between surface water and groundwater in this karst system.

The persistence of lead from past gasoline emissions and mining drainage in a large riparian system: Evidence from lead isotopes in the Sacramento River, California

USGS Publications Warehouse

Dunlap, C.E.; Alpers, Charles N.; Bouse, R.; Taylor, Howard E.; Unruh, D.M.; Flegal, A.R.

2008-01-01

Lead concentrations and isotope ratios measured in river water colloids and streambed sediment samples along 426 km of the Sacramento River, California reveal that the influence of lead from the historical mining of massive sulfide deposits in the West Shasta Cu-mining district (at the headwaters of the Sacramento River) is confined to a 60 km stretch of river immediately downstream of that mining region, whereas inputs from past leaded gasoline emissions and historical hydraulic Au-mining in the Sierra Nevadan foothills are the dominant lead sources in the remaining 370 km of the river. Binary mixing calculations suggest that more than 50% of the lead in the Sacramento River outside of the region of influence of the West Shasta Cu-mining district is derived from past depositions of leaded gasoline emissions. This predominance is the first direct documentation of the geographic extent of gasoline lead persistence throughout a large riparian system (>160,000 km2) and corroborates previous observations based on samples taken at the mouth of the Sacramento River. In addition, new analyses of sediment samples from the hydraulic gold mines of the Sierra Nevada foothills confirm the present-day fluxes into the Sacramento River of contaminant metals derived from historical hydraulic Au-mining that occurred during the latter half of the 19th and early part of the 20th centuries. These fluxes occur predominantly during periods of elevated river discharge associated with heavy winter precipitation in northern California. In the broadest context, the study demonstrates the potential for altered precipitation patterns resulting from climate change to affect the mobility and transport of soil-bound contaminants in the surface environment. ?? 2008 Elsevier Ltd.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Getting the Lead Out of Bermuda; The Legacy of a Forty Year Record in the North Atlantic Using a Transient Experiment in the Atmosphere and Water

NASA Astrophysics Data System (ADS)

Church, T. M.; Alleman, L. Y.; Veron, A. J. J.; Boyle, E. A.; Zurbrick, C.; Patterson, C. C.; Flegal, A. R., Jr.

2015-12-01

Some forty years ago, Schaule and Patterson established the first accurate profile of lead in waters off Bermuda. In evidence was a massive environmental insult from lead emissions being carried seaward by the atmosphere over the Sargasso Sea. Further documentation was possible using contiguous time series in the atmosphere on Bermuda, surface sea water nearby and recorded in local corals. Lead had then an overwhelming source from the combustion of gasoline, primarily in the USA and secondarily in Europe. These were carried to Bermuda on seasonally alternating temperate and trade winds from the west and east, respectively. The anthropogenic sources were well distinguished based on the unique radiogenic nature of stable lead isotopes in the gasoline being used by these countries. Subsequently, decreasing use in the west (USA) followed by that in the east (Europe) was isotopically evident. As such, the two signatures were subjected to transient mixing in the atmosphere and subsequently with depth in ocean. A transient experiment uses data during 1996-1998, a period of transition in leaded gasoline use in the USA and Europe. Here are complimentary records of lead concentration and stable isotopes in atmospheric deposition and surface waters. The results allow an isotopic mass balance, indicating much of the lead in Bermuda surface water at that time may not have been deposited locally. As such, it may be presumed to reflect easterly advection of some lead at the surface under limited scavenging via the prevailing subtropical gyre circulation. These annual circulation periods are consistent with both physical data and another lead isotopic mass balance in the east. Going forward, Bermuda time series of trace elements and isotopes such as lead could continue to record climatological (e.g. NAO) transients in atmospheric scavenging, potential impact on surface ecosystems, and changes in mixing into deeper waters of the Sargasso Sea and points further afield.

Use of Lead Isotopes to Identify Sources of Metal and Metalloid Contaminants in Atmospheric Aerosol from Mining Operations

PubMed Central

Félix, Omar I.; Csavina, Janae; Field, Jason; Rine, Kyle P.; Sáez, A. Eduardo; Betterton, Eric A.

2014-01-01

Mining operations are a potential source of metal and metalloid contamination by atmospheric particulate generated from smelting activities, as well as from erosion of mine tailings. In this work, we show how lead isotopes can be used for source apportionment of metal and metalloid contaminants from the site of an active copper mine. Analysis of atmospheric aerosol shows two distinct isotopic signatures: one prevalent in fine particles (< 1 μm aerodynamic diameter) while the other corresponds to coarse particles as well as particles in all size ranges from a nearby urban environment. The lead isotopic ratios found in the fine particles are equal to those of the mine that provides the ore to the smelter. Topsoil samples at the mining site show concentrations of Pb and As decreasing with distance from the smelter. Isotopic ratios for the sample closest to the smelter (650 m) and from topsoil at all sample locations, extending to more than 1 km from the smelter, were similar to those found in fine particles in atmospheric dust. The results validate the use of lead isotope signatures for source apportionment of metal and metalloid contaminants transported by atmospheric particulate. PMID:25496740

Genetic relations of oceanic basalts as indicated by lead isotopes

USGS Publications Warehouse

Tatsumoto, M.

1966-01-01

The isotopic compositions of lead and the concentrations of lead, uranium, and thorium in samples of oceanic tholeiite and alkali suites are determined, and the genetic relations of the oceanic basalts are discussed. Lead of the oceanic tholeiites has a varying lead-206 : lead-204 ratio between 17.8 and 18.8, while leads of the alkali basalt suites from Easter Island and Guadalupe Island are very radiogenic with lead-206 : lead-204 ratios between 19.3 and 20.4. It is concluded that (i) the isotopic composition of lead in oceanic tholeiite suggests that the upper mantle source region of the tholeiite was differentiated from an original mantle material more than 1 billion years ago and that the upper mantle is not homogeneous at the present time, (ii) less than 20 million years was required for the crystal differentiation within the alkali suite from Easter Island, (iii) no crustal contamination was involved in the course of differentiation of rocks from Easter Island; however, some crustal contamination may have affected Guadalupe Island rocks, and (iv) alkali basalt may be produced from the tholeiite in the oceanic region by crystal differentiation. Alternatively the difference in the isotopic composition of lead in oceanic basalts may be produced by partial melting at different depths of a differentiated upper mantle.

Al-Mg Isotopic Constraints on Alteration of Allende Ca-Al-rich Inclusions

NASA Astrophysics Data System (ADS)

Fagan, T. J.; Guan, Y.; MacPherson, G. J.

2006-03-01

Multiple stages of alteration of Allende CAIs are implied from SIMS analyses of Al-Mg isotopes in secondary minerals from one B2 and one FTA CAI. 26Mg-excesses are absent from most B2 analyses, but present in one B2 grossular and most FTA analyses.

Evidence for distillation in the formation of HAL and related hibonite inclusions. [from Allende, Dhajala, and Murchison chondrites

NASA Technical Reports Server (NTRS)

Ireland, Trevor R.; Zinner, Ernst K.; Fahey, Albert J.; Esat, Tezer M.

1992-01-01

New Ca- and Ti-isotopic analyses of DH-H1, 7-404, and 7-971, and Mg-isotopic analyses on DH-H1 and 7-404 are reported. O-isotopic analyses of HAL, 7-404, 7-971, and a variety of other refractory inclusions from Murchison were made in order to establish the presence or absence of FUN O-isotopic systematics. A higonite-rich residue produced by the evaporation of kaersutite was analyzed for its trace-element and isotopic abundances to see if any of the characteristics of FUN hibonite inclusions can be produced by distillation in the laboratory. These data are then used to evaluate for all four inclusions the HAL-type formation models originally proposed by Allen et al. (1980) and Lee et al. (1980). The four inclusions were found to have very similar chemical and isotopic features. All are characterized by large Ce depletions and very low Mg, Ti, and V concentrations compared to other meteoritic hibonites. All four inclusions have delta(C-48) within error of -5 per mil. Ca-, Ti-, and O-isotopic compositions are fractionated with enrichments of the heavy isotopes, and the Ti-isotopic mass fractionation is inversely correlated with Ti concentration. It is concluded that the inclusions formed primarily as distillation residues in accord with the early conclusions.

Coordinated In Situ Nanosims Analyses of H-C-O Isotopes in ALH 84001 Carbonates

NASA Technical Reports Server (NTRS)

Usui, T.; Alexander, C. M. O'D.; Wang, J.; Simon, J. I.; Jones, J. H.

2016-01-01

The surface geology and geomorphology of Mars indicate that it was once warm enough to maintain a large body of liquid water on its surface, though such a warm environment might have been transient. This study reports the hydrogen, carbon, and oxygen isotope compositions of the ancient atmosphere/hydrosphere of Mars based on in situ ion microprobe analyses of approximately 4 Ga-old carbonates in Allan Hills (ALH) 84001. The ALH 84001 carbonates are the most promising targets because they are thought to have formed from fluid that was closely associated with the Noachian atmosphere. While there are a number of carbon and oxygen isotope studies of the ALH 84001 carbonates, in situ hydrogen isotope analyses of these carbonates are limited and were reported more than a decade ago. Well-documented coordinated in situ analyses of carbon, oxygen and hydrogen isotopes provide an internally consistent dataset that can be used to constrain the nature of the Noachian atmosphere/hydrosphere and may eventually shed light on the hypothesis of ancient watery Mars.

Evaluation of the combined measurement uncertainty in isotope dilution by MC-ICP-MS.

PubMed

Fortunato, G; Wunderli, S

2003-09-01

The combination of metrological weighing, the measurement of isotope amount ratios by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) and the use of high-purity reference materials are the cornerstones to achieve improved results for the amount content of lead in wine by the reversed isotope dilution technique. Isotope dilution mass spectrometry (IDMS) and reversed IDMS have the potential to be a so-called primary method, with which close comparability and well-stated combined measurement uncertainties can be obtained. This work describes the detailed uncertainty budget determination using the ISO-GUM approach. The traces of lead in wine were separated from the matrix by ion exchange chromatography after HNO(3)/H(2)O(2) microwave digestion. The thallium isotope amount ratio ( n((205)Tl)/ n((203)Tl)) was used to correct for mass discrimination using an exponential model approach. The corrected lead isotope amount ratio n((206)Pb)/ n((208)Pb) for the isotopic standard SRM 981 measured in our laboratory was compared with ratio values considered to be the least uncertain. The result has been compared in a so-called pilot study "lead in wine" organised by the CCQM (Comité Consultatif pour la Quantité de Matière, BIPM, Paris; the highest measurement authority for analytical chemical measurements). The result for the lead amount content k(Pb) and the corresponding expanded uncertainty U given by our laboratory was:k(Pb)=1.329 x 10-10mol g-1 (amount content of lead in wine)U[k(Pb)]=1.0 x 10-12mol g-1 (expanded uncertainty U=kxuc, k=2)The uncertainty of the main influence parameter of the combined measurement uncertainty was determined to be the isotope amount ratio R(206,B) of the blend between the enriched spike and the sample.

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

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

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

1998-08-01

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

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.

Tables for determining lead, uranium, and thorium isotope ages

NASA Technical Reports Server (NTRS)

Schonfeld, E.

1974-01-01

Tables for determining lead, uranium, and thorium isotope ages are presented in the form of computer printouts. Decay constants, analytical expressions for the functions evaluated, and the precision of the calculations are briefly discussed.

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.

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

PubMed

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

2011-06-15

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

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

USGS Publications Warehouse

Ayuso, R.A.

1986-01-01

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

Stable isotope analyses reveal the importance of seagrass beds as feeding areas for juvenile Myrophic punctatus in Florida

EPA Science Inventory

The feeding habits and habitats of the speckled worm eel Myrophis punctatus were studied on the mangrove edge of the Indian River Lagoon (Florida) using stomach contents and stable isotope analyses of carbon (δ13C) and nitrogen (δ15N). Stomach dietary analyses identified four tax...

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.

Geochemical Treasure Hunt for Primary School Children

NASA Astrophysics Data System (ADS)

Tesmer, Maja; Frick, Daniel; Gerrits, Ruben; des GFZ-GeoWunderWerkstatt, Schülerlabor

2017-04-01

How can you inspire school children for geochemistry, and scientific exploratory urge? The key is to raise their curiosity and make learning new things a hands-on experience. The Fellows of the European Marie Curie Initial Training Network IsoNose designed and established a "Geochemical Treasure Hunt" to excite children for scientific investigations. This workshop explains primary school children the research and scientific methods of isotopic geochemistry, and their use to understand processes on the Earth's surface. From obtaining 'samples', performing various experiments, the school children gather clues leading them to the hidden treasure on the Telegrafenberg (campus of the GFZ Potsdam). The course was designed for school children to learn hands-on the meaning of elements, atoms and isotopes. In small groups the children conduct experiments of simplified methods being indispensable to any isotope geochemist. However, prior to working in any laboratory environment, a security briefing is necessary. For the course, two stages were implemented; firstly the use of harmful substances and dangerous equipment was minimised, and secondly children were equipped with size-matched personal protective equipment (lab coats, gloves, and safety googles). The purification of elements prior to isotopic analysis was visualised using colour chromatography. However, instead of using delicate mass spectrometers for the isotope ratio measurements, the pupils applied flame spectroscopy to analyse their dissolved and purified mineral solutions. Depending on the specific element present, a different colour was observed in the flame. The children plotted their colours of the flame spectroscopy onto a map and by interpreting the emerging colour patterns they localized the treasure on the map. In small teams they swarmed out on the Telegrafenberg to recover the hidden treasure. The project leading to this outreach activity has received funding from the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme FP7/2007-2013/ under REA grant agreement n° [608069].

Nd Isotope and U-Th-Pb Age Mapping of Single Monazite Grains by Laser Ablation Split Stream Analysis

NASA Astrophysics Data System (ADS)

Fisher, C. M.; Hanchar, J. M.; Miller, C. F.; Phillips, S.; Vervoort, J. D.; Martin, W.

2015-12-01

Monazite is a common accessory mineral that occurs in medium to high grade metamorphic and Ca-poor felsic igneous rocks, and often controls the LREE budget (including Sm and Nd) of the host rock in which it crystallizes. Moreover, it contains appreciable U and Th, making it an ideal mineral for determining U-Th-Pb ages and Sm-Nd isotopic compositions, both of which are readily determined using in situ techniques with very high spatial resolution like LA-MC-ICPMS. Here, we present the results of laser ablation split stream analyses (LASS), which allows for simultaneous determination of the age and initial Nd isotopic composition in a single analysis. Analyses were done using a 20mm laser spot that allowed for detailed Nd isotope mapping of monazite grains (~30 analyses per ~250mm sized grain). Combined with LREE ratios (e.g., Sm/Nd, Ce/Gd, and Eu anomalies) these results yield important petrogenetic constraints on the evolution of peraluminous granites from the Old Woman-Piute batholith in southeastern California. Our findings also allow an improved understanding of the causes of isotope heterogeneity in granitic rocks. U-Th-Pb age mapping across the crystals reveals a single Cretaceous age for all grains with precision and accuracy typical of laser ablation analyses (~2%). In contrast, the concurrent Nd isotope mapping yields homogeneous initial Nd isotope compositions for some grains and large initial intra-grain variations of up to 8 epsilon units in others. The grains that yield homogeneous Nd isotope compositions have REE ratios suggesting that they crystallized in a fractionally crystallizing magma. Conversely, other grains, which also record fractional crystallization of both feldspar and LREE rich minerals, demonstrate a change in the Nd isotope composition of the magma during crystallization of monazite. Comparison of inter- and intra-grain Nd isotope compositions reveals further details on the potential mechanisms responsible for isotope heterogeneity present in single rock samples. This method highlights the potential of single grain isotope mapping of LREE phases such as monazite, allanite, and titanite for understanding both igneous and metamorphic petrogenesis.

Medical Isotope Production Analyses In KIPT Neutron Source Facility

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

Talamo, Alberto; Gohar, Yousry

Medical isotope production analyses in Kharkov Institute of Physics and Technology (KIPT) neutron source facility were performed to include the details of the irradiation cassette and the self-shielding effect. An updated detailed model of the facility was used for the analyses. The facility consists of an accelerator-driven system (ADS), which has a subcritical assembly using low-enriched uranium fuel elements with a beryllium-graphite reflector. The beryllium assemblies of the reflector have the same outer geometry as the fuel elements, which permits loading the subcritical assembly with different number of fuel elements without impacting the reflector performance. The subcritical assembly is drivenmore » by an external neutron source generated from the interaction of 100-kW electron beam with a tungsten target. The facility construction was completed at the end of 2015, and it is planned to start the operation during the year of 2016. It is the first ADS in the world, which has a coolant system for removing the generated fission power. Argonne National Laboratory has developed the design concept and performed extensive design analyses for the facility including its utilization for the production of different radioactive medical isotopes. 99Mo is the parent isotope of 99mTc, which is the most commonly used medical radioactive isotope. Detailed analyses were performed to define the optimal sample irradiation location and the generated activity, for several radioactive medical isotopes, as a function of the irradiation time.« less

High Precision Oxygen Three Isotope Analysis of Wild-2 Particles and Anhydrous Chondritic Interplanetary Dust Particles

NASA Technical Reports Server (NTRS)

Nakashima, D.; Ushikubo, T.; Zolensky, Michael E.; Weisberg, M. K.; Joswiak, D. J.; Brownlee, D. E.; Matrajt, G.; Kita, N. T.

2011-01-01

One of the most important discoveries from comet Wild-2 samples was observation of crystalline silicate particles that resemble chondrules and CAIs in carbonaceous chondrites. Previous oxygen isotope analyses of crystalline silicate terminal particles showed heterogeneous oxygen isotope ratios with delta(sup 18)O to approx. delta(sup 17)O down to -50% in the CAI-like particle Inti, a relict olivine grain in Gozen-sama, and an olivine particle. However, many Wild-2 particles as well as ferromagnesian silicates in anhydrous interplanetary dust particles (IDPs) showed Delta(sup 17)O values that cluster around -2%. In carbonaceous chondrites, chondrules seem to show two major isotope reservoirs with Delta(sup 17)O values at -5% and -2%. It was suggested that the Delta(sup 17)O = -2% is the common oxygen isotope reservoir for carbonaceous chondrite chondrules and cometary dust, from the outer asteroid belt to the Kuiper belt region. However, a larger dataset with high precision isotope analyses (+/-1-2%) is still needed to resolve the similarities or distinctions among Wild-2 particles, IDPs and chondrules in meteorites. We have made signifi-cant efforts to establish routine analyses of small particles (< or =10micronsm) at 1-2% precision using IMS-1280 at WiscSIMS laboratory. Here we report new results of high precision oxygen isotope analyses of Wild-2 particles and anhydrous chondritic IDPs, and discuss the relationship between the cometary dust and carbonaceous chondrite chondrules.

Refined Proterozoic evolution of the Gawler Craton, South Australia, through U-Pb zircon geochronology

USGS Publications Warehouse

Fanning, C.M.; Flint, R.B.; Parker, A.J.; Ludwig, K. R.; Blissett, A.H.

1988-01-01

Through the application of both conventional U-Pb zircon analyses and small-sample U-Pb isotopic analyses, the nature and timing of tectonic events leading to the formation of the Gawler Craton have been defined more precisely. Constraints on deposition of Early Proterozoic iron formation-bearing sediments have been narrowed down to the period 1960-1847 Ma. Deformed acid volcanics, including the economically important Moonta Porphyry, have zircon ages of ??? 1790 and 1740 Ma. The voluminous acid Gawler Range Volcanics and correlatives to the east were erupted over a short interval at 1592 ?? 2 Ma, and were intruded by anorogenic granites at ??? 1575 Ma. Small-sample zircon analyses proved to be an extremely valuable adjunct to conventional analyses, generally yielding more-concordant data which forced a curved discordia through an upper intercept slightly younger than from a conventional straight-line discordia. ?? 1988.

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

NASA Astrophysics Data System (ADS)

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

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

Isotope-ratio measurements of lead in NIST standard reference materials by multiple-collector inductively coupled plasma mass spectrometry.

PubMed

Platzner, I; Ehrlich, S; Halicz, L

2001-07-01

The capability of a second-generation Nu Instruments multiple collector inductively coupled plasma mass spectrometer (MC-ICP-MS) has been evaluated for precise and accurate isotope-ratio determinations of lead. Essentially the mass spectrometer is a double-focusing instrument of Nier-Johnson analyzer geometry equipped with a newly designed variable-dispersion ion optical device, enabling the measured ion beams to be focused into a fixed array of Faraday collectors and an ion-counting assembly. NIST SRM Pb 981, 982, and 983 isotopic standards were used. Addition of thallium to the lead standards and subsequent simultaneous measurement of the thallium and lead isotopes enabled correction for mass discrimination, by use of the exponential correction law and 205Tl/203Tl = 2.3875. Six measurements of SRM Pb-982 furnished the results 206Pb/204Pb = 36.7326(68), 207Pb/204Pb = 17.1543(30), 208Pb/204Pb = 36.7249(69), 207Pb/206Pb = 0.46700(1), and 208Pb/206Pb = 0.99979(2); the NIST-certified values were 36.738(37), 17.159(25), 36.744(50), 0.46707(20), and 1.00016(36), respectively. Direct isotope lead analysis in silicates can be performed without any chemical separation. NIST SRM 610 glass was dissolved and introduced into the MC-ICP-MS by means of a micro concentric nebulizer. The ratios observed were in excellent agreement with previously reported data obtained by TIMS and laser ablation MC-ICP-MS, despite the high Ca/Pb concentration ratio (200/1) and the presence of many other elements at levels comparable with that of lead. Approximately 0.2 microg lead are sufficient for isotope analysis with ratio uncertainties between 240 and 530 ppm.

Lead isotope evolution across the Neoproterozoic boundary between craton and juvenile crust, Bayuda Desert, Sudan

NASA Astrophysics Data System (ADS)

Evuk, David; Lucassen, Friedrich; Franz, Gerhard

2017-11-01

Metaigneous mafic and ultramafic rocks from the juvenile Neoproterozoic Arabian Nubian Shield (ANS) and the Proterozoic, reworked Saharan Metacraton (SMC) have been analysed for major- and trace elements and Sr, Nd, and Pb isotopes. Most of the rocks are amphibolites metamorphosed at amphibolite facies conditions, some with relicts of a granulite facies stage. The other rocks are metapyroxenites, metagabbros, and some ultramafic rocks. Trace element compositions of the metabasaltic (dominantly tholeiitic) rocks resemble the patterns of island arcs and primitive lavas from continental arcs. Variable Sr and Nd isotope ratios indicate depleted mantle dominance for most of the samples. 207Pb/204Pb signatures distinguish between the influence of high 207Pb/204Pb old SMC crust and depleted mantle signatures of the juvenile ANS crust. The Pb isotope signatures for most metabasaltic rocks, metapyroxenites and metagabbros from SMC indicate an autochthonous formation. The interpretation of the new data together with published evidence from mafic xenoliths on SMC and ophiolite from ANS allows an extrapolation of mantle evolution in time. There are two lines of evolution in the regional mantle, one, which incorporates potential upper crust material during Neoproterozoic, and a second one with a depleted mantle signature since pre-Neoproterozoic that still is present in the Red Sea and Gulf of Aden spreading centres.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Modelling stable water isotopes during "high-precipitation" events at Dome C, Antarctica

NASA Astrophysics Data System (ADS)

Schlosser, Elisabeth; Masson-Delmotte, Valérie; Risi, Camille; Stenni, Barbara; Valt, Mauro; Powers, Jordan G.; Manning, Kevin W.; Duda, Michael G.; Cagnati, Anselmo

2014-05-01

For a correct paleoclimatologic interpretation of stable water isotopes from ice cores both pre- and post-depositional processes and their role for isotope fractionation have to be better understood. Our study focusses on "pre-depositional processes", namely the atmospheric processes that determine moisture transport and precipitation formation. At the deep ice core drilling site "Dome C", East Antarctica, fresh snow samples have been taken since 2006. These samples have been analysed crystallographically, which enables us to clearly distinguish between blowing snow, diamond dust, and "synoptic precipitation". Also the stable oxygen/hydrogen isotope ratios of the snow samples were measured, including measurements of 17-O. This is the first and only multi-year fresh-snow data series from an Antarctic deep drilling site. The Antarctic Mesoscale Prediction System (AMPS) employs Polar WRF for aviation weather forecasts in Antarctica. The data are archived and can be used for scientific purposes. The mesoscale atmospheric model was adapted especially for polar regions. The horizontal resolution for the domain that covers the Antarctic continent is 10 km. It was shown that precipitation at Dome C is temporally dominated by diamond dust. However, comparatively large amounts of precipitation are observed during several "high-precipitation" events per year, caused by synoptic activity in the circumpolar trough and related advection of relatively warm and moist air from lower latitudes to the interior of Antarctica. AMPS archive data are used to investigate the synoptic situations that lead to "high-precipitation" events at Dome C; in particular, possible moisture sources are determined using back-trajectories. With this meteorological information, the isotope ratios are calculated using two different isotope models, the Mixed Cloud Isotope Model, a simple Rayleigh-type model, and the LMDZ-iso (Laboratoire de Météorologie Dynamic Zoom), a General Circulation Model (GCM) with implementation of stable isotopes. The results are compared to the measured stable isotope ratios of the fresh snow samples.

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

NASA Astrophysics Data System (ADS)

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

2003-04-01

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

Preliminary mineralogic, fluid inclusion, and stable isotope study of the Mahd adh Dhahab gold mine, Kingdom of Saudi Arabia

USGS Publications Warehouse

Rye, Robert O.; Hall, W.E.; Cunningham, C.G.; Czamanske, G.K.; Afifi, A.M.; Stacey, J.S.

1983-01-01

The Mahd adh Dhahab mine, located about 280 km northeast of Jiddah, Kingdom of Saudi Arabia, has yielded more than 2 million ounces of gold from periodic production during the past 3,000 years. A new orebody on the southern side of the ancient workings, known as the South orebody, is being developed by Gold Fields-Mahd adh Dhahab Limited. A suite of samples was collected from the newly exposed orebody for preliminary mineralogic, stable isotope, fluid inclusion, and geochemical studies. The Mahd adh Dhahab deposit is in the carapace of a Proterozoic epizonal rhyolite stock that domed pyroclastic and metasedimentary rocks of the Proterozoic Halaban group. Ore of gold, silver, copper, zinc, tellurium, and lead is associated with north-trending, steeply dipping quartz veins in a zone 1,000 m long and 400 m wide. The veins include an assemblage of quartz-chlorite-pyrite-hematite-chalcopyrite-sphalerite-precious metals, which is similar to the mineral assemblage at the epithermal deposit at Creede, Colorado. The primary ore contains abundant chalcopyrite, sphalerite, and pyrite in addition to a complex precious metal assemblage. Gold and silver occur principally as minute grains of telluride minerals disseminated in quartz-chlorite-hematite and as inclusions in chalcopyrite and sphalerite. Telluride minerals include petzite, hessite, and sylvanite. Free gold is present but not abundant. All of the vein-quartz samples contained abundant, minute inclusions of both low-density, vapor-rich fluids and liquid-rich fluids. Primary fluid inclusions yielded homogenization temperatures of from 110? to 238? C. Preliminary light-stable isotope studies of the sulfide minerals and quartz showed that all of the d34S values are between 1.2 and 6.3 per mil, which is a typical range for hydrothermal sulfide minerals that derive their sulfur from an igneous source. The data-suggest that the sulfide sulfur isotope geochemistry was controlled by exchange with la large sulfur isotope reservoir at depth. The d18O values of all stages of vein quartz in the South orebody range between 8.5 and 11.1 per mil. This range is similar to that for quartz from the North orebody and indicates that the hydrothermal system consisted of dominantly exchanged meteoric water, which was uniform in temperature and d18O content throughout the area during the entire period of mineralization. Lead isotope analyses of two galena samples indicate that the lead in the South orebody is less radiogenic than that from the North orebody and confirm that the lead was derived from oceanic crust approximately 700 Ma ago.

Lead concentrations and isotope ratios in street dust determined by electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry.

PubMed

Nageotte, S M; Day, J P

1998-01-01

A major source of environmental lead, particularly in urban areas, has been from the combustion of leaded petrol. Street dust has previously been used to assess urban lead contamination, and the dust itself can also be a potential source of lead ingestion, particularly to children. The progressive reduction of lead in petrol, in recent years, would be expected to have been reflected in a reduction of lead in urban dust. We have tested this hypothesis by repeating an earlier survey of Manchester street dust and carrying out a comparable survey in Paris. Samples were collected from streets and parks, lead was extracted by digestion with concentrated nitric acid and determined by electrothermal atomic absorption spectrometry. Lead isotope ratios were measured by inductively coupled plasma mass spectrometry. Results for Manchester show that lead concentrations have fallen by about 40% (street dust averages, 941 micrograms g-1 (ppm) in 1975 down to 569 ppm in 1997). In Paris, the lead levels in street dust are much higher and significant differences were observed between types of street (not seen in Manchester). Additionally, lead levels in parks were much lower than in Manchester. Samples collected under the Eiffel Tower had very high concentrations and lead isotope ratios showed that this was unlikely to be fallout from motor vehicles but could be due to the paint used on the tower. Isotope ratios measurements also revealed that lead additives used in France and the UK come from different sources.

Microscopic model for the isotope effect in the high-Tc oxides

NASA Astrophysics Data System (ADS)

Kresin, V. Z.; Wolf, S. A.

1994-02-01

An unconventional microscopic mechanism relating Tc and the isotope substitution for the doped superconductors such as the high-Tc oxides is proposed. Strong nonadiabaticity, when it is impossible, strictly speaking, to separate fully the nuclear and electronic degrees of freedom, leads to a peculiar dependence of the carrier concentration n on the ionic mass M. This case corresponds, for example, to the isotopic substitution of the axial oxygen in YBa2Cu3O7-x. Because of the dependence of Tc on n, this leads to the dependence of Tc on M, that is to the isotope effect. The minimum value of the isotope coefficient corresponds to Tc=Tmaxc.

Lead isotopic compositions of soil and near-surface till profiles from a watershed containing arsenic-enriched groundwater in coastal Maine

USGS Publications Warehouse

Ayuso, Robert; Foley, Nora; Wandless, Gregory; Dillingham, Jeremy; Colvin, Anna

2005-01-01

Lead isotope compositions of soils and near-surface tills from an area of coastal Maine known to have groundwater with anomalously high arsenic contents were measured in order to determine the source of the lead and, by inference, possible sources of arsenic. Five soil and till sites were selected for detailed chemical and isotopic analysis. To construct profiles of the soil and till horizons, five samples were collected at 10-cm intervals from the surface to the base of each horizon. Total lead and arsenic concentrations and lead isotopic compositions were measured for 48 leaches and bulk residues. The soils and tills are underlain by sulfidic schists of the Penobscot Formation. Several generations of minerals containing arsenic and lead exist in the regional bedrock, including rock-forming silicates (feldspar and micas), sulfide minerals formed during diagenesis (for example, arsenic-rich pyrite), and sulfide and oxide minerals that formed as a result of Silurian metamorphic and igneous events (for example, arsenopyrite, galena, iron-oxides, and arsenic-sulfides). A young group of secondary minerals (for example, iron-hydroxides, arsenic-hydroxides, lead-sulfate, and arsenic-jarosite) formed from recent weathering and pedogenic processes.

Perchlorate isotope forensics

USGS Publications Warehouse

Böhlke, J.K.; Sturchio, N.C.; Gu, B.; Horita, J.; Brown, G.M.; Jackson, W.A.; Batista, J.; Hatzinger, P.B.

2005-01-01

Perchlorate has been detected recently in a variety of soils, waters, plants, and food products at levels that may be detrimental to human health. These discoveries have generated considerable interest in perchlorate source identification. In this study, comprehensive stable isotope analyses ( 37Cl/35Cl and 18O/17O/ 16O) of perchlorate from known synthetic and natural sources reveal systematic differences in isotopic characteristics that are related to the formation mechanisms. In addition, isotopic analyses of perchlorate extracted from groundwater and surface water demonstrate the feasibility of identifying perchlorate sources in contaminated environments on the basis of this technique. Both natural and synthetic sources of perchlorate have been identified in water samples from some perchlorate occurrences in the United States by the isotopic method. ?? 2005 American Chemical Society.

MIXING MODELS IN ANALYSES OF DIET USING MULTIPLE STABLE ISOTOPES: A CRITIQUE

EPA Science Inventory

Stable isotopes have become widely used in ecology to quantify the importance of different sources based on their isotopic signature. One example of this has been the determination of food webs, where the isotopic signatures of a predator and various prey items can be used to de...

Stable isotope analyses reveal the importance of seagrass beds as feeding areas for juvenile Myrophis punctatus (Angulliformes: Ophichthidae) inthe coastal waters of Florida

EPA Science Inventory

The feeding habits and habitats of the speckled worm eel Myrophis punctatus were studied on the mangrove edge of the Indian River Lagoon (Florida) using stomach contents and stable isotope analyses of carbon (δ13C) and nitrogen (δ15N). Stomach dietary analyses identified four tax...

Determination of tin isotope ratios in cassiterite by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Schulze, Marie; Ziegerick, Marco; Horn, Ingo; Weyer, Stefan; Vogt, Carla

2017-04-01

In comparison to isotope analysis of dissolved samples femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS) enables precise isotope ratio analyses consuming much less sample material and with a minimum effort in sample preparation. This is especially important for the investigation of valuable historical objects for which visual traces of sampling are unwanted. The present study provides a basis for tin isotope ratio measurements using LA-MC-ICP-MS technique. For this, in house isotope standards had to be defined. Investigations on interferences and matrix effects illustrate that beside Sb only high Te contents (with values above those to be expected in cassiterite) result in a significant shift of the measured tin isotope ratios. This effect can partly be corrected for using natural isotope abundances. However, a natural isotope fractionation of Te cannot be excluded. Tin beads reduced from cassiterite were analysed by laser ablation and after dissolution. It was shown that tin isotope ratios can be determined accurately by using fs-LA-MC-ICP-MS. Furthermore the homogeneity of tin isotope ratios in cassiterite was proven.

Levels and source apportionment of children's lead exposure: could urinary lead be used to identify the levels and sources of children's lead pollution?

PubMed

Cao, Suzhen; Duan, Xiaoli; Zhao, Xiuge; Wang, Beibei; Ma, Jin; Fan, Delong; Sun, Chengye; He, Bin; Wei, Fusheng; Jiang, Guibin

2015-04-01

As a highly toxic heavy metal, the pollution and exposure risks of lead are of widespread concern for human health. However, the collection of blood samples for use as an indicator of lead pollution is not always feasible in most cohort or longitudinal studies, especially those involving children health. To evaluate the potential use of urinary lead as an indicator of exposure levels and source apportionment, accompanying with environmental media samples, lead concentrations and isotopic measurements (expressed as (207)Pb/(206)Pb, (208)Pb/(206)Pb and (204)Pb/(206)Pb) were investigated and compared between blood and urine from children living in the vicinities of a typical coking plant and lead-acid battery factory. The results showed urinary lead might not be a preferable proxy for estimating blood lead levels. Fortunately, urinary lead isotopic measurements could be used as an alternative for identifying the sources of children's lead exposure, which coincided well with the blood lead isotope ratio analysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

ISOTOPIC COMPOSITION OF THE COMMON LEAD OF JAPAN

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

Sakai, H.; Sato, K.

1958-11-01

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

Stable Isotope Analyses of Phosphate Oxygen From Micro-samples of Biological Apatite: A new Routine Procedure for Silverphosphate Micro-precipitation and the Removal of Organic Contamination

NASA Astrophysics Data System (ADS)

Wiedemann-Bidlack, F. B.; Colman, A. S.; Fogel, M. L.

2003-12-01

Oxygen isotope analyses in bone and teeth of living and fossil animals are widely used for testing hypotheses about variability of diet and habitat. For the analysis of environmental or dietary changes in the past, tooth enamel has become the preferred study material, because its mineral content is higher than bone and dentine, and the relatively large size of the carbonato-apatite crystals of enamel make it more stable against post mortem diagenetic alteration than dentine or bone. Intra-tooth sampling of dental enamel is increasingly used for the investigation of seasonal climate variability, taking advantage of both the high correlation between an animal's drinking water and the δ 18O in its mineralized tissues and the incremental growth pattern of tooth enamel. The different oxygen-containing ions of bioapatite (phosphate, carbonate, and hydroxyl group) incorporate into the mineral lattice at different rates during enamel mineralization, and differ in their susceptibility against post mortem diagenetic alteration. In addition, it is difficult to account for the different reaction chemistries of phosphate, carbonate, and hydroxyl group using isotope analysis techniques that include all oxygen contained in the enamel (e.g., laser ablation). These problems can be addressed analyzing phosphate oxygen only. However, two major factors limit the potential of δ 18O analyses in dental enamel: A) the starting sample size for isotope analyzes often precludes the use of small teeth or the intra-tooth sampling of a given tooth; B) Small amounts of biogenic organic material in tooth enamel (less than 1% by wt) can reduce the precision and lead to anomalous analytical results in δ 18O measurements on Ag3PO4 produced from tooth enamel. A new procedure was developed for the pre-treatment and δ 18O analysis of phosphate from small samples (500 μ g) of tooth enamel containing organic matter. Ag3PO{4} was precipitated quantitatively for analysis of δ 18Ophosphate using a Thermoquest-Finnigan TC/EA coupled to Delta Plus XL. A sodium hypochlorite sample pre-treatment step was determined to remove organic matter quantitatively without altering the isotopic composition of the phosphate oxygen. The reproducibility of δ 18O values for pretreated samples (0.2-0.3 ‰ , 1σ ) is much better than for samples without pre-treatment (1.2 ‰ , 1σ ). Phosphate oxygen isotope standards processed using this technique gave measured values indistinguishable from the standard composition, demonstrating the accuracy of the new technique.

Lead mobilization during tectonic reactivation of the western Baltic Shield

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

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

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

Cs-Ba separation using N 2O as a reactant gas in a Multiple Collector-Inductively Coupled Plasma Mass Spectrometer collision-reaction cell: Application to the measurements of Cs isotopes in spent nuclear fuel samples

NASA Astrophysics Data System (ADS)

Granet, M.; Nonell, A.; Favre, G.; Chartier, F.; Isnard, H.; Moureau, J.; Caussignac, C.; Tran, B.

2008-11-01

In the general frameworks of the nuclear fuel cycle and environmental research field, the Cs isotopic composition must be known with high precision and accuracy. The direct determination of Cs isotopes by mass spectrometry techniques is generally hampered by the presence of Ba isobaric interferences however. Here we present a new method which takes advantage of the collision-reaction cell based Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) and allows to analyse Cs isotopes in the presence of Ba without prior separation step. The addition of N 2O gas in the cell leads to an antagonistic behavior of Cs + and Ba + as the latter reacts with the gas to form BaO + and BaOH + products whereas Cs + remains unreactive. The efficiency of the method was demonstrated for an UOx sample by comparing the results obtained (1) from the measurements of pure Cs fractions and (2) from Fission Products fractions containing more than 30 ionisable elements in addition to Cs, Ba, and where U and Pu were previously removed by using ion exchange resin. An excellent agreement is achieved between each set of experiments with an external reproducibility always better than 0.5% (RSD, k = 2). This study confirms the strong potential of collision-reaction cell to measure Cs isotopes in presence of interfering Ba, precluding therefore former systematic chemical separations.

Lead isotopic compositions of common arsenical pesticides used in New England

USGS Publications Warehouse

Ayuso, Robert; Foley, Nora; Robinson, Gilpin; Wandless, Gregory; Dillingham, Jeremy

2004-01-01

The three most important arsenical pesticides and herbicides that were extensively used on apple, blueberry, and potato crops in New England from mid-1800s to recent times are lead arsenate, calcium arsenate, and sodium arsenate. Lead arsenate was probably the most heavily used of the arsenical pesticides until it was banned in 1988. Other metal-arsenic pesticides were also used but in lesser amounts. A recent report identified areas in New England where arsenical pesticides were used extensively (Robinson and Ayuso, 2004). On the basis of factor analysis of metal concentrations in stream sediment samples, a positive correlation with pesticide use was shown in regions having stream sediment sample populations that contained concentrations of high arsenic and lead. Lead isotope compositions of stream sediments from areas with heavy use of the pesticides could not be entirely explained by lead originating from rock sulfides and their weathering products. An industrial lead contribution (mostly from atmospheric deposition of lead) was suggested in general to explain the lead isotopic distributions of the stream sediments that could not be accounted for by the natural lead in the environment. We concluded that when agricultural land previously contaminated with arsenical pesticides is urbanized, pesticide residues in the soils and stream sediments could be released into the groundwater. No lead isotopic data characterizing the compositions of pesticides were available for comparison. We have determined the lead isotopic compositions of commonly used pesticides in New England, such as lead arsenate, sodium metaarsenite, and calcium arsenate, in order to assist in future isotopic comparisons and to better establish anthropogenic sources of Pb and As. New data are also presented for copper acetoarsenite (or Paris green), methyl arsonic acid and methane arsonic acid, as well as for arsanilic acid, all of which are used as feed additives to promote swine and poultry growth. The new data characterize these anthropogenic sources. The data show that the arsenical pesticides have similar compositions: 208Pb/207Pb = 2.3839-2.4721, 206Pb/207Pb = 1.1035-1.2010, and 206Pb/204Pb = 17.070-18.759 and, more importantly, that the pesticides overlap the composition of the stream sediments that represent the areas with the most extensive agricultural use. Copper acetoarsenite (Paris green), arsenic oxide, methyl arsonic acid, methane arsonic acid, and arsanilic acid were also analyzed and have lead isotope compositions that range widely. An important source of arsenic and metals to most of the stream sediment samples in New England appears to be weathering products from rocks and industrial lead, but the extensive use of arsenical pesticides and herbicides up to about the 1960s can also be a significant anthropogenic source in agricultural regions.

Identifying microbial carbon sources during ethanol and toluene biodegradation in a pilot-scale experimental aquifer system using isotopic analysis

NASA Astrophysics Data System (ADS)

Clay, S.; McLeod, H.; Smith, J. E.; Roy, J. W.; Slater, G. F.

2013-12-01

Combining ethanol with gasoline has become increasingly common in order to create more environmentally conscience transportation fuels. These blended fuels are favourable alternatives since ethanol is a non-toxic and highly labile renewable biomass-based resource which is an effective fuel oxygenate that reduces air pollution. Recent research however, has indicated that upon accidental release into groundwater systems, the preferential microbial metabolism of ethanol can cause progressively reducing conditions leading to slower biodegradation of petroleum hydrocarbons. Therefore, the presence of ethanol can result in greater persistence of BTEX compounds and longer hydrocarbon plumes in groundwater systems. Microbial biodegradation and community carbon sources coupled to aqueous geochemistry were monitored in a pilot-scale laboratory tank (80cm x 525cm x 175cm) simulating an unconfined sand aquifer. Dissolved ethanol and toluene were continuously injected into the aquifer at a controlled rate over 330 days. Carbon isotope analyses were performed on phospholipid fatty acid (PLFA) samples collected from 4 different locations along the aquifer. Initial stable carbon isotope values measured over days 160-185 in the bacterial PLFA ranged from δ13C = -10 to -21‰, which is indicative of dominant ethanol incorporation by the micro-organisms based on the isotopic signature of ethanol derived from corn, a C4 plant. A negative shift to δ13C = -10 to -30‰ observed over days 185-200, suggests a change in microbial metabolisms associated with less ethanol incorporation. This generally corresponds to a decrease in ethanol concentrations from day 40 to full attenuation at approximately day 160, and the onset of toluene depletion observed on day 120 and continuing thereafter. In addition, aqueous methane concentrations first detected on day 115 continued to rise to 0.38-0.70 mmol/L at all monitoring locations, demonstrating a significant redox shift to low energy methanogenic metabolisms. On-going archaeal lipid analyses are expected to capture the establishment of methanogenic communities and provide insight into carbon use by these communities. Furthermore, radiocarbon analysis will aid in tracking the biodegradation of ethanol and toluene. Ultimately this research aims to illustrate the preferential biodegradation of ethanol in a gasoline mixture, and identify the carbon sources utilized by an evolving microbial community using isotopic analyses to improve assessments and remediation strategies at sites contaminated with ethanol-blended fuels.

Direct lead isotope analysis in Hg-rich sulfides by LA-MC-ICP-MS with a gas exchange device and matrix-matched calibration.

PubMed

Zhang, Wen; Hu, Zhaochu; Günther, Detlef; Liu, Yongsheng; Ling, Wenli; Zong, Keqing; Chen, Haihong; Gao, Shan

2016-12-15

In situ Pb isotope data of sulfide samples measured by LA-MC-ICP-MS provide valuable geochemical information for studies of the origin and evolution of ore deposits. However, the severe isobaric interference of 204 Hg on 204 Pb and the lack of matrix-matched sulfide reference materials limit the precision of Pb isotopic analyses for Hg-rich sulfides. In this study, we observe that Hg forms vapor and can be completely removed from sample aerosol particles produced by laser ablation using a gas exchange device. Additionally, this device does not influence the signal intensities of Pb isotopes. The within-run precision, the external reproducibility and the analytical accuracy are significantly improved for the Hg-rich sulfide samples using this mercury-vapor-removing device. Matrix effects are observed when using silicate glass reference materials as the external standards to assess the relationship of mass fractionation factors between Tl and Pb in sulfide samples, resulting in a maximum deviation of ∼0.20% for 20x Pb/ 204 Pb. Matrix-matched reference materials are therefore required for the highly precise and accurate Pb isotope analyses of sulfide samples. We investigated two sulfide samples, MASS-1 (the Unites States Geological Survey reference materials) and Sph-HYLM (a natural sphalerite), as potential candidates. Repeated analyses of the two proposed sulfide reference materials by LA-MC-ICP-MS yield good external reproducibility of <0.04% (RSD, k = 2) for 20x Pb/ 206 Pb and <0.06% (RSD, k = 2) for 20x Pb/ 204 Pb with the exception of 20x Pb/ 204 Pb in MASS-1, which provided an external reproducibility of 0.24% (RSD, k = 2). Because the concentration of Pb in MASS-1 (76 μg g -1 ) is ∼5.2 times lower than that in Sph-HYLM (394 ± 264 μg g -1 ). The in situ analytical results of MASS-1 and Sph-HYLM are consistent with the values obtained by solution MC-ICP-MS, demonstrating the reliability and robustness of our analytical protocol. Copyright © 2016 Elsevier B.V. All rights reserved.

Gas and hydrogen isotopic analyses of volcanic eruption clouds in Guatemala sampled by aircraft

USGS Publications Warehouse

Rose, W.I.; Cadle, R.D.; Heidt, L.E.; Friedman, I.; Lazrus, A.L.; Huebert, B.J.

1980-01-01

Gas samples were collected by aircraft entering volcanic eruption clouds of three Guatemalan volcanoes. Gas chromatographic analyses show higher H2 and S gas contents in ash eruption clouds and lower H2 and S gases in vaporous gas plumes. H isotopic data demonstrate lighter isotopic distribution of water vapor in ash eruption clouds than in vaporous gas plumes. Most of the H2O in the vaporous plumes is probably meteoric. The data are the first direct gas analyses of explosive eruptive clouds, and demonstrate that, in spite of atmospheric admixture, useful compositional information on eruptive gases can be obtained using aircraft. ?? 1980.

Assessing the sources and bioaccessibility of Lead in Soils from London

NASA Astrophysics Data System (ADS)

Cave, Mark R.; Wragg, Joanna; Chenery, Simon

2013-04-01

The lead content of soil is important since it is toxic to humans and particularly because children tend to more readily absorb lead than do adults: children absorb up to 40% into the bloodstream from ingested or inhaled lead, versus 5-15% in adults. Studies have shown that relatively low concentrations of lead in blood can lead to significant decrease in IQ of children (e.g. Jakubowski, 2011) leading to neuropathy and hypertension in adults. The British Geological Survey has recently completed a systematic high-density geochemical soil survey of the Greater London Area (GLA) in which over 6000 surface soil samples were collected and analysed for 50 elements. The Pb content of the soils range from 11 mg/kg to greater than 10000 mg/kg with mean and median values of 301 and 185 mg/kg, respectively. The ingestion bioaccessible fraction of Pb was measured using an in-vitro bioaccessibility test showing that 68% of the total Pb in London soils is bioaccessible. Measurement of Pb isotopic ratios in selected soils matched with those found in London air particulates and, to a lesser extent, with petrol lead. Self modelling mixture resolution of the 50 element geochemical data set was used to identify geochemically distinct components in the data with Pb being associated with 11 of the components which were of both natural and anthropogenic origin. Relationships between the soil components, the bioaccessible fraction and the Pb isotope ratios provided an indication of the sources of mobile lead in the London soils. References JAKUBOWSKI, M. 2011. Low-level environmental lead exposure and intellectual impairment in children - the current concepts of risk assessment. International Journal of Occupational Medicine and Environmental Health, Vol. 24, 1-7. APPLETON, J D, CAVE, M R, and WRAGG, J. 2012. Modelling lead bioaccessibility in urban topsoils based on data from Glasgow, London, Northampton and Swansea, UK. Environmental Pollution, Vol. 171, 265-272.

Profiling of new psychoactive substances (NPS) by using stable isotope ratio mass spectrometry (IRMS): study on the synthetic cannabinoid 5F-PB-22.

PubMed

Münster-Müller, S; Scheid, N; Holdermann, T; Schneiders, S; Pütz, M

2018-05-21

In this paper results of a pilot study on the profiling of the synthetic cannabinoid receptor agonist 5F-PB-22 (5F-QUPIC, pentylfluoro-1H-indole-3-carboxylic acid-8-quinolinyl ester) via isotope ratio mass spectrometry are presented. It is focused on δ 13 C, δ 15 N and δ 2 H isotope ratios, which are determined using elemental analyser (EA) and high temperature elemental analyser (TC/EA) coupled to an isotope ratio mass spectrometer (IRMS). By means of a sample of pure material of 5F-PB-22 it is shown that the extraction of 5F-PB-22 from herbal material, a rapid clean-up procedure, or preparative column chromatography had no influences on the isotope ratios. Furthermore, 5F-PB-22 was extracted from fourteen different herbal blend samples ("Spice products" from police seizures) and analysed via IRMS, yielding three clusters containing seven, five and two samples, distinguishable through their isotopic composition, respectively. It is assumed that herbal blends in each cluster have been manufactured from individual batches of 5F-PB-22. This article is protected by copyright. All rights reserved.

Isotopic and Chemical Evidence for Primitive Aqueous Alteration in the Tagish Lake Meteorite

NASA Astrophysics Data System (ADS)

Sakuma, Keisuke; Hidaka, Hiroshi; Yoneda, Shigekazu

2018-01-01

Aqueous alteration is one of the primitive activities that occurred on meteorite parent bodies in the early solar system. The Tagish Lake meteorite is known to show an intense parent body aqueous alteration signature. In this study, quantitative analyses of the alkaline elements and isotopic analyses of Sr and Ba from acid leachates of TL (C2-ungrouped) were performed to investigate effects of aqueous alteration. The main purpose of this study is to search for isotopic evidence of extinct 135Cs from the Ba isotopic analyses in the chemical separates from the Tagish Lake meteorite. Barium isotopic data from the leachates show variable 135Ba isotopic anomalies (ε = ‑2.6 ∼ +3.6) which correlatewith 137Ba and 138Ba suggesting a heterogeneous distribution of s- and r-rich nucleosynthetic components in the early solar system. The 87Rb–87Sr and 135Cs–135Ba decay systems on TL in this study do not provide any chronological information. The disturbance of the TL chronometers is likely a reflection of the selective dissolution of Cs and Rb given the relatively higher mobility of Cs and Rb compared to Ba and Sr, respectively, during fluid mineral interactions.

Validation of Electrochemically Modulated Separations Performed On-Line with MC-ICP-MS for Uranium and Plutonium Isotopic Analyses

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

Liezers, Martin; Olsen, Khris B.; Mitroshkov, Alexandre V.

2010-08-11

The most time consuming process in uranium or plutonium isotopic analyses is performing the requisite chromatographic separation of the actinides. Filament preparation for thermal ionization (TIMS) adds further delays, but is generally accepted due to the unmatched performance in trace isotopic analyses. Advances in Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) are beginning to rival the performance of TIMS. Methods, such as Electrochemically Modulated Separations (EMS) can efficiently pre-concentrate U or Pu quite selectively from small solution volumes in a matrix of 0.5 M nitric acid. When performed in-line with ICP-MS, the rapid analyte release from the electrode is fast,more » and large transient analyte signal enhancements of >100 fold can be achieved as compared to more conventional continuous nebulization of the original starting solution. This makes the approach ideal for very low level isotope ratio measurements. In this paper, some aspects of EMS performance are described. These include low level Pu isotope ratio behavior versus concentration by MC-ICP-MS and uranium rejection characteristics that are also important for reliable low level Pu isotope ratio determinations.« less

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

PubMed

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

2004-02-15

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

Lead Isotope Characterization of Petroleum Fuels in Taipei, Taiwan

PubMed Central

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

2015-01-01

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

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

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

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

2010-11-25

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

Tracing the dynamic life story of a Bronze Age Female

NASA Astrophysics Data System (ADS)

Margarita Frei, Karin; Mannering, Ulla; Kristiansen, Kristian; Allentoft, Morten E.; Wilson, Andrew S.; Skals, Irene; Tridico, Silvana; Louise Nosch, Marie; Willerslev, Eske; Clarke, Leon; Frei, Robert

2015-05-01

Ancient human mobility at the individual level is conventionally studied by the diverse application of suitable techniques (e.g. aDNA, radiogenic strontium isotopes, as well as oxygen and lead isotopes) to either hard and/or soft tissues. However, the limited preservation of coexisting hard and soft human tissues hampers the possibilities of investigating high-resolution diachronic mobility periods in the life of a single individual. Here, we present the results of a multidisciplinary study of an exceptionally well preserved circa 3.400-year old Danish Bronze Age female find, known as the Egtved Girl. We applied biomolecular, biochemical and geochemical analyses to reconstruct her mobility and diet. We demonstrate that she originated from a place outside present day Denmark (the island of Bornholm excluded), and that she travelled back and forth over large distances during the final months of her life, while consuming a terrestrial diet with intervals of reduced protein intake. We also provide evidence that all her garments were made of non-locally produced wool. Our study advocates the huge potential of combining biomolecular and biogeochemical provenance tracer analyses to hard and soft tissues of a single ancient individual for the reconstruction of high-resolution human mobility.

Tracing the dynamic life story of a Bronze Age Female

PubMed Central

Margarita Frei, Karin; Mannering, Ulla; Kristiansen, Kristian; Allentoft, Morten E.; Wilson, Andrew S.; Skals, Irene; Tridico, Silvana; Louise Nosch, Marie; Willerslev, Eske; Clarke, Leon; Frei, Robert

2015-01-01

Ancient human mobility at the individual level is conventionally studied by the diverse application of suitable techniques (e.g. aDNA, radiogenic strontium isotopes, as well as oxygen and lead isotopes) to either hard and/or soft tissues. However, the limited preservation of coexisting hard and soft human tissues hampers the possibilities of investigating high-resolution diachronic mobility periods in the life of a single individual. Here, we present the results of a multidisciplinary study of an exceptionally well preserved circa 3.400-year old Danish Bronze Age female find, known as the Egtved Girl. We applied biomolecular, biochemical and geochemical analyses to reconstruct her mobility and diet. We demonstrate that she originated from a place outside present day Denmark (the island of Bornholm excluded), and that she travelled back and forth over large distances during the final months of her life, while consuming a terrestrial diet with intervals of reduced protein intake. We also provide evidence that all her garments were made of non-locally produced wool. Our study advocates the huge potential of combining biomolecular and biogeochemical provenance tracer analyses to hard and soft tissues of a single ancient individual for the reconstruction of high-resolution human mobility. PMID:25994525

Discrete stages of core formation survive the Moon-forming impact

NASA Astrophysics Data System (ADS)

Jackson, C.; Bennett, N.; Du, Z.; Fei, Y.

2016-12-01

There is mounting evidence that Earth contains isotopic variations produced by short-lived systems, namely Hf-W and I-Xe. The lifetimes of these systems are 50 Ma and 80 Ma, respectively, requiring that chemical heterogeneities that were formed extremely early in solar system history and have survived within Earth's mantle to the modern day. The isotopic heterogeneity observed within Earth's mantle contrasts the isotopic similarity of bulk silicate Earth and bulk silicate Moon. This suggests the process(es) responsible for the isotopic variations within Earth predate the Moon-forming impact. Here, we focus on the potential role of core-formation in generating coupled isotopic variations associated with the Hf-W and I-Xe systems. We present metal-silicate partitioning data for W and I from experiments employing laser-heated diamond anvil cells. Experiments were conducted up to the pressure and temperature conditions directly relevant to core formation at GSECARS, APS. Samples were prepared using focused ion beam milling and analyzed by field emission electron microbeam techniques (EDS & WDS). These analyses demonstrate that W and I preferentially partition into the core under a wide range of conditions. In combination with literature data, this suggests that core formation left the residual mantle with an increased Hf/W ratio and a decreased I/Xe ratio. These parent-daughter fractionations lead to radiogenic W and unradiogenic Xe isotopic signatures compared to mantle that experienced the extraction of core material at a later date, on average. Relatively radiogenic W and unradiogenic Xe isotopic signatures are associated with plume rocks, potentially linking the plume source to mantle reservoirs that experienced early core extraction relative to the bulk mantle. Compositional variables, pressure, and temperature also affect the magnitude of Hf/W and I/Xe fractionation associated with core formation. The interplay of these variables will be evaluated alongside the timing of core formation in the context of generating short-lived isotopic variations associated with plume mantle.

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

PubMed

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

2014-12-02

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

Measuring 13 C-enriched CO2 in air with a cavity ring-down spectroscopy gas analyser: Evaluation and calibration.

PubMed

Dickinson, Dane; Bodé, Samuel; Boeckx, Pascal

2017-11-30

Cavity ring-down spectroscopy (CRDS) is becoming increasingly popular for δ 13 C-CO 2 analysis of air. However, little is known about the effect of high 13 C abundances on the performance of CRDS. Overlap between 12 CO 2 and 13 CO 2 spectral lines may adversely affect isotopic-CO 2 CRDS measurements of 13 C-enriched samples. Resolving this issue is important so that CRDS analysers can be used in CO 2 flux studies involving 13 C-labelled tracers. We tested a Picarro G2131-i CRDS isotopic-CO 2 gas analyser with specialty gravimetric standards of widely varying 13 C abundance (from natural to 20.1 atom%) and CO 2 mole fraction (xCO 2 : <0.1 to 2116 ppm) in synthetic air. The presence of spectroscopic interference between 12 CO 2 and 13 CO 2 bands was assessed by analysing errors in measurements of the standards. A multi-component calibration strategy was adopted, incorporating isotope ratio and mole fraction data to ensure accuracy and consistency in corrected values of δ 13 C-CO 2 , x 12 CO 2 , and x 13 CO 2 . CRDS measurements of x 13 CO 2 were found to be accurate throughout the tested range (<0.005 to 100 ppm). On the other hand, spectral cross-talk in x 12 CO 2 measurements of standards containing elevated levels of 13 CO 2 led to inaccuracy in x 12 CO 2 , total-xCO 2 (x 12 CO 2  + x 13 CO 2 ), and δ 13 C-CO 2 data. An empirical relationship for x 12 CO 2 measurements that incorporated the 13 C/ 12 C isotope ratio (i.e. 13 CO 2 / 12 CO 2 , RCO2) as a secondary (non-linear) variable was found to compensate for the perturbations, and enabled accurate instrument calibration for all CO 2 compositions covered by our standard gases. 13 C-enrichement in CO 2 leads to minor errors in CRDS measurements of x 12 CO 2 . We propose an empirical correction for measurements of 13 C-enriched CO 2 in air by CRDS instruments such as the Picarro G2131-i. Copyright © 2017 John Wiley & Sons, Ltd.

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

NASA Astrophysics Data System (ADS)

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

2014-07-01

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

Lead isotope systematics of some igneous rocks from the Egyptian Shield

NASA Technical Reports Server (NTRS)

Gillespie, J. G.; Dixon, T. H.

1983-01-01

Lead isotope data on whole-rock samples and two feldspar separates for a variety of Pan-African (late Precambrian) igneous rocks for the Egyptian Shield are presented. It is pointed out that the eastern desert of Egypt is a Late Precambrian shield characterized by the widespread occurrence of granitic plutons. The lead isotope ratios may be used to delineate boundaries between Late Precambrian oceanic and continental environments in northeastern Africa. The samples belong to three groups. These groups are related to a younger plutonic sequence of granites and adamellites, a plutonic group consisting of older tonalites to granodiorites, and the Dokhan volcanic suite.

Monitoring steel bridge renovation using lead isotopic tracing.

PubMed

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

2017-05-01

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

Uses of stable isotopes in fish ecology

EPA Science Inventory

Analyses of fish tissues (other than otoliths) for stable isotope ratios can provide substantial information on fish ecology, including physiological ecology. Stable isotopes of nitrogen and carbon frequently are used to determine the mix of diet sources for consumers. Stable i...

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

NASA Astrophysics Data System (ADS)

Bishop, Philip K.; Lloyd, John W.

1990-12-01

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

Stable carbon isotope analyses of nanogram quantities of particulate organic carbon (pollen) with laser ablation nano combustion gas chromatography/isotope ratio mass spectrometry

PubMed Central

Sluijs, Appy; Laks, Jelmer J.; Reichart, Gert‐Jan

2016-01-01

Rationale Analyses of stable carbon isotope ratios (δ 13C values) of organic and inorganic matter remains have been instrumental for much of our understanding of present and past environmental and biological processes. Until recently, the analytical window of such analyses has been limited to samples containing at least several μg of carbon. Methods Here we present a setup combining laser ablation, nano combustion gas chromatography and isotope ratio mass spectrometry (LA/nC/GC/IRMS). A deep UV (193 nm) laser is used for optimal fragmentation of organic matter with minimum fractionation effects and an exceptionally small ablation chamber and combustion oven are used to reduce the minimum sample mass requirement compared with previous studies. Results Analyses of the international IAEA CH‐7 polyethylene standard show optimal accuracy, and precision better than 0.5‰, when measuring at least 42 ng C. Application to untreated modern Eucalyptus globulus (C3 plant) and Zea mays (C4 plant) pollen grains shows a ~ 16‰ offset between these species. Within each single Z. mays pollen grain, replicate analyses show almost identical δ 13C values. Conclusions Isotopic offsets between individual pollen grains exceed analytical uncertainties, therefore probably reflecting interspecimen variability of ~0.5–0.9‰. These promising results set the stage for investigating both δ 13C values and natural carbon isotopic variability between single specimens of a single population of all kinds of organic particles yielding tens of nanograms of carbon. © 2016 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd. PMID:27766694

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

NASA Astrophysics Data System (ADS)

Pinti, D. L.; Hashizume, K.

2011-12-01

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

Climatic changes during the early Medieval and recent periods inferred from δ13C and δ18O of Siberian larch trees

NASA Astrophysics Data System (ADS)

Sidorova, O. V.; Matthias Saurer, Rolf Siegwolf

2010-12-01

We report unique isotope datasets for δ13C and δ18O of wood and cellulose of larch trees (Larix cajanderi Mayr.) from Northeastern Yakutia [70°N-148°E] for the early Medieval (AD 900-1000) and recent (AD 1880-2004) periods. During the recent period June, July, and August air temperatures were positively correlated with δ13C and δ18O of wood and cellulose, while July precipitation was negatively correlated. The positive correlation with one of the warmest months (July) in Northeastern Yakutia could indicate high photosynthetic capacity, because warm and dry conditions cause stomatal closure and lower the isotopic fractionation, leading to less negative δ13C values. Because during July, the soil water is still frozen at a soil depth of 20-30 cm, the water accessibility for trees is limited, which can lead to drought situations. An increase in water availability allows for a higher stomatal conductance, resulting in lower δ13C values, leading to a negative relationship with summer precipitation. Furthermore, the vapor pressure deficit of July and August was significantly correlated with δ13C of wood and cellulose, indicating decreased stomatal conductance, an expression of moderate drought. This leads to reduced 13CO2 discrimination and less negative δ13C values. The simultaneous increase of δ18O also indicates a reduction in stomatal conductance under rather dry conditions or drought. Comparative analyses between mean isotope values for the AD 900-1000 and AD 1880-2004 periods indicate similar ranges of climatic conditions, with the exception of the period AD 1950-2004, which is characterized by increased summer drought. Whilst isotopic ratios in cellulose are reliably related to climatic variables, those in whole wood showed even stronger relationships during some periods. Strong positive correlations between δ18O of cellulose and Greenland ice-core data were detected for the beginning of the Medieval period (r=0.86; p<0.05), indicating the reliability of isotope signals in tree rings for large-scale reconstructions. The recovery of multiple climate proxies from one archive, in this case annual tree rings, has the potential to identify more specific mechanistic links between the archive and varying climate. In this case, we enhance the existing quantitative reconstruction of early summer temperature from northeastern Yakutia with isotopic data, and gain a wider insight into the conditions under which the rings were formed. The multiple signals stored in tree rings, in particular isotope data, have the potential to increase our understanding of the influence of permafrost and precipitation on the mechanism of plant growth, and their response to this harsh climate in the vast Boreal zone. Acknowledgements: This work was supported by Marie Curie International Incoming Fellowship (FP7-235122), grants RFBR 09-05-98015 r_sibir_a. Thanks to Mukhtar Naurzbaev for sampling of the tree-ring material. Grants to Malcolm K Hughes, University of Arizona from the US National Science Foundation (9413327 and 0308525) supported the collection, dating, and ring-width measurement of material used in this study.

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

PubMed

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

2006-10-01

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

Comprehensive Isotopic and Elemental Analysis of a Multi-Oxide Glass By Multicollector ICP-MS in Isotope Substitution Studies

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

v, Mitroshkov; JV, Ryan

2016-04-07

Multicollector ICP-MS was used to comprehensively analyze different types of isotopically-modified glass created in order to investigate the processes of glass corrosion in the water. The analytical methods were developed for the analyses of synthesized, isotopically-modified solid glass and the release of glass constituents upon contact with deionized water. To validate the methods, results from an acid digestion sample of the Analytical Reference Glass (ARG) showed good agreement when compared to data from multiple prior analyses on the same glass [Smith-1]. In this paper, we present the results of this comprehensive analysis from the acid digestion of six types ofmore » isotopically-modified glass and the release of glass constituents into water corrosion after one year of aqueous corrosion.« less

Estimation of the formation rates of polyatomic species of heavy metals in plutonium analyses using a multicollector ICP-MS with a desolvating nebulizer

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

Mitroshkov, Alexandre V.; Olsen, Khris B.; Thomas, Linda M.

2015-01-01

The analyses of IAEA and environmental samples for Plutonium isotopic content are conducted normally at very low concentrations of Pu–usually in the range of part per trillion level and even more often at the parts per quadrillion level. To analyze such low concentrations, the interferences in the analytical solution must be reduced as much as possible. Polyatomic interferences (PIs), formed by the heavy metals (HMs) from Hf to Bi are known to create the problems for Pu isotopic analyses, because even the relatively high resolution of a modern multicollector ICP-MS is not enough to separate Pu isotopes from this PIsmore » in most of the cases. Desolvating nebulizers (DSN) (e.g. APEX and AridusII) reduce significantly the formation of PIs compare to the use of wet plasma. The purpose of this work was to investigate the rate of formation of PIs, produced by HMs, when high resolution MC ICP-MS with desolvating nebulizer was used for Pu isotopic analyses and to estimate the influence of the metals present in the sample on the results of analyses. The NU Plasma HR Multicollector and AridusII desolvating nebulizer were used in this investigation. This investigation was done for all Pu isotopes normally analyzed by ICP-MS, including ²⁴⁴Pu, with the exception of ²³⁸Pu, which most of the time can’t be analyzed by ICP-MS, because of the overwhelming presence of ²³⁸U in the solutions. The PI formation rates were determined and reported for all 12 HMs from Hf to Bi. Selected IAEA samples were scanned for the presence of HMs and the influence of HMs on the results of Pu isotopic analyses was evaluated. It was found that the implemented separation procedure provides sufficient separation of HM from Pu, although the effect of PIs on the measurement of low level isotopes like ²⁴¹Pu and ²⁴²Pu in some cases can still be observed.« less

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.

Pliocene and Pleistocene geologic and climatic evolution in the San Luis Valley of south-central Colorado

USGS Publications Warehouse

Rogers, K.L.; Larson, E.E.; Smith, G.; Katzman, D.; Smith, G.R.; Cerling, T.; Wang, Y.; Baker, R.G.; Lohmann, K.C.; Repenning, C.A.; Patterson, P.; Mackie, G.

1992-01-01

Sediments of the Alamosa Formation spanning the upper part of the Gauss and most of the Matuyama Chrons were recovered by coring in the high (2300 m) San Luis Valley of south-central Colorado. The study site is located at the northern end of the Rio Grande rift. Lithologic changes in the core sediments provide evidence of events leading to integration of the San Luis drainage basin into the Rio Grande. The section, which includes the Huckleberry Ridge Ash (2.02 Ma) and spans the entire Matuyama Chron, contains pollen, and invertebrate and vertebrate fossils. Stable isotope analyses of inorganic and biogenic carbonate taken over most of the core indicate substantially warmer temperatures than occur today in the San Luis Valley. At the end of the Olduvai Subchron, summer precipitation decreased, summer pan evaporation increased, and temperatures increased slightly compared to the earlier climate represented in the core. By the end of the Jaramillo Subchron, however, cold/wet and warm/dry cycles become evident and continue into the cold/wet regime associated with the deep-sea oxygen-isotope Stage 22 glaciation previously determined from outcrops at the same locality. Correspondence between the Hansen Bluff climatic record and the deep-sea oxygen-isotope record (oxygen-isotope stages from about 110-18) is apparent, indicating that climate at Hansen Bluff was responding to global climatic changes. ?? 1992.

The silicon isotope composition of the upper continental crust

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

On the 3He anomaly in hot subdwarf B stars

NASA Astrophysics Data System (ADS)

Schneider, David; Irrgang, Andreas; Heber, Ulrich; Nieva, Maria F.; Przybilla, Norbert

2017-12-01

Decades ago, 3He isotope enrichment in helium-weak B-type main-sequence, in blue horizontal branch and in hot subdwarf B (sdB) stars, i.e., helium-core burning stars of the extreme horizontal branch, were discovered. Diffusion processes in the atmosphere of these stars lead to the observed abundance anomalies. Quantitative spectral analyses of high-resolution spectra to derive photospheric isotopic helium abundance ratios for known 3He sdBs have not been performed yet. We present preliminary results of high-resolution and high S/N spectra to determine the 3He and 4He abundances of nine known 3He sdBs. We used a hybrid local/non-local thermodynamic equilibrium (LTE/NLTE) approach for B-type stars investigating multiple He i lines, including λ4922 Å and λ6678 Å, which show the strongest isotopic shifts in the optical spectral range.We also report the discovery of four new 3He sdBs from the ESO Supernova Progenitor survey. Most of the 3He sdBs cluster in a narrow temperature strip between ˜ 26000 K and ˜ 30000 K and have almost no atmospheric 4He at all. Interestingly, three 3He sdBs show evidence for vertical helium stratification.

Neodymium Isotopic Compositions of the Titanite Reference Materials Used in U-Pb Geochronology

NASA Astrophysics Data System (ADS)

Ma, Q.; Yang, Y.; Zhao, Z.

2017-12-01

Titanite (CaTiSiO5) is a widespread mineral and preferentially incorporates considerable uranium and significant light rare earth elements (LREEs) in its structure. Geochronology based upon U-Pb and Pb-Pb analyses of titanite has proven to be useful for understanding the P-T-t evolution of many igneous, metamorphic and hydrothermally altered rock samples (Scott and St-Onge, 1995). In the meantime, Sm-Nd isotopic composition in single titanite can be used to obtain initial Nd isotope composition at the time of titanite crystallization when combined with its U-Pb age, making titanite the most versatile mineral for dating metamorphism and tracing hydrothermal source (Amelin et al., 2009). The widely utilized in situ analyses by SIMS and LA-(MC)-ICP-MS have emphasized the significance for uniform and homogeneous reference materials for external correction (Liu et al., 2012, Sun et al., 2012, Yang et al., 2014). Here, we present U-Pb ages and Sm-Nd isotope analyses of twelve natural titanite crystals (12YQ82, T004, Ontario, BLR-1, OLT1, Khan, Qinghu, TLS-36, NW-IOA, C253, Pakistan and MKED1) acquired by Agilent 7500a Q-ICP-MS and Neptune MC-ICP-MS, respectively, combined a 193 nm ArF excimer laser ablation system. For U-Pb dating, elemental fractionation and instrumental drift were externally corrected using MKED1 titanite standard, showing results of U-Pb analyses all within error of those recommended values. With respect to Sm-Nd isotopes, we employed the interference-free 147Sm/149Sm to deduct 144Sm isobaric interference on 144Nd, and the fractionation between 147Sm and 144Nd was calibrated using BLR-1 titanite, which is proved homogenous in Sm-Nd isotopic system. The obtained Sm-Nd isotopic compositions for natural titanite samples are all consistent with those values determined by isotope dilution (ID) MC-ICP-MS, demonstrating the precision and accuracy currently available for in situ Sm-Nd analyses. Our results demonstrate that BLR-1, OLT1 and Ontario titanites are relatively uniform and homogeneous in Sm-Nd isotopic system and thus can serve as ideal reference materials for external calibration during in situ Sm-Nd analysis.

Deformation properties of lead isotopes

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

Tolokonnikov, S. V.; Borzov, I. N.; Lutostansky, Yu. S.

2016-01-15

The deformation properties of a long lead isotopic chain up to the neutron drip line are analyzed on the basis of the energy density functional (EDF) in the FaNDF{sup 0} Fayans form. The question of whether the ground state of neutron-deficient lead isotopes can have a stable deformation is studied in detail. The prediction of this deformation is contained in the results obtained on the basis of the HFB-17 and HFB-27 Skyrme EDF versions and reported on Internet. The present analysis reveals that this is at odds with experimental data on charge radii and magnetic moments of odd lead isotopes.more » The Fayans EDF version predicts a spherical ground state for all light lead isotopes, but some of them (for example, {sup 180}Pb and {sup 184}Pb) prove to be very soft—that is, close to the point of a phase transition to a deformed state. Also, the results obtained in our present study are compared with the predictions of some other Skyrme EDF versions, including SKM*, SLy4, SLy6, and UNE1. By and large, their predictions are closer to the results arising upon the application of the Fayans functional. For example, the SLy4 functional predicts, in just the same way as the FaNDF{sup 0} functional, a spherical shape for all nuclei of this region. The remaining three Skyrme EDF versions lead to a deformation of some light lead isotopes, but their number is substantially smaller than that in the case of the HFB-17 and HFB-27 functionals. Moreover, the respective deformation energy is substantially lower, which gives grounds to hope for the restoration of a spherical shape upon going beyond the mean-field approximation, which we use here. Also, the deformation properties of neutron-rich lead isotopes are studied up to the neutron drip line. Here, the results obtained with the FaNDF{sup 0} functional are compared with the predictions of the HFB-17, HFB-27, SKM*, and SLy4 Skyrme EDF versions. All of the EDF versions considered here predict the existence of a region where neutron-rich lead isotopes undergo deformations, but the size of this region is substantially different for the different functionals being considered. Once again, it is maximal for the HFB-17 and HFB-27 functionals, is substantially narrower for the FaNDF{sup 0} functional, and is still narrower for the SKM* and SLy4 functionals. The two-neutron drip line proved to be A{sub drip}{sup 2n} = 266 for all of the EDF versions considered here, with the exception of SKM*, for which it is shifted to A{sub drip}{sup 2n}(SKM*) = 272.« less

Effects of Simple Leaching of Crushed and Powdered Materials on High-precision Pb Isotope Analyses

NASA Astrophysics Data System (ADS)

Todd, E.; Stracke, A.

2013-12-01

We present new results of simple leaching experiments on the Pb isotope composition of USGS standard reference material powders and on ocean island basalt whole rock splits and powders. Rock samples were leached with 6N HCl in two steps, first hot and then in an ultrasonic bath, and washed with ultrapure H2O before conventional sample digestion and chromatographic purification of Pb. Pb isotope analyses were determined with Tl-doped MC-ICP-MS. Intra- and inter-session analytical reproducibility of repeated analyses of both synthetic Pb solutions and Pb from single digests of chemically processed natural samples were generally < 100 ppm (2 S.D.). The comparison of leached and unleached samples shows that leaching reliably removes variable amounts of different contaminants for different starting materials. For repeated digests of a single sample, the leached samples reproduce better than the unleached ones, showing that leaching effectively removes heterogeneously distributed extraneous Pb. However, the reproducibility of repeated digests of variably contaminated natural samples is up to an order of magnitude worse than the analytical reproducibility of ca. 100 ppm. More complex leaching methods (e.g., Nobre Silva et al., 2009) yield Pb isotope ratios within error of and with similar reproducibility to our method, showing that the simple leaching method is reliable. The remaining Pb isotope heterogeneity of natural samples, which typically exceeds 100 ppm, is thus attributed to inherent isotopic sample heterogeneity. Tl-doped MC-ICP-MS Pb ratio determination is therefore a sufficiently precise method for Pb isotope analyses in natural rocks. More precise Pb double- or triple-spike methods (e.g., Galer, 1999; Thirlwall, 2000), may exploit their full potential only in cases where natural isotopic sample heterogeneity is demonstrably negligible. References: Galer, S., 1999, Chem. Geol. 157, 255-274. Nobre Silva, et al. 2009, Geochemistry Geophysics Geosystems 10, Q08012. Thirlwall, M.F., 2000, Chem. Geol. 163, 299-322.

Stable Isotope Tracers of Process in Great Lakes Food Webs

EPA Science Inventory

Stable isotope analyses of biota are now commonly used to discern trophic pathways between consumers and their foods. However, those same isotope data also hold information about processes that influence the physicochemical setting of food webs as well as biological processes ope...

Urban water - a new frontier in isotope hydrology.

PubMed

Ehleringer, James R; Barnette, Janet E; Jameel, Yusuf; Tipple, Brett J; Bowen, Gabriel J

2016-01-01

Isotope hydrology has focused largely on landscapes away from densely inhabited regions. In coming decades, it will become increasingly more important to focus on water supplies and dynamics within urban systems. Stable isotope analyses provide important information to water managers within large cities, particularly in arid regions where evaporative histories of water sources, vulnerabilities, and reliabilities of the water supplies can be major issues. Here the spatial and vertical understanding of water supporting urban systems that comes from stable isotope analyses can serve as a useful management tool. We explore this research frontier using the coupled natural-human landscape of the Salt Lake Valley, USA, with its greater than one million inhabitants. We first provide data on the stable isotope ratios of the hydrologic system's primary components: precipitation, incoming surface waters, and terminus waters in this closed basin. We then explore the spatial and temporal patterns of drinking waters within the urban landscape and the new opportunities to better link isotope ratio data with short- and long-term management interests of water managers.

Can we use high precision metal isotope analysis to improve our understanding of cancer?

PubMed

Larner, Fiona

2016-01-01

High precision natural isotope analyses are widely used in geosciences to trace elemental transport pathways. The use of this analytical tool is increasing in nutritional and disease-related research. In recent months, a number of groups have shown the potential this technique has in providing new observations for various cancers when applied to trace metal metabolism. The deconvolution of isotopic signatures, however, relies on mathematical models and geochemical data, which are not representative of the system under investigation. In addition to relevant biochemical studies of protein-metal isotopic interactions, technological development both in terms of sample throughput and detection sensitivity of these elements is now needed to translate this novel approach into a mainstream analytical tool. Following this, essential background healthy population studies must be performed, alongside observational, cross-sectional disease-based studies. Only then can the sensitivity and specificity of isotopic analyses be tested alongside currently employed methods, and important questions such as the influence of cancer heterogeneity and disease stage on isotopic signatures be addressed.

Isotopic niches support the resource breadth hypothesis

USGS Publications Warehouse

Rader, Jonathan A.; Newsome, Seth D.; Sabat, Pablo; Chesser, R. Terry; Dillon, Michael E.; Martinez del Rio, Carlos

2017-01-01

Because a broad spectrum of resource use allows species to persist in a wide range of habitat types, and thus permits them to occupy large geographical areas, and because broadly distributed species have access to more diverse resource bases, the resource breadth hypothesis posits that the diversity of resources used by organisms should be positively related with the extent of their geographic ranges.We investigated isotopic niche width in a small radiation of South American birds in the genus Cinclodes. We analysed feathers of 12 species of Cinclodes to test the isotopic version of the resource breadth hypothesis and to examine the correlation between isotopic niche breadth and morphology.We found a positive correlation between the widths of hydrogen and oxygen isotopic niches (which estimate breadth of elevational range) and widths of the carbon and nitrogen isotopic niches (which estimates the diversity of resources consumed, and hence of habitats used). We also found a positive correlation between broad isotopic niches and wing morphology.Our study not only supports the resource breadth hypothesis but it also highlights the usefulness of stable isotope analyses as tools in the exploration of ecological niches. It is an example of a macroecological application of stable isotopes. It also illustrates the importance of scientific collections in ecological studies.

Lead isotope ratios in tree bark pockets: an indicator of past air pollution in the Czech Republic.

PubMed

Conkova, M; Kubiznakova, J

2008-10-15

Tree bark pockets were collected at four sites in the Czech Republic with differing levels of lead (Pb) pollution. The samples, spanning 1923-2005, were separated from beech (Fagus sylvatica) and spruce (Picea abies). Elevated Pb content (0.1-42.4 microg g(-1)) reflected air pollution in the city of Prague. The lowest Pb content (0.3-2.6 microg g(-1)) was found at the Kosetice EMEP "background pollution" site. Changes in (206)Pb/(207)Pb and (208)Pb/(206)Pb isotope ratios were in agreement with operation times of the Czech main anthropogenic Pb sources. Shortly after the Second World War, the (206)Pb/(207)Pb isotope ratio in bark pockets decreased from 1.17 to 1.14 and the (208)Pb/(206)Pb isotope ratio increased from 2.12 to 2.16. Two dominant emission sources responsible for these changes, lignite and leaded petrol combustion, contributed to the shifts in Pb isotope ratios. Low-radiogenic petrol Pb ((206)Pb/(207)Pb of 1.11) lead to lower (206)Pb/(207)Pb in bark pockets over time. High-radiogenic lignite-derived Pb ((206)Pb/(207)Pb of 1.18 to 1.19) was detected in areas affected by coal combustion rather than by traffic.

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

USGS Publications Warehouse

Böhlke, John Karl; Mroczkowski, Stanley J.; Sturchio, Neil C.; Heraty, Linnea J.; Richman, Kent W.; Sullivan, Donald B.; Griffith, Kris N.; Gu, Baohua; Hatzinger, Paul B.

2017-01-01

RationalePerchlorate (ClO4−) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO4− source attribution and natural attenuation studies: δ37Cl, δ18O, and δ17O (or Δ17O or 17Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies.MethodsThree large batches of KClO4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O2, and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO4− to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO4 was reprecipitated as AgCl and converted into CH3Cl for DIIRMS.ResultsKClO4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO4− depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO42−, NO3−, ReO42−, and C-bearing contaminants include isotope mixing and fractionation effects on CO and O2, plus direct interference from CO2 in the mass spectrometer. The results highlight the importance of effective purification of ClO4− from environmental samples.ConclusionsKClO4 reference materials are available for testing methods and calibrating isotopic data for ClO4− and other substances with widely varying Cl or O isotopic compositions. Current ClO4−extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO4−, permitting isotopic evaluation of environmental ClO4− sources and natural attenuation.

On the similarity and apparent cycles of isotopic variations in East Antarctic snow pits

NASA Astrophysics Data System (ADS)

Laepple, Thomas; Münch, Thomas; Casado, Mathieu; Hoerhold, Maria; Landais, Amaelle; Kipfstuhl, Sepp

2018-01-01

Stable isotope ratios δ18O and δD in polar ice provide a wealth of information about past climate evolution. Snow-pit studies allow us to relate observed weather and climate conditions to the measured isotope variations in the snow. They therefore offer the possibility to test our understanding of how isotope signals are formed and stored in firn and ice. As δ18O and δD in the snowfall are strongly correlated to air temperature, isotopes in the near-surface snow are thought to record the seasonal cycle at a given site. Accordingly, the number of seasonal cycles observed over a given depth should depend on the accumulation rate of snow. However, snow-pit studies from different accumulation conditions in East Antarctica reported similar isotopic variability and comparable apparent cycles in the δ18O and δD profiles with typical wavelengths of ˜ 20 cm. These observations are unexpected as the accumulation rates strongly differ between the sites, ranging from 20 to 80 mm w. e. yr-1 ( ˜ 6-21 cm of snow per year). Various mechanisms have been proposed to explain the isotopic variations individually at each site; however, none of these are consistent with the similarity of the different profiles independent of the local accumulation conditions.Here, we systematically analyse the properties and origins of δ18O and δD variations in high-resolution firn profiles from eight East Antarctic sites. First, we confirm the suggested cycle length (mean distance between peaks) of ˜ 20 cm by counting the isotopic maxima. Spectral analysis further shows a strong similarity between the sites but indicates no dominant periodic features. Furthermore, the apparent cycle length increases with depth for most East Antarctic sites, which is inconsistent with burial and compression of a regular seasonal cycle. We show that these results can be explained by isotopic diffusion acting on a noise-dominated isotope signal. The firn diffusion length is rather stable across the Antarctic Plateau and thus leads to similar power spectral densities of the isotopic variations. This in turn implies a similar distance between isotopic maxima in the firn profiles.Our results explain a large set of observations discussed in the literature, providing a simple explanation for the interpretation of apparent cycles in shallow isotope records, without invoking complex mechanisms. Finally, the results underline previous suggestions that isotope signals in single ice cores from low-accumulation regions have a small signal-to-noise ratio and thus likely do not allow the reconstruction of interannual to decadal climate variations.

Generalists or Specialists: Stable Isotope Analysis of Humpback Whales (Megapteranoveangliae) to Infer Variation in Feeding Preferences

NASA Astrophysics Data System (ADS)

Brownstein, A.; Boswell, K. M.

2016-02-01

Though humpback whales (Megapteranovaeangliae) are commonly observed in coastal waters of the Gulf of Alaska, their massive size, behavior, and weather conditionsmake it difficult to make accurate observations regarding their feeding habits. These whales can be highly abundant during feeding aggregations, and given their large energetic needs, they have the potential to impact populations of ecologically important forage such as krill and herring. Previous studies in other areas, such as the Gulf of Maine and the North Pacific Ocean, classify humpback whales as generalists that can efficiently feed on both schooling fish and large zooplankton. In Prince William Sound, scientists have observed the humpbacks feedingprimarily on herring. It is unclear if these whalesfeed exclusively on fish prior to returning to the Sound, and can therefore be considered specialists. Stable isotope analysis of carbon and nitrogen were used to determine the preferred diet of humpback whales (N=22) in 6 sampling regions along the Gulf of Alaska. Isotope analyses were conducted on humpback whale skin, as well as local forage species and basal resources to be used in Bayesian isotope mixing models to elucidate the trophic relationships between whales and their prey, and provide insight to whether location is an important driver in prey selection. This information will not only lead to a better understanding of the potential to use tissue isotopes to elucidate foraging behaviors of humpback whales, but also offer insight into individual feeding preferences and how increasing whale populations may affect the populations of local forage in the future.

Determining tissue-lead levels in large game mammals harvested with lead bullets: human health concerns.

PubMed

Tsuji, L J S; Wainman, B C; Jayasinghe, R K; VanSpronsen, E P; Liberda, E N

2009-04-01

Recently, the use of lead isotope ratios has definitively identified lead ammunition as a source of lead exposure for First Nations people, but the isotope ratios for lead pellets and bullets were indistinguishable. Thus, lead-contaminated meat from game harvested with lead bullets may also be contributing to the lead body burden; however, few studies have determined if lead bullet fragments are present in big game carcasses. We found elevated tissue-lead concentrations (up to 5,726.0 microg/g ww) in liver (5/9) and muscle (6/7) samples of big game harvested with lead bullets and radiographic evidence of lead fragments. Thus, we would advise that the tissue surrounding the wound channel be removed and discarded, as this tissue may be contaminated by lead bullet fragments.

Isotopic and nutritional evidence for species- and site-specific responses to N deposition and elevated CO2 in temperate forests

NASA Astrophysics Data System (ADS)

Silva, Lucas C. R.; Gómez-Guerrero, Armando; Doane, Timothy A.; Horwath, William R.

2015-06-01

In this study we show that the effect of rising atmospheric CO2 levels on forest productivity is influenced by changes in nutrient availability caused by nitrogen (N) deposition. We used a dual-isotope approach (δ15N and δ13C), combined with dendrochronological and nutritional analyses, to evaluate the response of two dominant tree species in natural forest ecosystems near Mexico City (Pinus hartwegii—pine; Abies religiosa—fir). Our analysis focuses on changes that occurred over the past 50 years at two sites, one under high and one under low N deposition rates. Analyses of carbon isotope composition indicate increasing water-use efficiency in response to rising CO2 levels for both species and sites but this effect did not lead to improved tree growth. The magnitude and direction of shifts in 13C discrimination indicate a process of acclimation that varied with the rate of N deposition and species traits. Since the 1960s, strong negative responses to N deposition have been observed in fir trees, which showed altered foliar nutrition and growth decline, while the negative impacts of N deposition on pine trees remained undetectable until the 1990s. In recent years, both species have shown significant growth decline under high N deposition despite increasing atmospheric CO2. Multivariate analysis of leaf nutrients indicates that growth decline was prompted by depleted soil macronutrient (P, K, and Ca) and micronutrient (Cu, Fe, Zn, and Mn) availability. At both sites, fir trees were a better indicator of N deposition due to differences in canopy rainfall interception.

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

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

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

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

More than who eats who: Discerning ecological processes from stable isotopes data

EPA Science Inventory

Stable isotope analyses of biota are now commonly used to discern trophic pathways between consumers and their foods. However, those same isotope data also hold information about processes that influence the physicochemical setting of food webs as well as biological processes ope...

DETECTION OF GROUNDWATER AGES WITH 85 KR IN ARSENIC-BEARING, FRACTURED CRYSTALLINE BEDROCK OF THE GOOSE RIVER BASIN, MAINE

EPA Science Inventory

Young groundwater from various depths in crystalline bedrock of the Goose River basin, mid-coastal Maine, is documented from 85Kr isotope age analyses (1963 ? 1987) but not from 3H isotope age analyses. Elevated geogenic arsenic in drinking water from groundwater wells and sprin...

DETECTION OF 3 H AND 85KR IN GROUNDWATER FROM ARSENIC-BEARING CRYSTALLINE BEDROCK OF THE GOOSE RIVER BASIN, MAINE

EPA Science Inventory

Young groundwater from various depths in crystalline bedrock of the Goose River basin, mid-coastal Maine, is documented from 85Kr isotope age analyses (1963 ? 1987) but not from 3H isotope age analyses. Elevated geogenic arsenic in drinking water from groundwater wells and sprin...

A modified technique for the preparation of SO2 from sulphates and sulphides for sulphur isotope analyses.

PubMed

Han, L; Tanweer, A; Szaran, J; Halas, S

2002-09-01

A modified technique for the conversion of sulphates and sulphides to SO2 with the mixture of V2O5-SiO2 for sulphur isotopic analyses is described. This technique is more suitable for routine analysis of large number of samples. Modification of the reaction vessel and using manifold inlet system allows to analyse up to 24 samples every day. The modified technique assures the complete yield of SO2, consistent oxygen isotope composition of the SO2 gas and reproducibility of delta34S measurements being within 0.10 per thousand. It is observed, however, oxygen in SO2 produced from sulphides differs in delta18O with respect to that produced from sulphates.

Rates of carbonate soil evolution from carbon, U- and Th-series isotope studies: Example of the Astian sands (SE France)

NASA Astrophysics Data System (ADS)

Barbecot, Florent; Ghaleb, Bassam; Hillaire-Marcel, Claude

2015-04-01

In carbonate rich soils, C-isotopes (14C, 13C) and carbonate mass budget may inform on centennial to millennial time scale dissolution/precipitation processes and weathering rates, whereas disequilibria between in the U- and Th-decay series provide tools to document high- (228Ra-228Th-210Pb) to low- (234U, 230Th, 231Pa, 226Ra) geochemical processes rate, covering annual to ~ 1Ma time scales, governing both carbonate and silicate soil fractions. Because lithology constitutes a boundary condition, we intend to illustrate the behavior of such isotopes in soils developed over Astian sands formation (up to ~ 30% carbonate) from the Béziers area (SE France). A >20 m thick unsaturated zone was sampled firstly along a naturally exposed section, then in a cored sequence. Geochemical and mineralogical analyses, including stable isotopes and 14C-measurements, were complemented with 228U, 234U, 230Th, 226Ra, 210Pb and 228Th, 232Th measurements. Whereas the upper 7 m depict geochemical and isotopic features forced by dissolution/precipitation processes leading to variable radioactive disequilibria, but overall deficits in more soluble elements of the decay series, the lower part of the sequence shows strong excesses in 234U and 230Th over parent isotopes (i.e., 238U and 234U, respectively). These features might have been interpreted as the result of successive phases of U-loss and gains. However, 226Ra and 230Th are in near-equilibrium, thus leading to conclude at a more likely slow enrichment process in both 234Th(234U) and 230Th, which we link to dissolved U-decay during groundwater recharge events. In addition, 210Pb deficits (vs parent 226Ra) are observed down to 12 m along the natural outcropping section and below the top-soil 210Pb-excess in the cored sequence, due to gaseous 222Rn-diffusion over the cliff outcrop. Based on C-isotope and chemical analysis, reaction rates at 14C-time scale are distinct from those estimates at the short- or long-lived U-series isotopes, but provide a specific insight into carbonate budgets when confronted with data on dissolved and gaseous phases as well as on solid matter, and possibly best integrate the overall soil behavior through time. It is concluded from this example that if first order estimates of long-term geochemical fluxes in soils can be obtained from disequilibria in the 238U-234U-230Th sequence or from C-isotope data. While insights into recent to "Anthropocene" processes require information on the shorter-lived isotopes of the U and Th series, adding specific information on physical and chemical erosion budgets from 232Th data. As also illustrated in the present example, a robust assessment of overall chemical and physical erosion rates must be based on measurements in cored sequences away from natural or recent man-made cuts.

Detection of counterfeit antiviral drug Heptodin and classification of counterfeits using isotope amount ratio measurements by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) and isotope ratio mass spectrometry (IRMS).

PubMed

Santamaria-Fernandez, Rebeca; Hearn, Ruth; Wolff, Jean-Claude

2009-06-01

Isotope ratio mass spectrometry (IRMS) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) are highly important techniques that can provide forensic evidence that otherwise would not be available. MC-ICP-MS has proved to be a very powerful tool for measuring high precision and accuracy isotope amount ratios. In this work, the potential of combining isotope amount ratio measurements performed by MC-ICP-MS and IRMS for the detection of counterfeit pharmaceutical tablets has been investigated. An extensive study for the antiviral drug Heptodin has been performed for several isotopic ratios combining MC-ICP-MS and an elemental analyser EA-IRMS for stable isotope amount ratio measurements. The study has been carried out for 139 batches of the antiviral drug and analyses have been performed for C, S, N and Mg isotope ratios. Authenticity ranges have been obtained for each isotopic system and combined to generate a unique multi-isotopic pattern only present in the genuine tablets. Counterfeit tablets have then been identified as those tablets with an isotopic fingerprint outside the genuine isotopic range. The combination of those two techniques has therefore great potential for pharmaceutical counterfeit detection. A much greater power of discrimination is obtained when at least three isotopic systems are combined. The data from these studies could be presented as evidence in court and therefore methods need to be validated to support their credibility. It is also crucial to be able to produce uncertainty values associated to the isotope amount ratio measurements so that significant differences can be identified and the genuineness of a sample can be assessed.

Lead Isotope Geochemistry of Mississippi Valley-Type Pb-Zn Deposits of the Ozark Region, U.S. Midcontinent: Constraints on the Origin of Ore Metals

NASA Astrophysics Data System (ADS)

Potra, A.

2015-12-01

The Ozark region of the U.S. midcontinent is one of the world's most important provinces of MVT mineralization, hosting world-class ore deposits. The ores in the Tri-State (TS) and Northern Arkansas (NA) districts, dominated by sphalerite, are mainly hosted by platform carbonate rocks and vary in age from Ordovician and Mississippian for NA and Mississippian for TS. The deposits are considered to have formed from a regional hydrothermal flow system consisting of sedimentary brines discharged from the Arkoma basin and adjacent platform during the Late Pennsylvanian to Early Permian Ouachita orogeny. New MC-ICP-MS Pb isotope analyses of sphalerites are presented in order to compare and contrast the isotopic signature of ores from the NA and TS districts with those from other MVT districts from central and eastern US and trace metal sources. The Pb isotope ratios of ores from the TS District (208Pb/204Pb between 40.7443 and 41.2626; 207Pb/204Pb between 15.8633 and 15.9571; 206Pb/204Pb between 21.8373 and 22.1956) plot in an area that is superimposed on the Pb isotope field defined by samples from the Central Missouri District, suggesting similar metal sources. The sphalerites are less radiogenic than samples from the Upper Mississippi Valley District, but more radiogenic than samples from any other MVT district. Sphalerites from the NA District have lower Pb isotope values (208Pb/204Pb between 39.4633 and 40.8863; 207Pb/204Pb between 15.8216 and 15.9176; 206Pb/204Pb between 20.2396 and 21.6438) than the TS District ores; they plot below the field defined by samples from the Illinois-Kentucky district and overlap the field defined by ores from the Southeast Missouri (Viburnum and Old Lead Belt) district, implying similar metal sources. Current data suggest that basement of Grenvillian age (1 - 1.2 by), thought to be present in Arkansas, to the south of the Viburnum Trend, may be a likely source of the radiogenic Pb component. Pb data from ores in the NA and the Southeast Missouri districts are collinear with data from the TS and Central Missouri districts.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-03-01

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

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

Mittermayr, Florian, E-mail: f.mittermayr@tugraz.at; Baldermann, Andre; Kurta, Christoph

Understanding the mechanisms leading to chemical attack on concrete is crucial in order to prevent damage of concrete structures. To date, most studies on sulfate attack and thaumasite formation are based on empirical approaches, as the identification of associated reaction mechanisms and paths is known to be highly complex. In this study, sulfate damaged concrete from Austrian tunnels was investigated by mineralogical, chemical and isotope methods to identify the reactions which caused intense concrete alteration. Major, minor and trace elemental contents as well as isotope ratios of local ground water (GW), drainage water (DW) and interstitial solutions (IS), extracted frommore » damaged concrete material, were analyzed. Locally occurring GW contained 3 to 545 mg L{sup −1} of SO{sub 4} and is thus regarded as slightly aggressive to concrete in accordance to standard specifications (e.g. DIN EN 206-1). The concrete linings and drainage systems of the studied tunnels, however, have partly suffered from intensive sulfate attack. Heavily damaged concrete consisted mainly of thaumasite, secondary calcite, gypsum, and relicts of aggregates. Surprisingly, the concentrations of dissolved ions were extremely enriched in the IS with up to 30,000 and 12,000 mg L{sup −1} of SO{sub 4} and Cl, respectively. Analyses of aqueous ions with a highly conservative behavior, e.g. K, Rb and Li, as well as {sup 2}H/H and {sup 18}O/{sup 16}O isotope ratios of H{sub 2}O of the IS showed an intensive accumulation of ions and discrimination of the light isotopes vs. the GW. These isotope signals of the IS clearly revealed evaporation at distinct relative humidities. From ion accumulation and isotope fractionation individual total and current evaporation degrees were estimated. Our combined elemental and isotopic approach verified wetting–drying cycles within a highly dynamic concrete-solution-atmosphere system. Based on these boundary conditions, key factors controlling thaumasite formation are discussed regarding the development of more sulfate-resistant concrete and concrete structures.« less

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

USGS Publications Warehouse

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

1999-01-01

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

Characteristics of Martian Crustal Materials and Implications for Magmatic Assimilation: Preliminary Re-Os Isotope and Highly Siderophile Element Abundance Data for Nakhlites and Tissint

NASA Astrophysics Data System (ADS)

Mari, N.; Riches, A. J. V.; Hallis, L. J.; Lee, M. R.

2017-07-01

This project, for the first time, aims to integrate nakhlite Os-isotope compositions and HSE abundance data with S-isotope compositions for sample fractions for which textural information is constrained prior to destructive analyses.

USING STABLE ISOTOPES FOR FISH DIETARY ANALYSES: COPING WITH TOO MANY SOURCES

EPA Science Inventory

Stable isotope analysis can provide a useful tool for determining time-integrated measures of proportional food source contributions to fish diets. Ratios of stable (non-radioactive) isotopes of common elements (e.g., C,N,S) vary among food sources, and tissues of consumers (e.g...

Methane production and bubble emissions from arctic lakes: isotopic implications for source pathways and ages

Treesearch

K.M. Walter; J.P. Chanton; F.S. Chapin III; E.A.G. Schuur; S.A. Zimov

2008-01-01

This study reports an atmospheric methane (CH4) source term previously uncharacterized regarding strength and isotopic composition. Methane emissions from 14 Siberian lakes and 9 Alaskan lakes were characterized using stable isotopes (13C and D) and radiocarbon (14C) analyses. We classified ebullition...

Reporting of nitrogen-isotope abundances (Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Krouse, H.R.; Böhlke, John Karl

1992-01-01

To eliminate possible confusion in the reporting of nitrogen-isotope analyses, the Commission on Atomic Weights and Isotopic Abundances recommends that the value 272 be employed for the 14N/15N value of N2 in air for calculating atom percent 15N from measured δ15N values.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

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

PubMed

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

2013-05-01

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

Lead isotope systematics of some Apollo 17 soils and some separated components from 76501

NASA Technical Reports Server (NTRS)

Church, S. E.; Tilton, G. R.

1974-01-01

Isotopic lead data from bulk samples of Apollo 17 soils were analyzed, and they define a chord in a concordia diagram, showing the presence of a component or components containing excess radiogenic lead with Pb-207/Pb-206 equal to about 1.32. The chord is distinctly different from the cataclysm chord, for which Pb-207/Pb-206 is approximately 1.45. Nitric acid analysis of plagioclase indicates lead ages of around 4.35 AE, in agreement with previous findings. Agglutinates from soil 76501,34 show loss of approximately 15% of lead.

Lead in Martian Meteorites-- Observations and Inconsistencies: I. Chassigny

NASA Technical Reports Server (NTRS)

Jones, J. H.; Simon, J. I.; Usui, T.

2017-01-01

The history of Pb isotope analyses of the martian meteorites (SNC) and their interpretations is laden with difficulties. Two different analytical groups have interpreted their ancient (= 4 Ga) shergottite Pb ages as primary [1-5]. A Nakhla age of approximately 4.3 Ga has been interpreted to be primary as well [2]. This is in stark contrast to the young (= 1.4 Ga) crystallization ages defined by the Rb-Sr, Sm-Nd, Lu-Hf, and KAr systems [6]. Possibly, a better interpretation for the ancient Pb ages is that they reflect the formation times of the various SNC source regions [7]. A difficulty in dealing with Pb is that terrestrial contamination is ubiquitous, unlike the other chronometer systems noted above. This issue is complicated by the fact that radioactive decay causes localized mineral damage. So washing and leaching to remove Pb contamination tends to remove in situ radiogenic Pb. This issue is further compounded because U and Th are often concentrated in phosphates and other minor phases, so the leaching process tends to remove these, especially phosphates. Another difficulty is that it is not clear whether the observed Pb isotopic variation in leachates, residues, and ion-microprobe analyses is due to terrestrial or to indigenous martian Pb contamination [e.g., 8]. A third difficulty is that the shergottites on the one hand, and the nakhlites and chassignites on the other, appear to have come from separate source regions with different chemical compositions [e.g., 7]. Thus, it is expected that their Pb isotopic characteristics would be different. And even if all these meteorite types came from the same source region, their igneous ages differ considerably. The nakhlites and chassignites are 1.4 Ga and the shergottites are = 600 Ma [e.g., 6]. This age difference alone should assure that the two distinct SNC groups have differing Pb isotopic signatures.

Biomarkers and their stable isotopes in Cenozoic sediments above the Chicxulub impact crater

NASA Astrophysics Data System (ADS)

Grice, K.; Schaefer, B.; Coolen, M.; Greenwood, P. F.; Scarlett, A. G.; Freeman, K.; Lyons, S. L.

2017-12-01

The most widely accepted hypothesis for the cause of the End-Cretaceous mass extinction (K/Pg event) 66 Ma ago is the impact of an extra-terrestrial body, which produced the 200 km wide Chicxulub impact structure. This event led to an extinction of 75% of all species on Earth. The massive extinction in the terrestrial realm is partly attributed to the intense heat pulse, the widespread wild fires caused by the impact and the ensuing darkness, as dust and sulfate aerosols blocked out the sun leading to photosynthesis shut off and productivity collapse in both the terrestrial and marine realms. The marine realm may additionally have experienced ocean acidification resulting in mass extinction of plankton (foraminifera and coccolithophorids) and marine reptiles. Samples from the Cenozoic marine sediments including the Paleocene-Eocene Thermal Maximum (PETM) have been extracted for hydrocarbons and analysed to investigate the molecular and isotopic organic record of biotic and environmental change after the K/Pg boundary event. Specific biomarker-precursor relationship has been established by the direct correlation of sedimentary biomarkers with the biochemicals (e.g. lipids) of extant biological systems. The structural characterisation of biomarkers as well as their stable isotopic compositions (C, H and N) are used to evaluate the source(s) of organic matter (OM) and to reconstruct paleoenvironmental depositional conditions. Throughout the Cenozoic sediments (including the PETM) the biomarker distribution suggests a variation in the source of organic matter from terrestrial to marine. Furthermore, the presence of sulfurised biomarkers indicates euxinic environmental conditions at the time of deposition. Biomarker distributions indicative of green sulfur bacteria reveal persistent photic zone euxinic conditions at several intervals in the Cenozoic. Further compound specific isotope analyses will provide insights into the long-term biogeochemical cycling of C, H and S after the K/Pg extinction including the PETM.

The Influence of Non-spectral Matrix Effects on the Accuracy of Isotope Ratio Measurement by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Barling, J.; Shiel, A.; Weis, D.

2006-12-01

Non-spectral interferences in ICP-MS are caused by matrix elements effecting the ionisation and transmission of analyte elements. They are difficult to identify in MC-ICP-MS isotopic data because affected analyses exhibit normal mass dependent isotope fractionation. We have therefore investigated a wide range of matrix elements for both stable and radiogenic isotope systems using a Nu Plasma MC-ICP-MS. Matrix elements commonly enhance analyte sensitivity and change the instrumental mass bias experienced by analyte elements. These responses vary with element and therefore have important ramifications for the correction of data for instrumental mass bias by use of an external element (e.g. Pb and many non-traditional stable isotope systems). For Pb isotope measurements (Tl as mass bias element), Mg, Al, Ca, and Fe were investigated as matrix elements. All produced signal enhancement in Pb and Tl. Signal enhancement varied from session to session but for Ca and Al enhancement in Pb was less than for Tl while for Mg and Fe enhancement levels for Pb and Tl were similar. After correction for instrumental mass fractionation using Tl, Mg effected Pb isotope ratios were heavy (e.g. ^{208}Pb/204Pbmatrix > ^{208}Pb/204Pbtrue) for both moderate and high [Mg] while Ca effected Pb showed little change at moderate [Ca] but were light at high [Ca]. ^{208}Pb/204Pbmatrix - ^{208}Pb/204Pbtrue for all elements ranged from +0.0122 to - 0.0177. Isotopic shifts of similar magnitude are observed between Pb analyses of samples that have seen either one or two passes through chemistry (Nobre Silva et al, 2005). The double pass purified aliquots always show better reproducibility. These studies show that the presence of matrix can have a significant effect on the accuracy and reproducibility of replicate Pb isotope analyses. For non-traditional stable isotope systems (e.g. Mo(Zr), Cd(Ag)), the different responses of analyte and mass bias elements to the presence of matrix can result in del/amu for measured & mass bias corrected data that disagree outside of error. Either or both values can be incorrect. For samples, unlike experiments, the correct del/amu is not known in advance. Therefore, for sample analyses to be considered accurate, both measured and exponentially corrected del/amu should agree.

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

NASA Astrophysics Data System (ADS)

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

2004-12-01

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

Exploiting Stable Mercury Isotopic Analysis to Differentiate between Mercury Sources: Gold Mining vs. Land-Use Change (Invited)

NASA Astrophysics Data System (ADS)

Bergquist, B. A.; Adler Miserendino, R. A.; Guimarães, J. R.; Veiga, M.; Velasquez-López, P.; Lees, P. S.; Thibodeau, A. M.; Fernandez, L. E.

2013-12-01

In parts of the developing world, mercury (Hg) is used to extract gold by amalgamation during artisanal and small-scale gold mining (ASGM) and this can lead to contamination of downstream aquatic ecosystems. Differentiation between Hg from ASGM and from other sources of Hg, such as increased erosion from land cover and land use change (LCLUC), is challenging and has lead to heated debates over the dominant sources of elevated Hg in some ecosystems. Here, stable Hg isotopic analysis was applied in two aquatic ecosystems in South America: (1) the Amazonian aquatic ecosystem of Amapá, Brazil downstream of artisanal gold mining (AGM) and (2) the Puyango-Tumbes River ecosystem downstream of Portovelo-Zaruma, Ecuador, a large mining area where both AGM and small-scale gold mining (SGM) are in operation. The Hg isotopic analyses from Amapá, Brazil, do not support AGM as the source of elevated Hg in the downstream aquatic ecosystem. Instead, Hg isotopes are most consistent with the elevated Hg being from preferential migration of Hg from soil erosion, which is likely associated with land use change. Although soils are regarded as Hg sinks in the global Hg cycle, this work suggests that LCLUC can disrupt Hg stores with significant ecological consequences. In contrast in the Southwestern Andean region of Ecuador and Peru, analysis of Hg isotopes and other toxic metals (i.e., Pb, Zn, Cu), which are associated with the larger scale mining and cyanide used during SGM, demonstrate Hg used during gold mining is the predominant source of Hg downstream and can be traced far from the dominant mining area. Although it has been speculated that Hg from SGM in Ecuador was not that mobile or that Hg far downstream of SGM processing plants was from erosion due to LCLUC or from AGM taking place downstream, the isotopically heavy signature of Hg used during gold mining and elevated other metal concentrations were observed ~120 km downstream of Portovelo-Zaruma. Mercury isotopes appear able to differentiate mining Hg from the non-mining background, which includes runoff from soils and atmospheric deposition, but they cannot distinguish between Hg used during mining from different mining regions or Hg used during AGM versus SGM. Thus, other toxic metals were measured that are more likely to be associated with SGM as opposed to AGM. Together, these studies demonstrate that variations in stable Hg isotopes are a viable tool to differentiate between Hg sources. Although there are unconstrained or unknown aspects of the stable Hg isotope cycle, the isotopic differences between Hg used during ASGM and from background soil, sediment and atmospheric deposition are large enough not to be obscured by changes in isotopic distributions that may be induced as Hg is transported through the environment. This is likely because most of the Hg in the above aquatic ecosystems is bound to particles and colloids and transported such that most of the Hg does not undergo transformations that fractionate Hg isotopes. For example, in the Puyango-Tumbes River, greater than 95% of the Hg is transported in the particulate phase. Thus, in areas where Hg is transported primarily in the particulate or colloidal form, it can be traced if Hg sources are isotopically distinct. Additionally, the contrasting results in our two studies show that scale and processing differences between AGM and SGM influence the extent of Hg contamination.

Stable Isotopes in Evaluation of Greenhouse Gas Emissions

USDA-ARS?s Scientific Manuscript database

Isotopes offer a unique way to have natural tracers present in the ecosystem to track produced greenhouse gases (GHG) through multiple scales. Isotopes are simply atoms of the same element (same number of protons) with differing number of neutrons. This differing number of neutrons leads to differen...

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

NASA Astrophysics Data System (ADS)

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

2004-05-01

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

The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions

NASA Technical Reports Server (NTRS)

Keller, Lindsay P.; McKeegan, K. D.; Sharp, Z. D.

2012-01-01

MIL 090001 is a large (>6 kg) carbonaceous chondrite that was classified as a member of the CV reduced subgroup (CVred) that was recovered during the 2009-2010 ANSMET field season [1]. Based on the abundance of refractory inclusions and the extent of aqueous alteration, Keller [2] suggested a CV2 classification. Here we report additional mineralogical and petrographic data for MIL 090001, its whole-rock oxygen isotopic composition and ion microprobe analyses of individual phases. The whole rock oxygen isotopic analyses show that MIL 090001 should be classified as a CR chondrite.

Genetic variation in growth, carbon isotope discrimination, and foliar N concentration in Picea mariana: analyses from a half-diallel mating design using field-grown trees

Treesearch

Kurt H. Johnsen; Lawrence B. Flanagan; Dudley A. Huber; John E. Major

1999-01-01

The authors performed genetic analyses of growth, carbon isotope discrimination (?13C), and foliar N concentration using a half-diallel subset of a 7 × 7 complete diallel planted on three sites ranging in water availability. Trees were 22 years old. Heritabilities; general and...

Storm-Generated Sediment Distribution Along the Northwest Florida Inner Continental Shelf

DTIC Science & Technology

2009-10-04

grain shape, direct shear, radiocarbon isotope, and lignin -phenol analyses were performed on grab or vibracore samples collected after the storm...near-shore continental shelf. 15. SUBJECT TERMS Lignin , seafloor imagery, sedimentation, sediments 16. SECURITY CLASSIFICATION OF: a. REPORT...direct shear, radiocarbon isotope, and lignin -phenol analyses were performed on grab or vibracore samples collected after the storm. Sonar

Publications - GMC 425 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 425 Publication Details Title: Sr 87/86 isotope analyses of cuttings from the OCS Y-1092 Galahad #1 and OCS Y-0871 Corona #1 wells Authors: U.S. Geological Survey Publication Date: Jun 2014 Reference U.S. Geological Survey, 2014, Sr 87/86 isotope analyses of cuttings from the OCS Y-1092 Galahad #1

Coupling lead isotopes and element concentrations in epiphytic lichens to track sources of air emissions in the Alberta Oil Sands Region

EPA Science Inventory

A study was conducted that coupled use of element concentrations and lead (Pb) isotope ratios in the lichen Hypogymnia physodes collected during 2002 and 2008, to assess the impacts of air emissions from the Alberta Oil Sands Region (AOSR, Canada) mining and processing operations...

Validation of chlorine and oxygen isotope ratio analysis to differentiate perchlorate sources and to document perchlorate biodegradation

USGS Publications Warehouse

Paul B. Hatzinger,; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua

2013-01-01

Increased health concerns about perchlorate (ClO4-) during the past decade and subsequent regulatory considerations have generated appreciable interest in source identification. The key objective of the isotopic techniques described in this guidance manual is to provide evidence concerning the origin of ClO4- in soils and groundwater and, more specifically, whether that ClO4- is synthetic or natural. Chlorine and oxygen isotopic analyses of ClO4- provide the primary direct approach whereby different sources of ClO4- can be distinguished from each other. These techniques measure the relative abundances of the stable isotopes of chlorine (37Cl and 35Cl) and oxygen (18O, 17O, and 16O) in ClO4- using isotope-ratio mass spectrometry (IRMS). In addition, the relative abundance of the radioactive chlorine isotope 36Cl is measured using accelerator mass spectrometry (AMS). Taken together, these measurements provide four independent quantities that can be used to distinguish natural and synthetic ClO4- sources, to discriminate different types of natural ClO4-, and to detect ClO4- biodegradation in the environment. Other isotopic, chemical, and geochemical techniques that can be applied in conjunction with isotopic analyses of ClO4- to provide supporting data in forensic studies are also described.

Isotopic niches support the resource breadth hypothesis.

PubMed

Rader, Jonathan A; Newsome, Seth D; Sabat, Pablo; Chesser, R Terry; Dillon, Michael E; Martínez Del Rio, Carlos

2017-03-01

Because a broad spectrum of resource use allows species to persist in a wide range of habitat types, and thus permits them to occupy large geographical areas, and because broadly distributed species have access to more diverse resource bases, the resource breadth hypothesis posits that the diversity of resources used by organisms should be positively related with the extent of their geographic ranges. We investigated isotopic niche width in a small radiation of South American birds in the genus Cinclodes. We analysed feathers of 12 species of Cinclodes to test the isotopic version of the resource breadth hypothesis and to examine the correlation between isotopic niche breadth and morphology. We found a positive correlation between the widths of hydrogen and oxygen isotopic niches (which estimate breadth of elevational range) and widths of the carbon and nitrogen isotopic niches (which estimates the diversity of resources consumed, and hence of habitats used). We also found a positive correlation between broad isotopic niches and wing morphology. Our study not only supports the resource breadth hypothesis but it also highlights the usefulness of stable isotope analyses as tools in the exploration of ecological niches. It is an example of a macroecological application of stable isotopes. It also illustrates the importance of scientific collections in ecological studies. © 2016 The Authors. Journal of Animal Ecology © 2016 British Ecological Society.

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

NASA Astrophysics Data System (ADS)

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

2008-02-01

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

Reconstruction of historical lead contamination and sources in Lake Hailing, Eastern China: a Pb isotope study.

PubMed

Zhang, Rui; Guan, Minglei; Shu, Yujie; Shen, Liya; Chen, Xixi; Zhang, Fan; Li, Tiegang; Jiang, Tingchen

2016-05-01

The history records of lead and its stable isotopic ratios were determined in a sediment core to receive anthropogenic impacts on the Lake Hailing in eastern China. The sediment core was dated based on (210)Pb, (137)Cs, and (239+240)Pu. The historical changes of Pb/Al and Pb isotope ratios showed increasing trend upward throughout the core, suggesting changes in energy usage and correlating closely with the experience of a rapid economic and industrial development of the catchment, Linyi City, in eastern China. Based on the mixing end member model of Pb isotope ratios, coal combustion emission dominated anthropogenic Pb sources in the half part of the century contributing 13 to 43 % of total Pb in sediment. Moreover, contributions of chemical and organic fertilizer were 1-13 and 5-14 %, respectively. In contrast, the contribution of leaded gasoline was low than 8 %. The results indicated that historical records of Pb contamination predominantly sourced from coal combustion and chemical and organic fertilizer in the catchment. In addition, an increase of coal combustion source and fertilizers was found throughout the sediment core, whereas the contribution of leaded gasoline had declined after 2000s, which is attributed to the phaseout of leaded gasoline in China.

A modified lead-matrix separation procedure shown for lead isotope analysis in Trojan silver artefacts as an example.

PubMed

Vogl, Jochen; Paz, Boaz; Koenig, Maren; Pritzkow, Wolfgang

2013-03-01

A modified Pb-matrix separation procedure using NH4HCO3 solution as eluent has been developed and validated for determination of Pb isotope amount ratios by thermal ionization mass spectrometry. The procedure is based on chromatographic separation using the Pb·Spec resin and an in-house-prepared NH4HCO3 solution serving as eluent. The advantages of this eluent are low Pb blanks (<40 pg mL(-1)) and the property that NH4HCO3 can be easily removed by use of a heating step (>60 °C). Pb recovery is >95 % for water samples. For archaeological silver samples, however, the Pb recovery is reduced to approximately 50 %, but causes no bias in the determination of Pb isotope amount ratios. The validated procedure was used to determine lead isotope amount ratios in Trojan silver artefacts with expanded uncertainties (k = 2) <0.09 %.

Exposure assessment of lead from food and airborne dusts and biomonitoring in pregnant mothers, their fetus and siblings in Karachi, Pakistan and Shimotsuke, Japan.

PubMed

Kayama, Fujio; Fatmi, Zafar; Ikegami, Akihiko; Mizuno, Atsuko; Ohtsu, Mayumi; Mise, Nathern; Cui, Xiaoyi; Ogawa, Masanori; Sakamoto, Takako; Nakagi, Yoshiko; Yoshida, Takahiko; Sahito, Ambreen; Naeem, Shahla; Ghias, Kulsoom; Zuberi, Hina; Tariq, Kanwal; Kobayashi, Yayoi; Nohara, Keiko

2016-03-01

Exposure assessment of lead (Pb) and Arsenic (As) from food, water, and house dust intake were assessed among pregnant women, their children and fetuses in Pakistan and Japan, as well as their body burden of the metals in their blood. Fifty families which included a pregnant woman, a fetus and the 1-3-year-old siblings were recruited in Karachi and Khairpur in Pakistan, and Shimotsuke and Asahikawa in Japan, respectively. Their dietary exposure to Pb and As was measured in 3-day food duplicates and drinking water by ICP-MP. Pb in house dust and respirable dust was evaluated with an energy dispersive X-ray fluorescence spectrometry. Non-radioactive isotope Pb profiles of blood specimens will be compared with those of the exposure origins, such as food duplicates, respirable house dust, the soils nearby, and gasoline. Judging from the data collected and analyzed so far, contribution from dietary intake is highly correlated to higher body burden of Pb among Pakistani mothers. Additional data analyses will reveal the status of Pb and As body burden in Pakistani mothers, fetuses and their siblings, and causal sources of high body burden is delineated by Pb isotope profile analysis of different sources of Pb exposure.

Trace metal inventories and lead isotopic composition chronicle a forest fire's remobilization of industrial contaminants deposited in the angeles national forest.

PubMed

Odigie, Kingsley O; Flegal, A Russell

2014-01-01

The amounts of labile trace metals: [Co] (3 to 11 µg g-1), [Cu] (15 to 69 µg g-1), [Ni] (6 to 15 µg g-1), [Pb] (7 to 42 µg g-1), and [Zn] (65 to 500 µg g-1) in ash collected from the 2012 Williams Fire in Los Angeles, California attest to the role of fires in remobilizing industrial metals deposited in forests. These remobilized trace metals may be dispersed by winds, increasing human exposures, and they may be deposited in water bodies, increasing exposures in aquatic ecosystems. Correlations between the concentrations of these trace metals, normalized to Fe, in ash from the fire suggest that Co, Cu, and Ni in most of those samples were predominantly from natural sources, whereas Pb and Zn were enriched in some ash samples. The predominantly anthropogenic source of excess Pb in the ash was further demonstrated by its isotopic ratios (208Pb/207Pb: 206Pb/207Pb) that fell between those of natural Pb and leaded gasoline sold in California during the previous century. These analyses substantiate current human and environmental health concerns with the pyrogenic remobilization of toxic metals, which are compounded by projections of increases in the intensity and frequency of wildfires associated with climate change.

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

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

Isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS) for the certification of lead and cadmium in environmental standard reference materials.

PubMed

Murphy, K E; Beary, E S; Rearick, M S; Vocke, R D

2000-10-01

Lead (Pb) and cadmium (Cd) have been determined in six new environmental standard reference materials (SRMs) using isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS). The SRMs are the following: SRM 1944, New York-New Jersey Waterway Sediment, SRMs 2583 and 2584, Trace Elements in Indoor Dust, Nominal 90 mg/kg and 10,000 mg/kg Lead, respectively, SRMs 2586 and 2587, Trace Elements in Soil Containing Lead from Paint, Nominal 500 mg/kg and 3,000 mg/kg Lead, respectively, and SRM 2782, Industrial Sludge. The capabilities of ID ICP-MS for the certification of Pb and Cd in these materials are assessed. Sample preparation and ratio measurement uncertainties have been evaluated. Reproducibility and accuracy of the established procedures are demonstrated by determination of gravimetrically prepared primary standard solutions and by comparison with isotope dilution thermal ionization mass spectrometry (ID TIMS). Material heterogeneity was readily demonstrated to be the dominant source of uncertainty in the certified values.

Laser photochemical lead isotopes separation for harmless nuclear power engineering

NASA Astrophysics Data System (ADS)

Bokhan, P. A.; Fateev, N. V.; Kim, V. A.; Zakrevsky, D. E.

2016-09-01

The collisional quenching of the metastable 3 P 1,2 and 1 D 2 lead atoms is studied experimentally in the gas flow of the lead atoms, reagent-molecules and a carrier gas Ar. The experimental parameters were similar to the conditions that are required in the operation of the experimental setup for photochemical isotope separation. Excited atoms are generated under electron impact conditions created by a gas glow discharge through the mixture of gases and monitored photoelectrically by attenuation of atomic resonance radiation from hollow cathode 208Pb lamp. The decay of the excited atoms has been studied in the presence various molecules and total cross section data are reported. The flow tube measurements has allowed to separate the physical and chemical quenching channels and measure the rates of the chemical reaction excited lead with N2O, CH2Cl2, SF6 and CuBr molecules. These results are discussed in the prospects of the obtaining isotopically modified lead as a promising coolant in the reactors on the fast-neutron.

Chromium Stable Isotope Fractionation - An Indicator of Hexavalent Chromium Reduction.

NASA Astrophysics Data System (ADS)

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

2001-12-01

Chromium is a common anthropogenic contaminant in surface water and ground water, and is also of interest in oceanography. It is redox-active; the two common valences in natural waters are Cr(VI), which is highly soluble and toxic, and Cr(III), which is relatively insoluble. Redox reactions thus control Cr mobility in aqueous solutions, and reduction of Cr(VI) to Cr(III) is the most important reaction controlling attenuation of Cr in groundwater. Our results show that Cr(VI) reduction favors the lighter isotopes and leads to enrichment of heavier isotopes in the remaining Cr(VI). Cr isotope measurements thus show great promise as indicators of Cr(VI) reduction. We report here the first measurements of the magnitude of Cr isotope fractionation during Cr(VI) reduction and variations in δ 53Cr values obtained from three contaminated sites. Experiments were conducted to measure Cr isotope fractionation during Cr(VI) reduction by suspensions of magnetite and unamended sediments from a local pond, Urbana, IL and San Francisco Estuary near Martinez, CA. Suspensions were incubated anaerobically with constant shaking, and complete Cr(VI) reduction occurred within a few days. Cr(VI) from intermediate time points in the experiments was purified via ion exchange and 53Cr/52Cr ratios were measured via TIMS with a double isotope spike. The instantaneous per mil fractionation, ɛ , was calculated assuming a Rayleigh fractionation model. The ɛ for Cr(VI) reduction on magnetite surfaces yielded a fractionation of -3.5 ‰ . The ɛ values for the pond and estuary sediments were -3.5 ‰ and -3.3 ‰ respectively. The size of this Cr isotope fractionation is encouraging, as current precision is 0.2 \\permil. δ 53Cr values in dissolved Cr(VI) from three contaminated sites range from 1.1 ‰ to 5.8 ‰ , suggesting that Cr(VI) reduction has occurred and has induced isotopic fractionation in these settings. δ 53Cr values measured from Cr(VI) in plating baths show little or no fractionation during plating operations during up to 5 years of use. These results demonstrate that Cr stable isotope analyses should be a highly practical indicator of the critical chromate reduction reaction, and an otherwise useful geologic and oceanographic tool.

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

NASA Technical Reports Server (NTRS)

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

1990-01-01

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

Validation of tungsten cross sections in the neutron energy region up to 100 keV

NASA Astrophysics Data System (ADS)

Pigni, Marco T.; Žerovnik, Gašper; Leal, Luiz. C.; Trkov, Andrej

2017-09-01

Following a series of recent cross section evaluations on tungsten isotopes performed at Oak Ridge National Laboratory (ORNL), this paper presents the validation work carried out to test the performance of the evaluated cross sections based on lead-slowing-down (LSD) benchmarks conducted in Grenoble. ORNL completed the resonance parameter evaluation of four tungsten isotopes - 182,183,184,186W - in August 2014 and submitted it as an ENDF-compatible file to be part of the next release of the ENDF/B-VIII.0 nuclear data library. The evaluations were performed with support from the US Nuclear Criticality Safety Program in an effort to provide improved tungsten cross section and covariance data for criticality safety sensitivity analyses. The validation analysis based on the LSD benchmarks showed an improved agreement with the experimental response when the ORNL tungsten evaluations were included in the ENDF/B-VII.1 library. Comparison with the results obtained with the JEFF-3.2 nuclear data library are also discussed.

Target materials for exotic ISOL beams

NASA Astrophysics Data System (ADS)

Gottberg, A.

2016-06-01

The demand for intensity, purity, reliability and availability of short-lived isotopes far from stability is steadily high, and considerably exceeding the supply. In many cases the ISOL (Isotope Separation On-Line) method can provide beams of high intensity and purity. Limitations in terms of accessible chemical species and minimum half-life are driven mainly by chemical reactions and physical processes inside of the thick target. A wide range of materials are in use, ranging from thin metallic foils and liquids to refractory ceramics, while poly-phasic mixed uranium carbides have become the reference target material for most ISOL facilities world-wide. Target material research and development is often complex and especially important post-irradiation analyses are hindered by the high intrinsic radiotoxicity of these materials. However, recent achievements have proven that these investigations are possible if the effort of different facilities is combined, leading to the development of new material matrices that can supply new beams of unprecedented intensity and beam current stability.

Lead chromate detected as a source of atmospheric Pb and Cr (VI) pollution.

PubMed

Lee, Pyeong-Koo; Yu, Soonyoung; Chang, Hye Jung; Cho, Hye Young; Kang, Min-Ju; Chae, Byung-Gon

2016-10-25

Spherical black carbon aggregates were frequently observed in dust dry deposition in Daejeon, Korea. They were tens of micrometers in diameter and presented a mixture of black carbon and several mineral phases. Transmission electron microscopy (TEM) observations with energy-dispersive X-ray spectroscopy (EDS) and selected area diffraction pattern (SADP) analyses confirmed that the aggregates were compact and included significant amounts of lead chromate (PbCrO 4 ). The compositions and morphologies of the nanosized lead chromate particles suggest that they probably originated from traffic paint used in roads and were combined as discrete minerals with black carbon. Based on Pb isotope analysis and air-mass backward trajectories, the dust in Daejeon received a considerable input of anthropogenic pollutants from heavily industrialized Chinese cities, which implies that long-range transported aerosols containing PbCrO 4 were a possible source of the lead and hexavalent chromium levels in East Asia. Lead chromate should be considered to be a source of global atmospheric Pb and Cr(VI) pollution, especially given its toxicity.

Lead chromate detected as a source of atmospheric Pb and Cr (VI) pollution

NASA Astrophysics Data System (ADS)

Lee, Pyeong-Koo; Yu, Soonyoung; Chang, Hye Jung; Cho, Hye Young; Kang, Min-Ju; Chae, Byung-Gon

2016-10-01

Spherical black carbon aggregates were frequently observed in dust dry deposition in Daejeon, Korea. They were tens of micrometers in diameter and presented a mixture of black carbon and several mineral phases. Transmission electron microscopy (TEM) observations with energy-dispersive X-ray spectroscopy (EDS) and selected area diffraction pattern (SADP) analyses confirmed that the aggregates were compact and included significant amounts of lead chromate (PbCrO4). The compositions and morphologies of the nanosized lead chromate particles suggest that they probably originated from traffic paint used in roads and were combined as discrete minerals with black carbon. Based on Pb isotope analysis and air-mass backward trajectories, the dust in Daejeon received a considerable input of anthropogenic pollutants from heavily industrialized Chinese cities, which implies that long-range transported aerosols containing PbCrO4 were a possible source of the lead and hexavalent chromium levels in East Asia. Lead chromate should be considered to be a source of global atmospheric Pb and Cr(VI) pollution, especially given its toxicity.

Lead chromate detected as a source of atmospheric Pb and Cr (VI) pollution

PubMed Central

Lee, Pyeong-Koo; Yu, Soonyoung; Chang, Hye Jung; Cho, Hye Young; Kang, Min-Ju; Chae, Byung-Gon

2016-01-01

Spherical black carbon aggregates were frequently observed in dust dry deposition in Daejeon, Korea. They were tens of micrometers in diameter and presented a mixture of black carbon and several mineral phases. Transmission electron microscopy (TEM) observations with energy-dispersive X-ray spectroscopy (EDS) and selected area diffraction pattern (SADP) analyses confirmed that the aggregates were compact and included significant amounts of lead chromate (PbCrO4). The compositions and morphologies of the nanosized lead chromate particles suggest that they probably originated from traffic paint used in roads and were combined as discrete minerals with black carbon. Based on Pb isotope analysis and air-mass backward trajectories, the dust in Daejeon received a considerable input of anthropogenic pollutants from heavily industrialized Chinese cities, which implies that long-range transported aerosols containing PbCrO4 were a possible source of the lead and hexavalent chromium levels in East Asia. Lead chromate should be considered to be a source of global atmospheric Pb and Cr(VI) pollution, especially given its toxicity. PMID:27779222

Clumped isotope paleothermometry of eggshells as an indicator of vertebrate endothermy

NASA Astrophysics Data System (ADS)

Canavan, R. R.; Field, D. J.; Therrien, F.; Zelenitsky, D.; Affek, H. P.

2014-12-01

Isotopic analyses of the calcite or aragonite shells of aquatic organisms are often used in the study of the environmental conditions in which they grow; however, this approach is less straightforward in the terrestrial realm, where environments may be more heterogeneous. In such terrestrial localities, the bioapatite of vertebrate teeth comprises the typical archival material for isotopic analyses. The calcitic eggshells of birds and other reptiles may provide suitable material for isotopic analyses that are aimed at studying their physiology and ecology. Here we apply a novel thermometer, carbonate clumped isotopes (Δ47), to test for endothermy in extinct non-avian dinosaurs in the context provided by eggs of modern reptiles and birds. These Δ47-derived temperatures should reflect the temperature of shell formation, which in endothermic animals such as birds should represent the mother's internal body temperature. In ectothermic animals, the same is true although their body temperatures are more affected by the external environment and thus Δ47 temperatures could more accurately describe local environmental temperatures during eggshell formation. Fossil eggshells represent appropriate material for reconstructing internal body temperatures of extinct non-avian dinosaurs since they mineralized within the mother's body, and fragments of eggshell are commonly recovered from dinosaur-bearing fossil deposits. The dimensions of these fragments provide sufficient material for the relatively large sample required for clumped isotope analysis (~20mg). Fossil eggshell samples from several taxa of Late Cretaceous non-avian dinosaurs were analyzed using Δ47 paleothermometry. Textural inspection was used as a first test for diagenetic alteration of the original calcite, and histological indicators were used for broad taxonomic identifications. Preliminary results of Δ47-derived body temperature estimates from eggshells are consistent with previous body temperatures estimates from bioapatite Δ47 analyses performed on non-avian dinosaur teeth.

Ion microprobe analysis of {sup 18}O/{sup 16}O in authigenic and detrital quartz in the St. Peter Sandstone, Michigan Basin and Wisconsin Arch, USA: Contrasting diagenetic histories

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

Graham, C.M.; Valley, J.W.; Winter, B.L.

1996-12-01

The oxygen isotopic compositions of authigenic quartz cements in sandstones provide a monitor of the temperatures, compositions, and origins of pore-occluding fluids during diagenesis, but quartz overgrowths are too fine-grained to be amenable to conventional isotopic analysis. We have used a Cameca ims-4f ion microprobe to determine oxygen isotopic variations in authigenic and detrital quartz in four samples of the Ordovician St. Peter Sandstone from the Michigan Basin and Wisconsin Arch, midwestern USA. Ion microprobe isotopic analyses have been successfully accomplished with an internal precision of {+-}1{per_thousand} (1{sigma}) and a spatial resolution of 20-30 {mu}m at low mass resolution usingmore » a high voltage offset technique. Repeated analyses of the quartz standard demonstrate a reproducibility of close to {+-}1{per_thousand} (1 sd) in good agreement with that expected from counting statistics. Conventional and ion microprobe analyses are mutually consistent, supporting the accuracy of the ion microprobe analyses. Within-sample isotopic variations of up to 13{per_thousand} and micro-scale isotopic variations of at least 4{per_thousand} over a distance of 100 {mu}m have been measured within quartz overgrowths in a sandstone from the Wisconsin Arch. Overgrowths are uniformly higher in {delta}{sup 18}O than detrital grains, and gradients of up to 25% exist across a few microns. {sup 18}O-enriched quartz overgrowths in sandstones from the Wisconsin Arch show complex CL zonation and reflect one of two possible processes: (1) low-temperature quartz precipitation during mixing of meteoric waters with upwelling basinal fluids; (2) higher temperature quartz precipitation during episodic gravity-driven upwelling of warm basinal fluids (of comparable isotopic composition to Michigan Basin fluids) from the Illinois Basin, related to evolution of Mississippi Valley type Pb-Zn ore-forming fluids. 59 refs., 7 figs., 4 tabs.« less

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Tracking the weathering of basalts on Mars using lithium isotope fractionation models

PubMed Central

Losa‐Adams, Elisabeth; Gil‐Lozano, Carolina; Gago‐Duport, Luis; Uceda, Esther R.; Squyres, Steven W.; Rodríguez, J. Alexis P.; Davila, Alfonso F.; McKay, Christopher P.

2015-01-01

Abstract Lithium (Li), the lightest of the alkali elements, has geochemical properties that include high aqueous solubility (Li is the most fluid mobile element) and high relative abundance in basalt‐forming minerals (values ranking between 0.2 and 12 ppm). Li isotopes are particularly subject to fractionation because the two stable isotopes of lithium—7Li and 6Li—have a large relative mass difference (∼15%) that results in significant fractionation between water and solid phases. The extent of Li isotope fractionation during aqueous alteration of basalt depends on the dissolution rate of primary minerals—the source of Li—and on the precipitation kinetics, leading to formation of secondary phases. Consequently, a detailed analysis of Li isotopic ratios in both solution and secondary mineral lattices could provide clues about past Martian weathering conditions, including weathering extent, temperature, pH, supersaturation, and evaporation rate of the initial solutions in contact with basalt rocks. In this paper, we discuss ways in which Martian aqueous processes could have lead to Li isotope fractionation. We show that Li isotopic data obtained by future exploration of Mars could be relevant to highlighting different processes of Li isotopic fractionation in the past, and therefore to understanding basalt weathering and environmental conditions early in the planet's history. PMID:27642264

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.

On the Use of Biomineral Oxygen Isotope Data to Identify Human Migrants in the Archaeological Record: Intra-Sample Variation, Statistical Methods and Geographical Considerations

PubMed Central

Lightfoot, Emma; O’Connell, Tamsin C.

2016-01-01

Oxygen isotope analysis of archaeological skeletal remains is an increasingly popular tool to study past human migrations. It is based on the assumption that human body chemistry preserves the δ18O of precipitation in such a way as to be a useful technique for identifying migrants and, potentially, their homelands. In this study, the first such global survey, we draw on published human tooth enamel and bone bioapatite data to explore the validity of using oxygen isotope analyses to identify migrants in the archaeological record. We use human δ18O results to show that there are large variations in human oxygen isotope values within a population sample. This may relate to physiological factors influencing the preservation of the primary isotope signal, or due to human activities (such as brewing, boiling, stewing, differential access to water sources and so on) causing variation in ingested water and food isotope values. We compare the number of outliers identified using various statistical methods. We determine that the most appropriate method for identifying migrants is dependent on the data but is likely to be the IQR or median absolute deviation from the median under most archaeological circumstances. Finally, through a spatial assessment of the dataset, we show that the degree of overlap in human isotope values from different locations across Europe is such that identifying individuals’ homelands on the basis of oxygen isotope analysis alone is not possible for the regions analysed to date. Oxygen isotope analysis is a valid method for identifying first-generation migrants from an archaeological site when used appropriately, however it is difficult to identify migrants using statistical methods for a sample size of less than c. 25 individuals. In the absence of local previous analyses, each sample should be treated as an individual dataset and statistical techniques can be used to identify migrants, but in most cases pinpointing a specific homeland should not be attempted. PMID:27124001

Normalization of oxygen and hydrogen isotope data

USGS Publications Warehouse

Coplen, T.B.

1988-01-01

To resolve confusion due to expression of isotopic data from different laboratories on non-corresponding scales, oxygen isotope analyses of all substances can be expressed relative to VSMOW or VPDB (Vienna Peedee belemnite) on scales normalized such that the ??18O of SLAP is -55.5% relative to VSMOW. H3+ contribution in hydrogen isotope ratio analysis can be easily determined using two gaseous reference samples that differ greatly in deuterium content. ?? 1988.

Environmental Survey of the B-3 and Ford’s Farm Ranges,

DTIC Science & Technology

1983-08-01

reported have an estimated analytical error of *35% unless noted otherwise. 14 Isotopic Analysis The isotopic uranium analysis procedure used by UST...sulfate buffer and elec- trodeposited on a stainless steel disc, and isotopes of uranium (234U, 23 5U, and 2 38U) were determined by pulse height analysis ...measurements and some environmental sampling. Several special studies were also conducted, including analyses of the isotopic composition of uranium in

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

PubMed

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

2014-02-01

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

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

PubMed

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

2017-02-07

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

Natural isotope correction of MS/MS measurements for metabolomics and (13)C fluxomics.

PubMed

Niedenführ, Sebastian; ten Pierick, Angela; van Dam, Patricia T N; Suarez-Mendez, Camilo A; Nöh, Katharina; Wahl, S Aljoscha

2016-05-01

Fluxomics and metabolomics are crucial tools for metabolic engineering and biomedical analysis to determine the in vivo cellular state. Especially, the application of (13)C isotopes allows comprehensive insights into the functional operation of cellular metabolism. Compared to single MS, tandem mass spectrometry (MS/MS) provides more detailed and accurate measurements of the metabolite enrichment patterns (tandem mass isotopomers), increasing the accuracy of metabolite concentration measurements and metabolic flux estimation. MS-type data from isotope labeling experiments is biased by naturally occurring stable isotopes (C, H, N, O, etc.). In particular, GC-MS(/MS) requires derivatization for the usually non-volatile intracellular metabolites introducing additional natural isotopes leading to measurements that do not directly represent the carbon labeling distribution. To make full use of LC- and GC-MS/MS mass isotopomer measurements, the influence of natural isotopes has to be eliminated (corrected). Our correction approach is analyzed for the two most common applications; (13)C fluxomics and isotope dilution mass spectrometry (IDMS) based metabolomics. Natural isotopes can have an impact on the calculated flux distribution which strongly depends on the substrate labeling and the actual flux distribution. Second, we show that in IDMS based metabolomics natural isotopes lead to underestimated concentrations that can and should be corrected with a nonlinear calibration. Our simulations indicate that the correction for natural abundance in isotope based fluxomics and quantitative metabolomics is essential for correct data interpretation. © 2015 Wiley Periodicals, Inc.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields.

PubMed

Gulson, Brian; Kamenov, George D; Manton, William; Rabinowitz, Michael

2018-04-11

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208 Pb/ 206 Pb and 207 Pb/ 206 Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields

PubMed Central

Gulson, Brian; Manton, William; Rabinowitz, Michael

2018-01-01

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208Pb/206Pb and 207Pb/206Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields. PMID:29641487

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.

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

PubMed

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

2017-04-01

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

Evidence of transboundary mercury and other pollutants in the Puyango-Tumbes River basin, Ecuador-Peru.

PubMed

Marshall, Bruce G; Veiga, Marcello M; Kaplan, Robert J; Adler Miserendino, Rebecca; Schudel, Gary; Bergquist, Bridget A; Guimarães, Jean R D; Sobral, Luis G S; Gonzalez-Mueller, Carolina

2018-04-25

In Portovelo in southern Ecuador, 87 gold processing centers along the Puyango-Tumbes River produce an estimated 6 tonnes of gold per annum using a combination of mercury amalgamation and/or cyanidation and processing poly-metallic ores. We analysed total Hg, Hg isotopes, total arsenic, cadmium, copper, lead and zinc in water and sediment along the Puyango in 2012-2014. The highest total mercury (THg) concentrations in sediments were found within a 40 km stretch downriver from the processing plants, with levels varying between 0.78-30.8 mg kg-1 during the dry season and 1.80-70.7 mg kg-1 during the wet season, with most concentrations above the CCME (Canadian Council of Ministers of the Environment) Probable Effect Level (PEL) of 0.5 mg kg-1. Data from mercury isotopic analyses support the conclusion that mercury use during gold processing in Portovelo is the source of Hg pollution found downstream in the Tumbes Delta in Peru, 160 km away. The majority of the water and sediment samples collected from the Puyango-Tumbes River had elevated concentrations of, arsenic, cadmium, copper, lead and zinc exceeding the CCME thresholds for the Protection of Aquatic Life. At monitoring points immediately below the processing plants, total dissolved concentrations of these metals exceeded the thresholds by 156-3567 times in surface waters and by 19-740 times in sediment. The results illustrate a significant transboundary pollution problem involving Hg and other toxic metals, amplified by the fact that the Puyango-Tumbes River is the only available water source in the semi-arid region of northern Peru.

Constraints on Martian Differentiation Processes from Rb-Sr and Sm-Nd Isotopic Analyses of the Basaltic Shergottite QUE 94201

NASA Technical Reports Server (NTRS)

Borg, Lars E.; Nyquist, Larry E.; Taylor, Larry A.; Wiesmann, Henry; Shih, Chi-Y.

1997-01-01

Isotopic analyses of mineral, leachate, and whole rock fractions from the Martian shergottite meteorite QUE 94201 yield Rb-Sr and Sm-Nd crystallization ages of 327 +/- 12 and 327 +/- 19 Ma, respectively. These ages are concordant, although the isochrons are defined by different fractions within the meteorite. Comparison of isotope dilution Sm and Nd data for the various QUE 94201 fractions with in situ ion microprobe data for QUE 94201 minerals from the literature demonstrate the presence of a leachable crustal component in the meteorite. This component is likely to have been added to QUE 94201 by secondary alteration processes on Mars, and can affect the isochrons by selectively altering the isotopic systematics of the leachates and some of the mineral fractions. The absence of crustal recycling processes on Mars may preserve the geochemical evidence for early differentiation and the decoupling of the Rb-Sr and Sm-Nd isotopic systems, underscoring one of the fundamental differences between geologic processes on Mars and the Earth.

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Quantitative assessment of Pb sources in isotopic mixtures using a Bayesian mixing model.

PubMed

Longman, Jack; Veres, Daniel; Ersek, Vasile; Phillips, Donald L; Chauvel, Catherine; Tamas, Calin G

2018-04-18

Lead (Pb) isotopes provide valuable insights into the origin of Pb within a sample, typically allowing for reliable fingerprinting of their source. This is useful for a variety of applications, from tracing sources of pollution-related Pb, to the origins of Pb in archaeological artefacts. However, current approaches investigate source proportions via graphical means, or simple mixing models. As such, an approach, which quantitatively assesses source proportions and fingerprints the signature of analysed Pb, especially for larger numbers of sources, would be valuable. Here we use an advanced Bayesian isotope mixing model for three such applications: tracing dust sources in pre-anthropogenic environmental samples, tracking changing ore exploitation during the Roman period, and identifying the source of Pb in a Roman-age mining artefact. These examples indicate this approach can understand changing Pb sources deposited during both pre-anthropogenic times, when natural cycling of Pb dominated, and the Roman period, one marked by significant anthropogenic pollution. Our archaeometric investigation indicates clear input of Pb from Romanian ores previously speculated, but not proven, to have been the Pb source. Our approach can be applied to a range of disciplines, providing a new method for robustly tracing sources of Pb observed within a variety of environments.

A new serial pooling method of shifted tree ring blocks to construct millennia long tree ring isotope chronologies with annual resolution.

PubMed

Boettger, Tatjana; Friedrich, Michael

2009-03-01

The study presents a new serial pooling method of shifted tree ring blocks for the building of isotope chronologies. This method combines the advantages of traditional 'serial' and 'intertree' pooling, and can be recommended for the construction of sub-regional long isotope chronologies with sufficient replication, and on annual resolution, especially for the case of extremely narrow tree rings. For Scots pines (Pinus sylvestris L., Khibiny Low Mountains, NW Russia) and Silver firs (Abies alba Mill., Franconia, Southern Germany), serial pooling of five consecutive tree rings seems appropriate because the species- and site-specific particularities lead to blurs of climate linkages in their tree rings for the period up to ca. five years back. An equivalent to a five-year running means that curve gained on the base annual data sets of single trees can be derived from the analysis of yearly shifted five-year blocks of consecutive tree rings, and therefore, with approximately 20% of the expense. Good coherence of delta(13)C- and delta(18)O-values between calculated means of annual total rings or late wood data and means of five-year blocks of consecutive total tree rings analysed experimentally on most similar material confirms this assumption.

Unthinned slow-growing ponderosa pine (Pinus ponderosa) trees contain muted isotopic signals in tree rings as compared to thinned trees

EPA Science Inventory

We analysed the oxygen isotopic values of wood (δ18Ow) of 12 ponderosa pine (Pinus ponderosa) trees from control, moderately, and heavily thinned stands and compared them with existing wood-based estimates of carbon isotope discrimination (∆13C), basal area increment (BAI), and g...

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

USGS Publications Warehouse

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

1986-01-01

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

Lead concentration and isotope chronology in two coastal environments in Western and South East Asia

NASA Astrophysics Data System (ADS)

Carrasco, G. G.; Chen, M.; Boyle, E. A.; Zhao, N.; Nurhati, I. S.; Gevao, B.; al Ghadban, A.; Switzer, A.; Lee, J. M.

2014-12-01

Lead is a trace metal that is closely related to anthropogenic activity, mainly via leaded gasoline and coal combustion. The study of lead concentrations and isotopes in seawater, sediments, corals and aerosols allows for a systematic look at its sources and their time evolution in a natural environment. We will discuss results from two projects in Western and South East Asia, regions that have seen dramatic socio-economical changes over the past half-century that may have left environmental signals. These results highlight the usefulness of the method, indicate the degree of complexity of these systems, and point to the need for a continuous monitoring of anthropogenic trace metals in the small-medium coastal scale to be able to asses the larger scale effects of human activity. On the one hand, coastal Kuwait is heavily influenced by the Shat al-Arab river and shows a clear anthropogenic signature from Kuwait city. A mix of two sources can be tracked through the coral and sediment chronological records, with Pb206/Pb207 ratios (1.202 and 1.151) that approach the suspected source values (1.21 and 1.12) and eliminate the possibility of other sources. Through a wide sediment geographic distribution, the strength of the anthropogenic signature is modulated. On the other hand, Singapore offers a more complex system, where an apparent mix of two sources (extreme isotope ratios 1.215 and ~1.14) occurs also, but where either an unresolved potentially important third source (isotope ratio ~1.18), or an isotope exchange process should be invoked. The sediment and coral records allows us to track the changes through time; however, there seems to be incongruence with the aerosol isotope record. Further potential sources are being explored currently and will be discussed.

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

Bowman, J.R.; Rohrs, D.T.

The isotopic compositions of hydrogen and oxygen have been determined for spring waters and thermal fluids from the Roosevelt Hot Springs and Cove Fort-Sulphurdale thermal areas, for clay mineral separates from shallow alteration of the acid-sulfate type in the Roosevelt Hot Springs area, and for spring and well waters from the Goshen Valley area of central Utah. The water analyses in the Roosevelt Hot Springs thermal area confirm the origin of the thermal fluids from meteoric water in the Mineral Range. The water analyses in the Cove Fort-Sulphurdale thermal area restrict recharge areas for this system to the upper elevationsmore » of the Pavant and/or Tushar Ranges. The low /sup 18/O shift observed in these thermal fluids (+0.7 permil) implies either high water/rock ratios or incomplete isotope exchange or both, and further suggests minimal interaction between the thermal fluid and marble country rock in the system. Hydrogen and oxygen-isotope data for clay mineral separates from shallow alteration zones in the Roosevelt Hot Springs thermal system suggest that the fluids responsible for the shallow acid-sulfate alteration were in part derived from condensed steam produced by boiling of the deep reservoir fluid. The isotope evidence supports the chemical model proposed by Parry et al. (1980) for origin of the acid-sulfate alteration at Roosevelt Hot Springs. The isotope analyses of spring and well waters from the Goshen Valley area indicate only a general correlation of isotope composition, salinity and chemical temperatures.« less

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

Facchetti, S.

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

Laboratory Protocol for Genetic Gut Content Analyses of Aquatic Macroinvertebrates Using Group-specific rDNA Primers.

PubMed

Koester, Meike; Gergs, René

2017-10-05

Analyzing food webs is essential for a better understanding of ecosystems. For example, food web interactions can undergo severe changes caused by the invasion of non-indigenous species. However, an exact identification of field predator-prey interactions is difficult in many cases. These analyses are often based on a visual evaluation of gut content or the analysis of stable isotope ratios (δ 15 N and δ 13 C). Such methods require comprehensive knowledge about, respectively, morphologic diversity or isotopic signature from individual prey organisms, leading to obstacles in the exact identification of prey organisms. Visual gut content analyses especially underestimate soft bodied prey organisms, because maceration, ingestion and digestion of prey organisms make identification of specific species difficult. Hence, polymerase chain reaction (PCR) based strategies, for example the use of group-specific primer sets, provide a powerful tool for the investigation of food web interactions. Here, we describe detailed protocols to investigate the gut contents of macroinvertebrate consumers from the field using group-specific primer sets for nuclear ribosomal deoxyribonucleic acid (rDNA). DNA can be extracted either from whole specimens (in the case of small taxa) or out of gut contents of specimens collected in the field. Presence and functional efficiency of the DNA templates need to be confirmed directly from the tested individual using universal primer sets targeting the respective subunit of DNA. We also demonstrate that consumed prey can be determined further down to species level via PCR with unmodified group-specific primers combined with subsequent single strand conformation polymorphism (SSCP) analyses using polyacrylamide gels. Furthermore, we show that the use of different fluorescent dyes as labels enables parallel screening for DNA fragments of different prey groups from multiple gut content samples via automated fragment analysis.

Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets

NASA Technical Reports Server (NTRS)

Boering, Kristie A.; Connell, Peter; Rotman, Douglas

2004-01-01

We investigated the isotopic fractionation of CH4 and hydrogen (H2) in the stratosphere by incorporating isotope-specific rate coefficients into the Lawrence Livermore National Laboratory (LLNL) 2D model and comparing the model results with new observations from the NASA ER-2 aircraft (funded through a separate task under the Upper Atmosphere Research Program). The model results reveal that fractionation which occurs in the stratosphere has a significant influence on isotope compositions in the free troposphere, an important point which had previously been ignored, unrecognized or unquantified for many long-lived trace gases, including CH4 and H2 which we have focused our efforts on to date. Our analyses of the model results and new isotope observations have also been used to test how well the kinetic isotope effects are known, at least to within the uncertainties in model chemistry and transport. Overall, these results represent an important step forward in our understanding of isotope fractionation in the atmosphere and demonstrate that stratospheric isotope fractionation cannot be ignored in modeling studies which use isotope observations in the troposphere to infer the global budgets of CH4 (an important greenhouse gas) and of H2 (a gas whose atmospheric budget must be better quantified, particularly before a large human perturbation from fuel cell use is realized). Our analyses of model results and observations from the NASA ER-2 aircraft are briefly summarized separately below for CH4, H2, and H2O and for the contribution of these modeling studies to date to our understanding of isotope fractionation for N2O, CO2, and O3 as well.

Geochronological and lead-isotope evidences for rapid crust formation in middle-proterozoic time: The Labrador example

NASA Technical Reports Server (NTRS)

Schaerer, Urs

1988-01-01

Extensive U-Pb geochronological studies in the Grenville and Makkovik provinces have shown that eastern Labrador is underlain by two distinct crustal blocks. In order to substantiate the juvenile character of the middle-Proterozoic crustal block, the isotopic compositon of lead in leached k-feldspars from the same rocks were analyzed. The results of the analysis are briefly discussed.

The Cd and Zn Isotope Compositions of PM10 in the Atmosphere of Paris: New Tools for Discrimination and Tracking of the Origin of Metallic Pollution

NASA Astrophysics Data System (ADS)

Petelet-Giraud, E.; Widory, D.; Innocent, C.; Quetel, C.; Le Bihan, O.; Fraboulet, I.; Forti, L.; Joos, E.; Goupil, G.; Canard, E.

2008-12-01

Due to their relatively high concentration in urban environments (from 10 to more than 50 μg.m-3), atmospheric particles (PM10) have potential damaging effects on the Public Health. Hence, the development of measures dealing with fine particulate matter is considered a priority by the EU Clean Air For Europe (CAFE) Program. Still, the origin of these airborne particles is subject to debate, as classical chemical methods showed their limitations. Recent studies have shown that stable isotopes of elements such as carbon, nitrogen or lead could be of great help in the search of new particle air pollution tracking tools. We will present here preliminary results on the pioneer use of stable isotope compositions of cadmium, zinc and mercury to help decipher the different possible origins of PM10 pollution in the atmosphere of Paris (France). Main potential sources were characterized: (1) waste incineration, (2) road traffic, (3) central heating and (4) coal-fired power plants. Results show that the use of cadmium (d114Cd) and zinc (d66Zn) isotopes, and the combination of both provides a reliable and precise tool for discriminating the different families of particle vectors. The isotope systematic of mercury (d200Hg) is more difficult to apprehend due to the low levels encountered (mercury is mainly present under gaseous form, but is still observed at low concentrations in particles), but does show significant variations between the different sources. Daily cumulative air samples were taken on three different locations, covering different scenarios in Paris city: 1) background pollution in Paris, 2) under the plume of a major pollution source and 3) Paris vicinity. Corresponding chemical and isotope analyses help identify the main vectors for the three elements (Cd, Zn and Hg) considered as well as assess their respective contributions to the levels of pollution observed.

Evolving Pb isotope signatures of London airborne particulate matter (PM 10)-constraints from on-filter and solution-mode MC-ICP-MS.

PubMed

Noble, Stephen R; Horstwood, Matthew S A; Davy, Pamela; Pashley, Vanessa; Spiro, Baruch; Smith, Steve

2008-07-01

Pb isotope compositions of biologically significant PM(10) atmospheric particulates from a busy roadside location in London UK were measured using solution- and laser ablation-mode MC-ICP-MS. The solution-mode data for PM(10) sampled between 1998-2001 document a dramatic shift to increasingly radiogenic compositions as leaded petrol was phased out. LA-MC-ICP-MS isotope analysis, piloted on a subset of the available samples, is shown to be a potential reconnaissance analytical technique. PM(10) particles trapped on quartz filters were liberated from the filter surface, without ablating the filter substrate, using a 266 nm UV laser and a dynamic, large diameter, low-fluence ablation protocol. The Pb isotope evolution noted in the London data set obtained by both analytical protocols is similar to that observed elsewhere in Western Europe following leaded petrol elimination. The data therefore provide important baseline isotope composition information useful for continued UK atmospheric monitoring through the early 21(st) century.

Lead isotopic studies of lunar soils - Their bearing on the time scale of agglutinate formation

NASA Technical Reports Server (NTRS)

Church, S. E.; Tilton, G. R.; Chen, J. H.

1976-01-01

Fines (smaller than 75 microns) and bulk soil were studied to analyze loss of volatile lead; losses of the order of 10% to 30% radiogenic lead during the production of agglutinates are assessed. Lead isotope data from fine-agglutinate pairs are analyzed for information on the time scale of micrometeorite bombardment, from the chords generated by the data in concordia diagrams. Resulting mean lead loss ages were compared to spallogenic gas exposure ages for all samples. Labile parentless radiogenic Pb residing preferentially on or in the fines is viewed as possibly responsible for aberrant lead loss ages. Bulk soils plot above the concordia curve (in a field of excess radiogenic Pb) for all samples with anomalous ages.

Precambrian ophiolites of Arabia; a summary of geologic settings, U-Pb geochronology, lead isotope characteristics, and implications for microplate accretion, Kingdom of Saudi Arabia

USGS Publications Warehouse

Pallister, John S.; Stacey, J.S.; Fischer, L.B.; Premo, W.R.

1988-01-01

Feldspar lead-isotope data are of three types: 1) lead from the ophiolitic rocks and arc tonalites of the northwestern Arabian Shield and ophiolitic rocks of the Nabitah suture zone is similar to lead in present midocean ridge basalt, 2) anomalous radiogenic data from the Thurwah ophiolite are from rocks that contain zircons from pre-late Proterozoic continental crust, and 3) feldspar from the Urd ophiolite shows retarded uranogenic lead growth and is related either to an anomalous oceanic mantle source, or in an unknown manner to ancient continental mantle or lower crust of the eastern Arabian Shield.

Improved Discrimination for Brassica Vegetables Treated with Agricultural Fertilizers Using a Combined Chemometric Approach.

PubMed

Yuan, Yuwei; Hu, Guixian; Chen, Tianjin; Zhao, Ming; Zhang, Yongzhi; Li, Yong; Xu, Xiahong; Shao, Shengzhi; Zhu, Jiahong; Wang, Qiang; Rogers, Karyne M

2016-07-20

Multielement and stable isotope (δ(13)C, δ(15)N, δ(2)H, δ(18)O, (207)Pb/(206)Pb, and (208)Pb/(206)Pb) analyses were combined to provide a new chemometric approach to improve the discrimination between organic and conventional Brassica vegetable production. Different combinations of organic and conventional fertilizer treatments were used to demonstrate this authentication approach using Brassica chinensis planted in experimental test pots. Stable isotope analyses (δ(15)N and δ(13)C) of B. chinensis using elemental analyzer-isotope ratio mass spectrometry easily distinguished organic and chemical fertilizer treatments. However, for low-level application fertilizer treatments, this dual isotope approach became indistinguishable over time. Using a chemometric approach (combined isotope and elemental approach), organic and chemical fertilizer mixes and low-level applications of synthetic and organic fertilizers were detectable in B. chinensis and their associated soils, improving the detection limit beyond the capacity of individual isotopes or elemental characterization. LDA shows strong promise as an improved method to discriminate genuine organic Brassica vegetables from produce treated with chemical fertilizers and could be used as a robust test for organic produce authentication.

Deep reaching fluid flow in the North East German Basin: origin and processes of groundwater salinisation

NASA Astrophysics Data System (ADS)

Tesmer, M.; Möller, P.; Wieland, S.; Jahnke, C.; Voigt, H.; Pekdeger, A.

2007-11-01

Major element chemistry, rare-earth element distribution, and H and O isotopes are conjointly used to study the sources of salinisation and interaquifer flow of saline groundwater in the North East German Basin. Chemical analyses from hydrocarbon exploration campaigns showed evidence of the existence of two different groups of brines: halite and halite Ca-Cl brines. Residual brines and leachates are identified by Br-/Cl- ratios. Most of the brines are dissolution brines of Permian evaporites. New analyses show that the pattern of rare-earth elements and yttrium (REY) are closely linked to H and O isotope distribution. Thermal brines from deep wells and artesian wells indicate isotopically evaporated brines, which chemically interacted with their aquifer environment. Isotopes and rare-earth element patterns prove that cross flow exists, especially in the post-Rupelian aquifer. However, even at depths exceeding 2,000 m, interaquifer flow takes place. The rare-earth element pattern and H and O isotopes identify locally ascending brines. A large-scale lateral groundwater flow has to be assumed because all pre-Rupelian aquifer systems to a depth of at least 500 m are isotopically characterised by Recent or Pleistocene recharge conditions.

Analyses of microstructure, composition and retention of hydrogen isotopes in divertor tiles of JET with the ITER-like wall

NASA Astrophysics Data System (ADS)

Masuzaki, S.; Tokitani, M.; Otsuka, T.; Oya, Y.; Hatano, Y.; Miyamoto, M.; Sakamoto, R.; Ashikawa, N.; Sakurada, S.; Uemura, Y.; Azuma, K.; Yumizuru, K.; Oyaizu, M.; Suzuki, T.; Kurotaki, H.; Hamaguchi, D.; Isobe, K.; Asakura, N.; Widdowson, A.; Heinola, K.; Jachmich, S.; Rubel, M.; contributors, JET

2017-12-01

Results of the comprehensive surface analyses of divertor tiles and dusts retrieved from JET after the first ITER-like wall campaign (2011-2012) are presented. The samples cored from the divertor tiles were analyzed. Numerous nano-size bubble-like structures were observed in the deposition layer on the apron of the inner divertor tile, and a beryllium dust with the same structures were found in the matter collected from the inner divertor after the campaign. This suggests that the nano-size bubble-like structures can make the deposition layer to become brittle and may lead to cracking followed by dust generation. X-ray photoelectron spectroscopy analyses of chemical states of species in the deposition layers identified the formation of beryllium-tungsten intermetallic compounds on an inner vertical tile. Different tritium retention profiles along the divertor tiles were observed at the top surfaces and at deeper regions of the tiles by using the imaging plate technique.

Lead isotope ratio measurements as indicators for the source of lead poisoning in Mute swans (Cygnus olor) wintering in Puck Bay (northern Poland).

PubMed

Binkowski, Łukasz J; Meissner, Włodzimierz; Trzeciak, Marta; Izevbekhai, Kelvin; Barker, James

2016-12-01

Lead (Pb) poisoning is most commonly linked amongst anthropogenically-caused deaths in waterfowl and this is often associated with hunting and fishing activities. However, the exact identification of the source may be difficult with commonly-used techniques. We have studied isotope ratios using Inductively-Coupled Plasma Mass Spectrometry (ICP-MS) to investigate the source of Pb in the blood of Mute swans (n = 49) wintering in northern Poland. We compared the values of isotopic ratios from blood and ammunition pellets available on the Polish market. The mean Pb concentrations found was 0.241 μg/g (w/w) and nearly half of the blood specimens had elevated Pb levels (higher than the cited 0.23 μg/g w/w threshold of poisoning). Only the mean 208/206 Pb isotope ratio was similar in blood and pellet samples. Mean ratios of isotopes 206/204, 206/207 and 208/207 in swans' blood and in pellets differed significantly. Moreover, coefficients of variation were higher in blood samples than in pellets. These discrepancies and significant differences in abundance of 204 Pb and 207 Pb isotopes in both materials indicated that pellets available today on the Polish market were not the source of Pb in the blood of Mute swans wintering in northern Poland. Copyright © 2016 Elsevier Ltd. All rights reserved.

Carbon isotope geochemistry and geobiology

NASA Technical Reports Server (NTRS)

Desmarais, D.

1985-01-01

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

In-situ Pb isotope analysis of Fe-Ni-Cu sulphides by laser ablation multi-collector ICPMS: New insights into ore formation in the Sudbury impact melt sheet

NASA Astrophysics Data System (ADS)

Darling, J. R.; Storey, C. D.; Hawkesworth, C. J.; Lightfoot, P. C.

2012-12-01

Laser-ablation (LA) multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) is ideally suited to in situ determination of isotope ratios in sulphide minerals. Using samples of magmatic sulphide ore from the Sudbury impact structure, we test LA-MC-ICPMS analytical protocols that aim to meet a range of analytical challenges in the analysis of Pb isotopes. These include: potential matrix sensitive isotopic fractionation; interferences on Pb isotopes; low melting points of many sulphide minerals; the availability of standards. Magmatic sulphides of wide ranging mineralogy (pyrrhotite, pentlandite, chalcopyrite, pyrite and sphalerite) were analysed for Pb isotopic composition, using the silicate glass NIST SRM 610 as an external standard to correct for instrumental mass-fractionation. Despite matrix sensitive melting and re-deposition around ablation pits, several lines of evidence indicate that all analyses are accurate, within typical analytical uncertainties of 0.003-2% (2σ), and that the defined approach is insensitive to compositional diversity in sample matrix: (a) laser ablation and dissolution based measurements of sulphide powders are in agreement; (b) analyses from each sample define isochron ages within uncertainty of the known crystallization age (1850 Ma); (c) the results of sulphide measurements by laser ablation are consistent with age-corrected feldspar analyses from the same samples. The results have important implications for ore formation in Sudbury. The Pb isotope data regressions are consistent with age corrected feldspar analyses from each respective sample, which together with time integrated Th/U ratios that match whole rock values (3.1, 4.0 and 6.1 for the Worthington, Copper Cliff and Parkin Offset Dykes, respectively) indicate chemical equilibrium between the silicate and sulphide systems during ore formation. The sulphides within each respective sample have indistinguishable model initial Pb isotope ratios (207Pb/204Pbm), irrespective of mineralogy or texture, indicating a common origin for ores within each of three different Offset Dykes. Furthermore, variations between Offset Dykes (e.g., 207Pb/204Pbm = 15.514 ± 0.012, 15.399 ± 0.009 and 15.275 ± 0.003) show that the ores have differing crustal sources on previously unrecognized scales. Mass balance considerations, particularly for MgO, Ni and Cu, indicate that the spatial distribution of mafic target rocks played a significant role in controlling the mineralization potential in different parts of the melt sheet.

Seawater osmium isotope evidence for a middle Miocene flood basalt event in ferromanganese crust records

USGS Publications Warehouse

Klemm, V.; Frank, M.; Levasseur, S.; Halliday, A.N.; Hein, J.R.

2008-01-01

Three ferromanganese crusts from the northeast, northwest and central Atlantic were re-dated using osmium (Os) isotope stratigraphy and yield ages from middle Miocene to the present. The three Os isotope records do not show evidence for growth hiatuses. The reconstructed Os isotope-based growth rates for the sections older than 10??Ma are higher than those determined previously by the combined beryllium isotope (10Be/9Be) and cobalt (Co) constant-flux methods, which results in a decrease in the maximum age of each crust. This re-dating does not lead to significant changes to the interpretation of previously determined radiogenic isotope neodymium, lead (Nd, Pb) time series because the variability of these isotopes was very small in the records of the three crusts prior to 10??Ma. The Os isotope record of the central Atlantic crust shows a pronounced minimum during the middle Miocene between 15 and 12??Ma, similar to a minimum previously observed in two ferromanganese crusts from the central Pacific. For the other two Atlantic crusts, the Os isotope records and their calibration to the global seawater curve for the middle Miocene are either more uncertain or too short and thus do not allow for a reliable identification of an isotopic minimum. Similar to pronounced minima reported previously for the Cretaceous/Tertiary and Eocene/Oligocene boundaries, possible interpretations for the newly identified middle Miocene Os isotope minimum include changes in weathering intensity and/or a meteorite impact coinciding with the formation of the No??rdlinger Ries Crater. It is suggested that the eruption and weathering of the Columbia River flood basalts provided a significant amount of the unradiogenic Os required to produce the middle Miocene minimum. ?? 2008 Elsevier B.V.

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

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

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

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

Evaluation of the plasma hydrogen isotope content by residual gas analysis at JET and AUG

NASA Astrophysics Data System (ADS)

Drenik, A.; Alegre, D.; Brezinsek, S.; De Castro, A.; Kruezi, U.; Oberkofler, M.; Panjan, M.; Primc, G.; Reichbauer, T.; Resnik, M.; Rohde, V.; Seibt, M.; Schneider, P. A.; Wauters, T.; Zaplotnik, R.; ASDEX-Upgrade, the; EUROfusion MST1 Teams; contributors, JET

2017-12-01

The isotope content of the plasma reflects on the dynamics of isotope changeover experiments, efficiency of wall conditioning and the performance of a fusion device in the active phase of operation. The assessment of the isotope ratio of hydrogen and methane molecules is used as a novel method of assessing the plasma isotope ratios at JET and ASDEX-Upgrade (AUG). The isotope ratios of both molecules in general shows similar trends as the isotope ratio detected by other diagnostics. At JET, the absolute values of RGA signals are in relatively good agreement with each other and with spectroscopy data, while at AUG the deviation from neutral particle analyser data are larger, and the results show a consistent spatial distribution of the isotope ratio. It is further shown that the isotope ratio of the hydrogen molecule can be used to study the degree of dissociation of the injected gas during changeover experiments.

U-Pb isotopic systematics of shock-loaded and annealed baddeleyite: Implications for crystallization ages of Martian meteorite shergottites

NASA Astrophysics Data System (ADS)

Niihara, Takafumi; Kaiden, Hiroshi; Misawa, Keiji; Sekine, Toshimori; Mikouchi, Takashi

2012-08-01

Shock-recovery and annealing experiments on basalt-baddeleyite mixtures were undertaken to evaluate shock effects on U-Pb isotopic systematics of baddeleyite. Shock pressures up to 57 GPa caused fracturing of constituent phases, mosaicism of olivine, maskelynitization of plagioclase, and melting, but the phase transition from monoclinic baddeleyite structure to high-pressure/temperature polymorphs of ZrO2 was not confirmed. The U-Pb isotopic systems of the shock-loaded baddeleyite did not show a large-scale isotopic disturbance. The samples shock-recovered from 47 GPa were then employed for annealing experiments at 1000 or 1300 °C, indicating that the basalt-baddeleyite mixture was almost totally melted except olivine and baddeleyite. Fine-grained euhedral zircon crystallized from the melt was observed around the relict baddeleyite in the sample annealed at 1300 °C for 1 h. The U-Pb isotopic systems of baddeleyite showed isotopic disturbances: many data points for the samples annealed at 1000 °C plotted above the concordia. Both radiogenic lead loss/uranium gain and radiogenic lead gain/uranium loss were observed in the baddeleyite annealed at 1300 °C. Complete radiogenic lead loss due to shock metamorphism and subsequent annealing was not observed in the shock-loaded/annealed baddeleyites studied here. These results confirm that the U-Pb isotopic systematics of baddeleyite are durable for shock metamorphism. Since shergottites still preserve Fe-Mg and/or Ca zonings in major constituent phases (i.e. pyroxene and olivine), the shock effects observed in Martian baddeleyites seem to be less intense compared to that under the present experimental conditions. An implication is that the U-Pb systems of baddeleyite in shergottites will provide crystallization ages of Martian magmatic rocks.

Isotope effect in the organic superconductor β_H-(BEDT-TTF)2I3 where BEDT-TTF is bis (ethylenedithiotetrathiafulvalene)

NASA Astrophysics Data System (ADS)

Auban-Senzier, P.; Bourbonnais, C.; Jérome, D.; Lenoir, C.; Batail, P.; Canadell, E.; Buisson, J. P.; Lefrant, S.

1993-03-01

We have performed the simultaneous investigation of the isotope effect on the superconducting transition and on the Raman spectra in the organic superconductor β_H-(BEDT-TTF)2I3 (T_c = 8 K). For this purpose, we substitute ^{13}C for ^{12}C on the carbon sites of the central double bond of BEDT-TTF molecule. The isotope shifts measured by Raman experiments can be fairly well explained by standard molecular dynamics. However, the critical temperature is lowered by 0.2 K in the ^{13}C enriched material. We analyse the possible sources of this remarkable downward shift which leads to an isotope coefficient higher than the BCS value. The extended-Hückel calculations of the density of states for the two HOMO bands of β_H-(BEDT-TTF)2I3 do show that, within the framework of a weak coupling theory, its sizeable variation on the scale of ω_D cannot account for the observed isotope effect. On the other hand, we discuss how inelastic electronic scattering observed in resistivity measurements just above T_c can lead through a pair breaking mechanism to a sizeable increase of the isotope coefficient. Nous présentons une étude simultanée d'effet isotopique sur la transition supraconductrice et les spectres Raman dans le supraconducteur organique β_H-(BEDT-TTF)2I3 (T_c = 8 K). Pour cela, nous avons synthétisé le composé dans lequel les atomes de carbone de la double liaison centrale de la molécule BEDT-TTF sont substitués par l'isotope ^{13}C. Les déplacements isotopiques mesurés par spectroscopie Raman sont bien expliqués par la dynamique moléculaire standard. Cependant, la température critique est abaissée de 0.2 K dans le matériau enrichi en ^{13}C. Nous étudions les origines possibles de cet effet qui permet d'obtenir un coefficient isotopique supérieur à la valeur BCS. Des calculs de la densité d'états effectués par la méthode de Hückel étendue pour les deux bandes HOMO du composé montrent que, dans le cadre d'une théorie de couplage faible, son importante variation à l'échelle de ω_D ne peut expliquer l'effet observé. D'autre part, nous expliquons comment la diffusion électronique inélastique observée en résistivité juste au-dessus de T_c peut conduire via un mécanisme de brisure de paires, à une augmentation significative du coefficient isotopique.

What's all the stink about BO-? Using negative molecular ions to measure boron isotopes in samples with trace boron

NASA Astrophysics Data System (ADS)

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

2011-12-01

Boron isotope fractionation depends strongly on the coordination of boron in coexisting phases. When boron is tetrahedrally coordinated in one phase and trigonally coordinated in another, equilibrium fractionation can record parameters such as temperature (over a surprisingly wide T for a stable isotope system) or the pH at which phases precipitated from low temperature solutions. The heavy isotope of B is strongly partitioned into fluid phases relative to minerals containing tetrahedrally-coordinated boron and thus B isotope ratios can provide evidence for separation of hydrous fluids from subducted materials and from silicate melts in volcanoes. However, in many cases, the B concentration of relevant solid phases is very low, leading to large errors in the isotope ratio. For example, common analytical protocols for the microanalysis of B on our secondary ion mass spectrometer (SIMS, Cameca 6f) use an O- primary beam, and detection of positive secondary ions at moderate mass resolving power. On samples containing a few ppm B, analyses may require up to ~2 hours to give integrated signals corresponding to errors of +/- 7 per mil (2 sigma). Increases in ion intensity would result from simply increasing the primary current (at the expense of beam diameter) or increasing transmission by reducing mass resolving power (at the expense of including 10BH+ ions on the 11B+ peak). Large magnetic sector SIMS instruments achieve higher transmission at high resolution, but the challenges of obtaining desired precision (+/- 1 permil) remain when boron is present at <2 ppm levels. Another direction to pursue is to find a B-containing ion that is formed more readily than the elemental positive ion. The logical choice is BO-, an ion isoelectronic with F-, and one we would expect to show very high ion yields. However, BO- can be unpleasant to deal with. Isobaric interferences include the toxic species of CN-: various combinations of the two carbon and nitrogen isotopes are silent but deadly additions to the mass spectrum requiring mass resolving powers exceeding 12000 (M/ΔM) for complete separation. In our preliminary studies, we have used a Cs+ primary beam, detection of negative secondary ions and the normal-incidence electron gun for neutralizing positive charge build-up in the crater. The observation of abundant carbon and nitrogen in clay mineral samples reveal the challenges of conducting these analyses. However, carbon and nitrogen contents in other phases of interest are very low, and contaminants can be controlled using careful sample preparation, ultra-high vacuum conditions, and restricting secondary ion detection to the central part of the analyzed crater. Using these conditions, BO- reeks with intensities up to 100x the elemental negative ion! Through a lot of sweat equity, we will demonstrate the use and limitations of BO- in isotope microanalyses of low-B samples. We thank the NSF EAR Instruments and Facilities program for encouraging us to explore new analytical techniques.

Comprehensive Pb-Sr-Nd-Hf isotopic, trace element, and mineralogical characterization of mafic to ultramafic rock reference materials

NASA Astrophysics Data System (ADS)

Fourny, Anaïs.; Weis, Dominique; Scoates, James S.

2016-03-01

Controlling the accuracy and precision of geochemical analyses requires the use of characterized reference materials with matrices similar to those of the unknown samples being analyzed. We report a comprehensive Pb-Sr-Nd-Hf isotopic and trace element concentration data set, combined with quantitative phase analysis by XRD Rietveld refinement, for a wide range of mafic to ultramafic rock reference materials analyzed at the Pacific Centre for Isotopic and Geochemical Research, University of British Columbia. The samples include a pyroxenite (NIM-P), five basalts (BHVO-2, BIR-1a, JB-3, BE-N, GSR-3), a diabase (W-2), a dolerite (DNC-1), a norite (NIM-N), and an anorthosite (AN-G); results from a leucogabbro (Stillwater) are also reported. Individual isotopic ratios determined by MC-ICP-MS and TIMS, and multielement analyses by HR-ICP-MS are reported with 4-12 complete analytical duplicates for each sample. The basaltic reference materials have coherent Sr and Nd isotopic ratios with external precision below 50 ppm (2SD) and below 100 ppm for Hf isotopes (except BIR-1a). For Pb isotopic reproducibility, several of the basalts (JB-3, BHVO-2) require acid leaching prior to dissolution. The plutonic reference materials also have coherent Sr and Nd isotopic ratios (<50 ppm), however, obtaining good reproducibility for Pb and Hf isotopic ratios is more challenging for NIM-P, NIM-N, and AN-G due to a variety of factors, including postcrystallization Pb mobility and the presence of accessory zircon. Collectively, these results form a comprehensive new database that can be used by the geochemical community for evaluating the radiogenic isotope and trace element compositions of volcanic and plutonic mafic-ultramafic rocks.

Assessing connectivity of estuarine fishes based on stable isotope ratio analysis

NASA Astrophysics Data System (ADS)

Herzka, Sharon Z.

2005-07-01

Assessing connectivity is fundamental to understanding the population dynamics of fishes. I propose that isotopic analyses can greatly contribute to studies of connectivity in estuarine fishes due to the high diversity of isotopic signatures found among estuarine habitats and the fact that variations in isotopic composition at the base of a food web are reflected in the tissues of consumers. Isotopic analysis can be used for identifying nursery habitats and estimating their contribution to adult populations. If movement to a new habitat is accompanied by a shift to foods of distinct isotopic composition, recent immigrants and residents can be distinguished based on their isotopic ratios. Movement patterns thus can be reconstructed based on information obtained from individuals. A key consideration is the rate of isotopic turnover, which determines the length of time that an immigrant to a given habitat will be distinguishable from a longtime resident. A literature survey indicated that few studies have measured turnover rates in fishes and that these have focused on larvae and juveniles. These studies reveal that biomass gain is the primary process driving turnover rates, while metabolic turnover is either minimal or undetectable. Using a simple dilution model and biomass-specific growth rates, I estimated that young fishes with fast growth rates will reflect the isotopic composition of a new diet within days or weeks. Older or slower-growing individuals may take years or never fully equilibrate. Future studies should evaluate the factors that influence turnover rates in fishes during various stages of the life cycle and in different tissues, as well as explore the potential for combining stable isotope and otolith microstructure analyses to examine the relationship between demographic parameters, movement and connectivity.

High-precision 87Sr/86Sr analyses in wines and their use as a geological fingerprint for tracing geographic provenance.

PubMed

Marchionni, Sara; Braschi, Eleonora; Tommasini, Simone; Bollati, Andrea; Cifelli, Francesca; Mulinacci, Nadia; Mattei, Massimo; Conticelli, Sandro

2013-07-17

The radiogenic isotopic compositions of inorganic heavy elements such as Sr, Nd, and Pb of the food chain may constitute a reliable geographic fingerprint, their isotopic ratios being inherited by the geological substratum of the territory of production. The Sr isotope composition of geomaterials (i.e., rocks and soils) is largely variable, and it depends upon the age of the rocks and their nature (e.g., genesis, composition). In this study we developed a high-precision analytical procedure for determining Sr isotopes in wines at comparable uncertainty levels of geological data. With the aim of verifying the possibility of using Sr isotope in wine as a reliable tracer for geographic provenance, we performed Sr isotope analyses of 45 bottled wines from four different geographical localities of the Italian peninsula. Their Sr isotope composition has been compared with that of rocks from the substrata (i.e., rocks) of their vineyards. In addition wines from the same winemaker but different vintage years have been analyzed to verify the constancy with time of the (87)Sr/(86)Sr. Sr isotope compositions have been determined by solid source thermal ionization mass spectrometry following purification of Sr in a clean laboratory. (87)Sr/(86)Sr of the analyzed wines is correlated with the isotopic values of the geological substratum of the vineyards, showing little or no variation within the same vineyard and among different vintages. Large (87)Sr/(86)Sr variation is observed among wines from the different geographical areas, reinforcing the link with the geological substratum of the production territory. This makes Sr isotopes a robust geochemical tool for tracing the geographic authenticity and provenance of wine.

Isotopic composition and identification of the origins of individuals buried in a Neolithic collective grave at Bronocice (southern Poland).

PubMed

Szostek, K; Haduch, E; Stepańczak, B; Kruk, J; Szczepanek, A; Pawlyta, J; Głąb, H; Milisauskas, S

2014-04-01

The oxygen present in a human organism comes from numerous sources, but the major factor that causes variation in the isotopic composition of this element in a tissue is available drinking water. The isotopic ratio of oxygen in an organism's tissue, including that found in bones and teeth, reflects the isotopic oxygen composition typical for the area where a given individual developed and lived. Of particular interest with regard to this issue were a series of skeletons from the multiple grave discovered at the Funnel Beaker-Baden settlement at Bronocice (southern Poland). The question therefore arose whether the specimens buried in this grave were part of the local community. The oxygen isotope level was established using apatite isolated from bones or teeth. A femur and root dentine samples taken from permanent teeth were subjected to oxygen isotope analysis. The oxygen isotope level of the site was established on the basis of local water precipitation and measurements taken from the oxygen isotope concentration in apatite samples isolated from the bones of animals co-occurring with the studied human group. It has been found that the oxygen isotope levels in the bones and dentine of almost all the analysed specimens from the excavated site at Bronocice were within the established range for the area's environment, providing evidence for their local origin. Thus, it can be assumed that the analysed group inhabiting the macrosettlement at Bronocice during the Funnel Beaker phase of the Baden culture was most probably of local origin. Copyright © 2013 Elsevier GmbH. All rights reserved.

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

USGS Publications Warehouse

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

1992-01-01

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

Quantifying N2O reduction to N2 based on N2O isotopocules - validation with independent methods (helium incubation and 15N gas flux method)

NASA Astrophysics Data System (ADS)

Lewicka-Szczebak, Dominika; Augustin, Jürgen; Giesemann, Anette; Well, Reinhard

2017-02-01

Stable isotopic analyses of soil-emitted N2O (δ15Nbulk, δ18O and δ15Nsp = 15N site preference within the linear N2O molecule) may help to quantify N2O reduction to N2, an important but rarely quantified process in the soil nitrogen cycle. The N2O residual fraction (remaining unreduced N2O, rN2O) can be theoretically calculated from the measured isotopic enrichment of the residual N2O. However, various N2O-producing pathways may also influence the N2O isotopic signatures, and hence complicate the application of this isotopic fractionation approach. Here this approach was tested based on laboratory soil incubations with two different soil types, applying two reference methods for quantification of rN2O: helium incubation with direct measurement of N2 flux and the 15N gas flux method. This allowed a comparison of the measured rN2O values with the ones calculated based on isotopic enrichment of residual N2O. The results indicate that the performance of the N2O isotopic fractionation approach is related to the accompanying N2O and N2 source processes and the most critical is the determination of the initial isotopic signature of N2O before reduction (δ0). We show that δ0 can be well determined experimentally if stable in time and then successfully applied for determination of rN2O based on δ15Nsp values. Much more problematic to deal with are temporal changes of δ0 values leading to failure of the approach based on δ15Nsp values only. For this case, we propose here a dual N2O isotopocule mapping approach, where calculations are based on the relation between δ18O and δ15Nsp values. This allows for the simultaneous estimation of the N2O-producing pathways' contribution and the rN2O value.

Unravelling spatiotemporal tree-ring signals in Mediterranean oaks: a variance-covariance modelling approach of carbon and oxygen isotope ratios.

PubMed

Shestakova, Tatiana A; Aguilera, Mònica; Ferrio, Juan Pedro; Gutiérrez, Emilia; Voltas, Jordi

2014-08-01

Identifying how physiological responses are structured across environmental gradients is critical to understanding in what manner ecological factors determine tree performance. Here, we investigated the spatiotemporal patterns of signal strength of carbon isotope discrimination (Δ(13)C) and oxygen isotope composition (δ(18)O) for three deciduous oaks (Quercus faginea (Lam.), Q. humilis Mill. and Q. petraea (Matt.) Liebl.) and one evergreen oak (Q. ilex L.) co-occurring in Mediterranean forests along an aridity gradient. We hypothesized that contrasting strategies in response to drought would lead to differential climate sensitivities between functional groups. Such differential sensitivities could result in a contrasting imprint on stable isotopes, depending on whether the spatial or temporal organization of tree-ring signals was analysed. To test these hypotheses, we proposed a mixed modelling framework to group isotopic records into potentially homogeneous subsets according to taxonomic or geographical criteria. To this end, carbon and oxygen isotopes were modelled through different variance-covariance structures for the variability among years (at the temporal level) or sites (at the spatial level). Signal-strength parameters were estimated from the outcome of selected models. We found striking differences between deciduous and evergreen oaks in the organization of their temporal and spatial signals. Therefore, the relationships with climate were examined independently for each functional group. While Q. ilex exhibited a large spatial dependence of isotopic signals on the temperature regime, deciduous oaks showed a greater dependence on precipitation, confirming their higher susceptibility to drought. Such contrasting responses to drought among oak types were also observed at the temporal level (interannual variability), with stronger associations with growing-season water availability in deciduous oaks. Thus, our results indicate that Mediterranean deciduous and evergreen oaks constitute two clearly differentiated functional groups in terms of their carbon and water economies, despite co-existing in a wide range of environments. In contrast, deciduous oaks form a rather homogeneous group in terms of climate sensitivity. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

You are not always what we think you eat: selective assimilation across multiple whole-stream isotopic tracer studies

Treesearch

W. K. Dodds; S. M. Collins; S. K. Hamilton; J. L. Tank; S. Johnson; J. R. Webster; K. S. Simon; M. R. Whiles; H. M. Rantala; W. H. McDowell; S. D. Peterson; T. Riis; C. L. Crenshaw; S. A. Thomas; P. B. Kristensen; B. M. Cheever; A. S. Flecker; N. A. Griffiths; T. Crowl; E. J. Rosi-Marshall; R. El-Sabaawi; E. Martí

2014-01-01

Analyses of 21 15N stable isotope tracer experiments, designed to examine food web dynamics in streams around the world, indicated that the isotopic composition of food resources assimilated by primary consumers (mostly invertebrates) poorly reflected the presumed food sources. Modeling indicated that consumers assimilated only 33–50% of the N...

Reappraising Accretion to Vesta and the Angrite Parent Body Through Mineral-Scale Platinum Group Element and Os-Isotope Analyses

NASA Astrophysics Data System (ADS)

Riches, A. J. V.; Burton, K. W.; Nowell, G. M.; Dale, C. W.; Ottley, C. J.

2016-08-01

New methods presented here enable quantitative determination of mineral-scale PGE-abundances and Os-isotope compositions in meteorite materials thereby providing valuable new insight into planetary evolution.

Si Isotopes in Enstatite Chondrites: Implications to Accretion and Differentiation Event of the Earth

NASA Astrophysics Data System (ADS)

Sikdar, J.; Rai, V. K.

2018-05-01

The abstract summarizes the recent results on high precision Si isotope analyses in various micro milled components of Enstatite chondrites with implications towards the accretion and primary differentiation event of the Earth.

A NICHE FOR ISOTOPIC ECOLOGY

EPA Science Inventory

Fifty years ago, GE Hutchinson defined the ecological niche as a hypervolume in n-dimensional space with environmental variables as axes. Ecologists have recently developed renewed interest in the concept, and technological advances now allow us to use stable isotope analyses to ...

Concentrations and activity ratios of uranium isotopes in groundwater from Doñana National Park, South of Spain

NASA Astrophysics Data System (ADS)

Bolívar, J. P.; Olías, M.; González-García, F.; García-Tenorio, R.

2008-08-01

The levels and distribution of natural radionuclides in groundwaters from the unconfined Almonte-Marismas aquifer, upon which Doñana National Park is located, have been analysed. Most sampled points were multiple piezometers trying to study the vertical distribution of the hydrogeochemical characteristics in the aquifer. Temperature, pH, electrical conductivity, dissolved oxygen and redox potential were determined in the field. A large number of parameters, physico-chemical properties, major and minor ions, trace elements and natural radionuclides (U-isotopes, Th-isotopes, Ra-isotopes and 210Po), were also analysed. In the southern zone, where aeolian sands crop out, water composition is of the sodium chloride type, and the lower U-isotopes concentrations have been obtained. As water circulates through the aquifer, bicarbonate and calcium concentrations increase slightly, and higher radionuclides concentrations were measured. Finally, we have demonstrated that 234U/238U activity ratios can be used as markers of the type of groundwater and bedrock, as it has been the case for old waters with marine origin confined by a marsh in the south-east part of aquifer.

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

Rasmussen, K.A.; Neumann, A.C.; Haddad, R.I.

The stable-isotope composition ({delta}{sup 13}C) of total organic carbon (TOC) was measured as a function of depth throughout a 217-cm-thick sequence of Holocene carbonate sediment within the Bight of Abaco lagoon, Little Bahama Bank. Biofacies and lithofacies analyses indicate progressive banktop submergence and paleoenvironmental response during Holocene sea-level rise. Stable-isotope values shift markedly from {minus}27.7{per thousand} within the 7900 B.P. paleosol at the base of the core to {minus}11.1{per thousand} at the present-day sediment-water interface. An abrupt excursion toward heavy-isotope values records the first establishment of Thalassia seagrass upon open-marine flooding. A multitracer approach, combining biofacies, lithofacies, and stable-isotope analysismore » of TOC confirms that the dramatic +17{per thousand} shift observed in {delta}{sup 13}C was a direct result of sea-level rise and associated environmental changes over the banktop; there is little evidence of spurious diagenetic overprint. Stable-isotope analyses of organic carbon may enhance the reconstruction of carbonate sequences by revealing a distinctive geochemical signature of banktop flooding, including the onset of growth of otherwise unpreservable Thalassia seagrass.« less

Kinetic analysis of lead metabolism in healthy humans

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

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

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

Lead isotope ratios for bullets, a descriptive approach for investigative purposes and a new method for sampling of bullet lead.

PubMed

Sjåstad, Knut-Endre; Simonsen, Siri Lene; Andersen, Tom H

2014-11-01

To establish a link between a bullet fired from a suspected firearm, investigation of striation marks are one of the corner stones in the forensic laboratory. Nevertheless, on some occasions, the bullet may be deformed to such extent that traditional investigation of striation marks will be impossible. Fragments of lead can be investigated by lead isotope ratio determination in order to distinguish between bullets with different origin. This approach initially seems reasonable, since the abundance of lead isotopes varies significantly in nature. To make a method valid for forensic purposes, it is important to have a fundamental understanding of the variation within a box of lead bullets and the expected variation between boxes. Studies of variability within and between boxes of ammunition are imperative to perform any type of forensic interpretation, both in an investigative and evaluative context. This work presents an extensive study of variability within and between boxes of ammunition by use of multicollector inductive coupled mass spectrometry. As a first approximation to classify bullets to any given source, a simple and robust graphical method is presented. In addition, an easy-to-use sampling procedure of lead is presented. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

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

NASA Technical Reports Server (NTRS)

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

2016-01-01

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

Pb isotopes of Gorgona Island (Colombia): isotopic variations correlated with magma type

NASA Astrophysics Data System (ADS)

Dupré, B.; Echeverría, L. M.

1984-02-01

Lead isotopic results obtained on komatiites and basalts from Gorgona Island provide evidence of large isotopic variations within a restricted area (8 × 2.5 km). The variations are correlated with differences in volcanic rock type. The highest isotopic ratios ( 206Pb/ 204Pb˜ 19.75 ) correspond to tholeiites which make up most of the island. The lowest ratios (18.3) correspond to the komatiites of the west coast of the island. Other rock types (komatiites of the east coast, K-tholeiites, picrites and tuffs) have isotopic characteristics intermediate between these two extreme values. These results are explained by the existence of two distinct mantle source regions, and by mixing or contamination between them.

Statistical clumped isotope signatures

PubMed Central

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

2016-01-01

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

Changes in the mean square charge radii and electromagnetic moments of neutron-deficient Bi isotopes

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

Barzakh, A. E., E-mail: barzakh@mail.ru; Batist, L. Kh.; Fedorov, D. V.

In-source laser spectroscopy experiments for neutron deficient bismuth isotopes at the 306.77 nm atomic transition were carried out at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility of Petersburg Nuclear Physics Institute (PNPI). New data on isotope shifts and hyperfine structure for {sup 189–198,} {sup 211}Bi isotopes and isomers were obtained. The changes in the mean-square charge radii and the magnetic moment values were deduced. Marked deviation from the nearly spherical behavior for ground states of bismuth isotopes at N < 109 is demonstrated, in contrast to the lead and thallium isotopic chains. The big isomer shift between Imore » = 1/2 (intruder) and I = 9/2 (normal) states for odd Bi isotopes (A = 193, 195, 197) was found.« less

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

USGS Publications Warehouse

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

2004-01-01

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

Evaluation of the accuracy of the determination of lead isotope ratios in wine by ICP MS using quadrupole, multicollector magnetic sector and time-of-flight analyzers.

PubMed

Barbaste, M; Halicz, L; Galy, A; Medina, B; Emteborg, H; C Adams, F; Lobinski, R

2001-04-12

Different mass analysers [(quadrupole (Q), time-of-flight (TOF) and multicollector (MC) sector-field (SF)] of ions produced in an inductively coupled plasma were evaluated for the determination of lead isotope ratios in wine samples. A population of 20 wines of different origin including two reference wines from the EC Standards, Measurement and Testing Programme with concentrations varying between 7-140 mug Pb l(-1) was investigated. Wines were analyzed directly by Q ICP MS and MC ICP MS. The poor sensitivity of the TOF instrument, further aggravated by matrix signal suppression, did not allow the acquisition of data for wine samples that contained less than 50 mug l(-1) in the direct sample introduction mode. The separation and preconcentration of lead were therefore required. The precision obtained for the (206)Pb/(207)Pb and (208)Pb/(206)Pb were similar and equal to 0.14-2.7% for Q ICP MS, 0.04-0.17% for TOF ICP MS and 0.01-0.12% for MC ICP MS. The precision for (206)Pb/(204)Pb was 0.44-5.29, 0.15-1.7, 0.08-1.6%, respectively. On the level of accuracy, the data from TOF ICP MS and MC ICP MS were in good agreement. The accuracy of Q ICP MS data was judged satisfactory in comparison with the other techniques but their poor precision was a significant obstacle on the way of using these data for the determination of the geographic origin of wine.

Atmospheric trace metal inputs in the Misten bog (East Belgium): Special attention to sampling techniques and site-spatial variability.

NASA Astrophysics Data System (ADS)

Allan, Mohammed; Fagel, Nathalie; de Vleeschouwer, François; Mattielli, Nadine; Piotrowska, Natalia; Sikorski, Jarek; Sonke, Jeroen E.; Le Roux, Gaël.

2010-05-01

Peat bogs have a great potential to record anthropogenic inputs via their constituting mosses, because they draw their nutrients only from the atmosphere. These atmospheric inputs can be studied thanks to geochemical characteristics such as trace metal concentrations. Coupling lead isotopes to elemental geochemistry allows one to decipher between natural (erosion of rocks) and anthropogenic (pollution due to industrial development, vehicles...) inputs. The purpose of our work was to study the pollution history of trace metals in the region of Misten (Belgium) at a local and a regional level, and to place modern industrial pollution in this region in a wider historical perspective. Four peat cores (01W, 04W, 05W and 06W) were collected in 2008 in the Misten bog (Hautes-Fagnes plateau, E-Belgium) and studied for their trace metal and lead isotopic signatures. Analyses were accompanied by coupled 210Pb-14C age models in order to estimate the mercury and lead accumulation rates in each core and compare them to other European records. The Hg record was compared to the various anthropogenic sources as determined by Pb isotopes. The Hg concentration profiles resemble those of Pb, an element known to be immobile in peatlands. The correlation between these two metals suggests a predominant anthropogenic source of Hg (and Pb). In the W06 core, low and stable Hg accumulation rates (0.9-3.1 μg m-2 yr-1) are found in the lower layers (503-1823AD). High Hg accumulation rates are found in the surface and sub-surface layers (post-1823AD) and peak at 123.3 μg m-2 yr-1 (1969AD). In 01W, the lead enrichment factor (Pb E.F.) coupled with the continuous drop in 206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb isotopic ratios since 539 AD until 1973AD indicates the growing importance of the non-radiogenic Pb released from anthropogenic activities. The highest concentrations of Pb (613-662 µg g-1) have been found near the surface of the bog dated between 1902 and 1954AD. The Pb E.F. also significantly increased during the Industrial Revolution, and subsequently decreased due to the phasing out of leaded gasoline. Main results for Pb in 01W and Hg in 06W will be compared with the 2 other cores and previously published results collected in 2007 at another location in the same peatland. Differences in concentrations and chronology will be discussed in terms of (1) differences in the topography of the bog, (2) differences in the surface vegetation of the bog, which could have led to differential trapping and retention of lead, for example, and different retention of vegetation during sampling at the sites where the corers were inserted, (3) different effects induced by the operating mechanism of the corers, (4) operator-induced effects, e.g. leading to loss of surface material before or during coring.

Improved radiocarbon analyses of modern human hair to determine the year-of-death by cross-flow nanofiltered amino acids: common contaminants, implications for isotopic analysis, and recommendations.

PubMed

Santos, Guaciara M; De La Torre, Hector A Martinez; Boudin, Mathieu; Bonafini, Marco; Saverwyns, Steven

2015-10-15

In forensic investigation, radiocarbon ((14)C) measurements of human tissues (i.e., nails and hair) can help determine the year-of-death. However, the frequent use of cosmetics can bias hair (14)C results as well as stable isotope values. Evidence shows that hair exogenous impurities percolate beyond the cuticle layer, and therefore conventional pretreatments are ineffective in removing them. We conducted isotopic analysis ((14)C, δ(13)C, δ(15)N and C/N) of conventionally treated and cross-flow nanofiltered amino acid (CFNAA)-treated samples (scalp- and body-hair) from a single female subject using fingernails as a reference. The subject studied frequently applies a permanent dark-brown dye kit to her scalp-hair and uses other care products for daily cleansing. We also performed pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) analyses of CFNAA-treated scalp-hair to identify contaminant remnants that could possibly interfere with isotopic analyses. The conventionally treated scalp- and body-hair showed (14)C offsets of ~21‰ and ~9‰, respectively. These offsets confirm the contamination by petrochemicals in modern human hair. A single CFNAA extraction reduced those offsets by ~34%. No significant improvement was observed when sequential extractions were performed, as it appears that the procedure introduced some foreign contaminants. A chromatogram of the CFNAA scalp-hair pyrolysis products showed the presence of petroleum and plant/animal compound residues, which can bias isotopic analyses. We have demonstrated that CFNAA extractions can partially remove cosmetic contaminants embedded in human hair. We conclude that fingernails are still the best source of keratin protein for year-of-death determinations and isotopic analysis, with body-hair and/or scalp-hair coupled with CFNAA extraction a close second. Copyright © 2015 John Wiley & Sons, Ltd.

Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

NASA Astrophysics Data System (ADS)

Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

2015-12-01

Chondrichthyan teeth (sharks, rays, and chimaeras) are mineralized in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are generally consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the hybodont shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

NASA Astrophysics Data System (ADS)

Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

2015-08-01

Chondrichthyan teeth (sharks, rays and chimaeras) are mineralised in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered as a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the primitive shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

Relating Carbon and Nitrogen Isotope Effects to Reaction Mechanisms during Aerobic or Anaerobic Degradation of RDX (Hexahydro-1,3,5-Trinitro-1,3,5-Triazine) by Pure Bacterial Cultures

PubMed Central

Heraty, Linnea; Condee, Charles W.; Vainberg, Simon; Sturchio, Neil C.; Böhlke, J. K.; Hatzinger, Paul B.

2016-01-01

ABSTRACT Kinetic isotopic fractionation of carbon and nitrogen during RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) biodegradation was investigated with pure bacterial cultures under aerobic and anaerobic conditions. Relatively large bulk enrichments in 15N were observed during biodegradation of RDX via anaerobic ring cleavage (ε15N = −12.7‰ ± 0.8‰) and anaerobic nitro reduction (ε15N = −9.9‰ ± 0.7‰), in comparison to smaller effects during biodegradation via aerobic denitration (ε15N = −2.4‰ ± 0.2‰). 13C enrichment was negligible during aerobic RDX biodegradation (ε13C = −0.8‰ ± 0.5‰) but larger during anaerobic degradation (ε13C = −4.0‰ ± 0.8‰), with modest variability among genera. Dual-isotope ε13C/ε15N analyses indicated that the three biodegradation pathways could be distinguished isotopically from each other and from abiotic degradation mechanisms. Compared to the initial RDX bulk δ15N value of +9‰, δ15N values of the NO2− released from RDX ranged from −7‰ to +2‰ during aerobic biodegradation and from −42‰ to −24‰ during anaerobic biodegradation. Numerical reaction models indicated that N isotope effects of NO2− production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε15N-NO2− values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO2− formation associated with anaerobic ring cleavage. These results indicate the potential for isotopic analysis of residual RDX for the differentiation of degradation pathways and indicate that further efforts to examine the isotopic composition of potential RDX degradation products (e.g., NOx) in the environment are warranted. IMPORTANCE This work provides the first systematic evaluation of the isotopic fractionation of carbon and nitrogen in the organic explosive RDX during degradation by different pathways. It also provides data on the isotopic effects observed in the nitrite produced during RDX biodegradation. Both of these results could lead to better understanding of the fate of RDX in the environment and help improve monitoring and remediation technologies. PMID:27016566

Results of chemical and isotopic analyses of sediment and water from alluvium of the Canadian River near a closed municipal landfill, Norman, Oklahoma

USGS Publications Warehouse

Breit, George N.; Tuttle, Michele L.W.; Cozzarelli, Isabelle M.; Christenson, Scott C.; Jaeschke, Jeanne B.; Fey, David L.; Berry, Cyrus J.

2005-01-01

Results of physical and chemical analyses of sediment and water collected near a closed municipal landfill at Norman, Oklahoma are presented in this report. Sediment analyses are from 40 samples obtained by freeze-shoe coring at 5 sites, and 14 shallow (depth <1.3 m) sediment samples. The sediment was analyzed to determine grain size, the abundance of extractable iron species and the abundances and isotopic compositions of forms of sulfur. Water samples included pore water from the freeze-shoe core, ground water, and surface water. Pore water from 23 intervals of the core was collected and analyzed for major and trace dissolved species. Thirteen ground-water samples obtained from wells within a few meters of the freeze-shoe core sites and one from the landfill were analyzed for major and trace elements as well as the sulfur and oxygen isotope composition of dissolved sulfate. Samples of surface water were collected at 10 sites along the Canadian River from New Mexico to central Oklahoma. These river-water samples were analyzed for major elements, trace elements, and the isotopic composition of dissolved sulfate.

Chemical Evidence for Episodic Growth of a Fibrous Antitaxial Calcite Vein From Externally Derived Fluid

NASA Astrophysics Data System (ADS)

Barker, S. L.; Cox, S. F.; Eggins, S. M.; Gagan, M. K.

2005-12-01

Fibrous, massive and crustiform textured quartz and calcite veins occur within a deformed limestone-shale sequence at Taemas, in the Lachlan Fold Belt, eastern New South Wales, Australia. Stable isotope analyses of veins and host rock indicate that these veins formed from upwardly migrating, externally derived fluids. High spatial resolution (100 μm) analyses reveal per mil scale variations of stable C and O isotope ratios, and radiogenic Sr isotope ratios in a 1.5 cm thick, fibrous, antitaxial-growth calcite vein. LA-ICP-MS analyses (30 μm resolution) demonstrate significant variations in Fe, Mn, Sr, REE and Eu/Eu* parallel to the long axes of fibres. Stable and radiogenic isotopic ratio variations, and trace and REE concentration changes correlate with different cathodoluminesence zones, and slight changes in fibre orientation and thickness. The covariance of calcite textures and chemistry indicate that this fibrous vein grew episodically. Moreover, calcite in this vein was precipitated from externally derived fluid, which underwent variable fluid-rock interaction, and had a fluctuating oxidation state. This fibrous, antitaxial growth vein likely formed from fluid that migrated along fracture-controlled flow pathways.

Laser microprobe analyses of noble gas isotopes and halogens in fluid inclusions: Analyses of microstandards and synthetic inclusions in quartz

USGS Publications Warehouse

Böhlke, J.K.; Irwin, J.J.

1992-01-01

Ar, Kr, Xe, Cl, Br, I, and K abundances and isotopic compositions have been measured in microscopic fluid inclusions in minerals by noble gas mass spectrometry following neutron irradiation and laser extraction. The laser microprobe noble gas mass spectrometric (LMNGMS) technique was quantified by use of microstandards, including air-filled capillary tubes, synthetic basalt glass grains, standard hornblende grains, and synthetic fluid inclusions in quartz. Common natural concentrations of halogens (Cl, Br, and I) and noble gases (Ar and Kr) in trapped groundwaters and hydrothermal fluids can be analyzed simultaneously by LMNGMS in as little as 10−11 L of inclusion fluid, with accuracy and precision to within 5–10% for element and isotope ratios. Multicomponent element and isotope correlations indicate contaminants or persistent reservoirs of excess Xe and/or unfractionated air in some synthetic and natural fluid inclusion samples. LMNGMS analyses of natural fluid inclusions using the methods and calibrations reported here may be used to obtain unique information on sources of fluids, sources of fluid salinity, mixing, boiling (or unmixing), and water-rock interactions in ancient fluid flow systems.

Trace Metal Inventories and Lead Isotopic Composition Chronicle a Forest Fire’s Remobilization of Industrial Contaminants Deposited in the Angeles National Forest

PubMed Central

Odigie, Kingsley O.; Flegal, A. Russell

2014-01-01

The amounts of labile trace metals: [Co] (3 to 11 µg g−1), [Cu] (15 to 69 µg g−1), [Ni] (6 to 15 µg g−1), [Pb] (7 to 42 µg g−1), and [Zn] (65 to 500 µg g−1) in ash collected from the 2012 Williams Fire in Los Angeles, California attest to the role of fires in remobilizing industrial metals deposited in forests. These remobilized trace metals may be dispersed by winds, increasing human exposures, and they may be deposited in water bodies, increasing exposures in aquatic ecosystems. Correlations between the concentrations of these trace metals, normalized to Fe, in ash from the fire suggest that Co, Cu, and Ni in most of those samples were predominantly from natural sources, whereas Pb and Zn were enriched in some ash samples. The predominantly anthropogenic source of excess Pb in the ash was further demonstrated by its isotopic ratios (208Pb/207Pb: 206Pb/207Pb) that fell between those of natural Pb and leaded gasoline sold in California during the previous century. These analyses substantiate current human and environmental health concerns with the pyrogenic remobilization of toxic metals, which are compounded by projections of increases in the intensity and frequency of wildfires associated with climate change. PMID:25259524

Seasonal variations in the sources of natural and anthropogenic lead deposited at the East Rongbuk Glacier in the high-altitude Himalayas.

PubMed

Burn-Nunes, Laurie; Vallelonga, Paul; Lee, Khanghyun; Hong, Sungmin; Burton, Graeme; Hou, Shugui; Moy, Andrew; Edwards, Ross; Loss, Robert; Rosman, Kevin

2014-07-15

Lead (Pb) isotopic compositions and concentrations, and barium (Ba) and indium (In) concentrations have been analysed at sub-annual resolution in three sections from a <110 m ice core dated to the 18th and 20th centuries, as well as snow pit samples dated to 2004/2005, recovered from the East Rongbuk Glacier in the high-altitude Himalayas. Ice core sections indicate that atmospheric chemistry prior to ~1,953 was controlled by mineral dust inputs, with no discernible volcanic or anthropogenic contributions. Eighteenth century monsoon ice core chemistry is indicative of dominant contributions from local Himalayan sources; non-monsoon ice core chemistry is linked to contributions from local (Himalayan), regional (Indian/Thar Desert) and long-range (North Africa, Central Asia) sources. Twentieth century monsoon and non-monsoon ice core data demonstrate similar seasonal sources of mineral dust, however with a transition to less-radiogenic isotopic signatures that suggests local and regional climate/environmental change. The snow pit record demonstrates natural and anthropogenic contributions during both seasons, with increased anthropogenic influence during non-monsoon times. Monsoon anthropogenic inputs are most likely sourced to South/South-East Asia and/or India, whereas non-monsoon anthropogenic inputs are most likely sourced to India and Central Asia. Copyright © 2014 Elsevier B.V. All rights reserved.

Bunburra Rockhole: Exploring the geology of a new differentiated asteroid

NASA Astrophysics Data System (ADS)

Benedix, G. K.; Bland, P. A.; Friedrich, J. M.; Mittlefehldt, D. W.; Sanborn, M. E.; Yin, Q.-Z.; Greenwood, R. C.; Franchi, I. A.; Bevan, A. W. R.; Towner, M. C.; Perrotta, G. C.; Mertzman, S. A.

2017-07-01

Bunburra Rockhole is the first recovered meteorite of the Desert Fireball Network. We expanded a bulk chemical study of the Bunburra Rockhole meteorite to include major, minor and trace element analyses, as well as oxygen and chromium isotopes, in several different pieces of the meteorite. This was to determine the extent of chemical heterogeneity and constrain the origin of the meteorite. Minor and trace element analyses in all pieces are exactly on the basaltic eucrite trend. Major element analyses show a slight deviation from basaltic eucrite compositions, but not in any systematic pattern. New oxygen isotope analyses on 23 pieces of Bunburra Rockhole shows large variation in both δ17O and δ18O, and both are well outside the HED parent body fractionation line. We present the first Cr isotope results of this rock, which are also distinct from HEDs. Detailed computed tomographic scanning and back-scattered electron mapping do not indicate the presence of any other meteoritic contaminant (contamination is also unlikely based on trace element chemistry). We therefore conclude that Bunburra Rockhole represents a sample of a new differentiated asteroid, one that may have more variable oxygen isotopic compositions than 4 Vesta. The fact that Bunburra Rockhole chemistry falls on the eucrite trend perhaps suggests that multiple objects with basaltic crusts accreted in a similar region of the Solar System.

Rb-Sr and Sm-Nd Ages of Zagami DML and SR Isotopic Heterogeneity in Zagami

NASA Technical Reports Server (NTRS)

Nyquist, L.aurenceE.; Shih, C.-Y.; Reese, Y. D.

2010-01-01

Zagami contains lithologic heterogeneity suggesting that it did not form in a homogeneous, thick lava flow [1]. We have previously investigated the Sr and Nd isotopic systematics of Coarse-Grained (CG) and Fine-Grained (FG) lithologies described by [2]. Both appear to belong to Normal Zagami (NZ) [1,3], but their initial Sr-isotopic compositions differ [4,5]. Here we report new analyses of the Dark Mottled Lithology (DML, [3]) that show its age and initial Sr and Nd isotopic compositions to be identical within error limits with those of CG, but Sr initial isotopic compositions differ from those of FG.

High-precision isotopic characterization of USGS reference materials by TIMS and MC-ICP-MS

NASA Astrophysics Data System (ADS)

Weis, Dominique; Kieffer, Bruno; Maerschalk, Claude; Barling, Jane; de Jong, Jeroen; Williams, Gwen A.; Hanano, Diane; Pretorius, Wilma; Mattielli, Nadine; Scoates, James S.; Goolaerts, Arnaud; Friedman, Richard M.; Mahoney, J. Brian

2006-08-01

The Pacific Centre for Isotopic and Geochemical Research (PCIGR) at the University of British Columbia has undertaken a systematic analysis of the isotopic (Sr, Nd, and Pb) compositions and concentrations of a broad compositional range of U.S. Geological Survey (USGS) reference materials, including basalt (BCR-1, 2; BHVO-1, 2), andesite (AGV-1, 2), rhyolite (RGM-1, 2), syenite (STM-1, 2), granodiorite (GSP-2), and granite (G-2, 3). USGS rock reference materials are geochemically well characterized, but there is neither a systematic methodology nor a database for radiogenic isotopic compositions, even for the widely used BCR-1. This investigation represents the first comprehensive, systematic analysis of the isotopic composition and concentration of USGS reference materials and provides an important database for the isotopic community. In addition, the range of equipment at the PCIGR, including a Nu Instruments Plasma MC-ICP-MS, a Thermo Finnigan Triton TIMS, and a Thermo Finnigan Element2 HR-ICP-MS, permits an assessment and comparison of the precision and accuracy of isotopic analyses determined by both the TIMS and MC-ICP-MS methods (e.g., Nd isotopic compositions). For each of the reference materials, 5 to 10 complete replicate analyses provide coherent isotopic results, all with external precision below 30 ppm (2 SD) for Sr and Nd isotopic compositions (27 and 24 ppm for TIMS and MC-ICP-MS, respectively). Our results also show that the first- and second-generation USGS reference materials have homogeneous Sr and Nd isotopic compositions. Nd isotopic compositions by MC-ICP-MS and TIMS agree to within 15 ppm for all reference materials. Interlaboratory MC-ICP-MS comparisons show excellent agreement for Pb isotopic compositions; however, the reproducibility is not as good as for Sr and Nd. A careful, sequential leaching experiment of three first- and second-generation reference materials (BCR, BHVO, AGV) indicates that the heterogeneity in Pb isotopic compositions, and concentrations, could be directly related to contamination by the steel (mortar/pestle) used to process the materials. Contamination also accounts for the high concentrations of certain other trace elements (e.g., Li, Mo, Cd, Sn, Sb, W) in various USGS reference materials.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

High precision isotope ratio measurements of mercury isotopes in cinnabar ores using multi-collector inductively coupled plasma mass spectrometry.

PubMed

Hintelmann, Holger; Lu, ShengYong

2003-06-01

Variations in Hg isotope ratios in cinnabar ores obtained from different countries were detected by high precision isotope ratio measurements using multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Values of delta198/202Hg varied from 0.0-1.3 percent per thousand relative to a NIST SRM 1641d Hg solution. The typical external uncertainty of the delta values was 0.06 to 0.26 percent per thousand. Hg was introduced into the plasma as elemental Hg after reduction by sodium borohydride. A significant fractionation of lead isotopes was observed during the simultaneous generation of lead hydride, preventing normalization of the Hg isotope ratios using the measured 208/206Pb ratio. Hg ratios were instead corrected employing the simultaneously measured 205/203T1 ratio. Using a 10 ng ml(-1) Hg solution and 10 min of sampling, introducing 60 ng of Hg, the internal precision of the isotope ratio measurements was as low as 14 ppm. Absolute Hg ratios deviated from the representative IUPAC values by approximately 0.2% per u. This observation is explained by the inadequacy of the exponential law to correct for mass bias in MC-ICP-MS measurements. In the absence of a precisely characterized Hg isotope ratio standard, we were not able to determine unambiguously the absolute Hg ratios of the ore samples, highlighting the urgent need for certified standard materials.

Tracing source pollution in soils using cadmium and lead isotopes.

PubMed

Cloquet, C; Carignan, J; Libourel, G; Sterckeman, T; Perdrix, E

2006-04-15

Tracing the source of heavy metals in the environment is of key importance for our understanding of their pollution and natural cycles in the surface Earth reservoirs. Up to now, most exclusively Pb isotopes were used to effectively trace metal pollution sources in the environment. Here we report systematic variations of Cd isotope ratios measured in polluted topsoils surrounding a Pb-Zn refinery plant in northern France. Fractionated Cd was measured in soil samples surrounding the refinery, and this fractionation can be attributed to the refining processes. Despite the Cd isotopic ratios being precisely measured, the obtained uncertainties are still large compared to the total isotopic variation. Nevertheless, for the first time, Cd isotopically fractionated by industrial processes may be traced in the environment. On the same samples, Pb isotope systematics suggested that materials actually used by the refinery were not the major source of Pb in soils, probably because refined ore origins changed over the 100 years of operation. On the other hand, Cd isotopes and concentrations measured in topsoils allowed identification of three main origins (industrial dust and slag and agriculture), assuming that all Cd ores are not fractionated, as suggested by terrestrial rocks so far analyzed, and calculation of their relative contributions for each sampling point. Understanding that this refinery context was an ideal situation for such a study, our results lead to the possibility of tracing sources of anthropogenic Cd and better constrain mixing processes, fluxes, transport, and phasing out of industrial input in nature.

Winter diets of immature green turtles (Chelonia mydas) on a northern feeding ground: integrating stomach contents and stable isotope analyses

USGS Publications Warehouse

Williams, Natalie C.; Bjorndal, Karen A.; Lamont, Margaret M.; Carthy, Raymond R.

2015-01-01

The foraging ecology and diet of the green turtle, Chelonia mydas, remain understudied, particularly in peripheral areas of its distribution. We assessed the diet of an aggregation of juvenile green turtles at the northern edge of its range during winter months using two approaches. Stomach content analyses provide a single time sample, and stable isotope analyses integrate diet over a several-month period. We evaluated diet consistency in prey choice over time by comparing the results of these two approaches. We examined stomach contents from 43 juvenile green turtles that died during cold stunning events in St. Joseph Bay, Florida, in 2008 and 2011. Stomach contents were evaluated for volume, dry mass, percent frequency of occurrence, and index of relative importance of individual diet items. Juvenile green turtles were omnivorous, feeding primarily on seagrasses and tunicates. Diet characterizations from stomach contents differed from those based on stable isotope analyses, indicating the turtles are not feeding consistently during winter months. Evaluation of diets during warm months is needed.

Multiple Nebular Gas Reservoirs Recorded by Oxygen Isotope Variation in a Spinel-rich CAI in CO3 MIL 090019

NASA Technical Reports Server (NTRS)

Simon, J. I.; Simon, S. B.; Nguyen, A. N.; Ross, D. K.; Messenger, S.

2017-01-01

We conducted NanoSIMS O-isotopic imaging of a primitive spinel-rich CAI spherule (27-2) from the MIL 090019 CO3 chondrite. Inclusions such as 27-2 are proposed to record inner nebula processes during an epoch of rapid solar nebula evolution. Mineralogical and textural analyses suggest that this CAI formed by high temperature reactions, partial melting, and condensation. This CAI exhibits radial O-isotopic heterogeneity among multiple occurrences of the same mineral, reflecting interactions with distinct nebular O-isotopic reservoirs.

Zn/Cd ratios and cadmium isotope evidence for the classification of lead-zinc deposits

PubMed Central

Wen, Hanjie; Zhu, Chuanwei; Zhang, Yuxu; Cloquet, Christophe; Fan, Haifeng; Fu, Shaohong

2016-01-01

Lead-zinc deposits are often difficult to classify because clear criteria are lacking. In recent years, new tools, such as Cd and Zn isotopes, have been used to better understand the ore-formation processes and to classify Pb-Zn deposits. Herein, we investigate Cd concentrations, Cd isotope systematics and Zn/Cd ratios in sphalerite from nine Pb-Zn deposits divided into high-temperature systems (e.g., porphyry), low-temperature systems (e.g., Mississippi Valley type [MVT]) and exhalative systems (e.g., sedimentary exhalative [SEDEX]). Our results showed little evidence of fractionation in the high-temperature systems. In the low-temperature systems, Cd concentrations were the highest, but were also highly variable, a result consistent with the higher fractionation of Cd at low temperatures. The δ114/110Cd values in low-temperature systems were enriched in heavier isotopes (mean of 0.32 ± 0.31‰). Exhalative systems had the lowest Cd concentrations, with a mean δ114/110Cd value of 0.12 ± 0.50‰. We thus conclude that different ore-formation systems result in different characteristic Cd concentrations and fraction levels and that low-temperature processes lead to the most significant fractionation of Cd. Therefore, Cd distribution and isotopic studies can support better understanding of the geochemistry of ore-formation processes and the classification of Pb-Zn deposits. PMID:27121538

A 500 year sediment lake record of anthropogenic and natural inputs to Windermere (English Lake District) using double-spike lead isotopes, radiochronology, and sediment microanalysis.

PubMed

Miller, Helen; Croudace, Ian W; Bull, Jonathan M; Cotterill, Carol J; Dix, Justin K; Taylor, Rex N

2014-07-01

A high-resolution record of pollution is preserved in recent sediments from Windermere, the largest lake in the English Lake District. Data derived from X-ray core scanning (validated against wavelength dispersive X-ray fluorescence), radiochronological techniques ((210)Pb and (137)Cs) and ultrahigh precision, double-spike mass spectrometry for lead isotopes are combined to decipher the anthropogenic inputs to the lake. The sediment record suggests that while most element concentrations have been stable, there has been a significant increase in lead, zinc, and copper concentrations since the 1930s. Lead isotope down-core variations identify three major contributory sources of anthropogenic (industrial) lead, comprising gasoline lead, coal combustion lead (most likely source is coal-fired steam ships), and lead derived from Carboniferous Pb-Zn mineralization (mining activities). Periods of metal workings do not correlate with peaks in heavy metals due to the trapping efficiency of up-system lakes in the catchment. Heavy metal increases could be due to flood-induced metal inwash after the cessation of mining and the weathering of bedrock in the catchment. The combination of sediment analysis techniques used provides new insights into the pollutant depositional history of Windermere and could be similarly applied to other lake systems to determine the timing and scale of anthropogenic inputs.

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

PubMed

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

2005-04-14

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

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

PubMed

Halliday, Alex N

2008-11-28

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

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Isotopic studies in returned lunar samples

NASA Technical Reports Server (NTRS)

Alexander, E. C., Jr.

1971-01-01

Analysis of lunar soil samples returned by Apollo 11 and 12 flights are discussed. Isotopic studies of the rare gases from Apollo 11 flight lunar samples are presented. The lunar soil analyses indicated the following: (1) high concentrations of solar wind rare gases, (2) isotopic match between solar wind gases and gas components in gas-rich meteorites, and (3) rare gases attributable to spallation reactions induced in heavier nuclides by cosmic ray particles.

Dolomitization in a mixing zone of near-seawater composition, Late Pleistocene, northeastern Yucatan Peninsula

USGS Publications Warehouse

Ward, W. C.; Halley, Robert B.

1985-01-01

18O compositions of Yucatecan dolomite and of modern ground water suggest dolomite precipitation from mixed water ranging from about 75% seawater, 25% freshwater to nearly all seawater. (Isotope analyses are for the most stable calcian dolomites; more soluble, calcium-rich dolomite presumably is analyzed with calcite and thought to be isotopically lighter than the less soluble dolomite.) In the cement sequence, the most stable dolomite is followed by more soluble dolomite as ground water becomes less saline. Isotope analyses, together with position of dolomite in the cement sequence, suggest the most stable calcian dolomite (including limpid dolomite) precipitated from mixed water with large proportions of seawater, and the less stable, more calcian dolomite precipitated from fresher mixed water.

Examining the response of larch needle carbohydrates to climate using compound-specific δ13C and concentration analyses

NASA Astrophysics Data System (ADS)

Rinne, Katja T.; Saurer, Matthias; Kirdyanov, Alexander V.; Bryukhanova, Marina V.; Prokushkin, Anatoly S.; Churakova Sidorova, Olga V.; Siegwolf, Rolf T. W.

2016-04-01

Little is known about the dynamics of concentrations and carbon isotope ratios of individual carbohydrates in leaves in response to climatic and physiological factors. Improved knowledge of the isotopic ratio in sugars will enhance our understanding of the tree ring isotope ratio and will help to decipher environmental conditions in retrospect more reliably. Carbohydrate samples from larch (Larix gmelinii) needles of two sites in the continuous permafrost zone of Siberia with differing growth conditions were analysed with the Compound-Specific Isotope Analysis (CSIA). We compared concentrations and carbon isotope values (δ13C) of sucrose, fructose, glucose and pinitol combined with phenological data. The results for the variability of the needle carbohydrates show high dynamics with distinct seasonal characteristics between and within the studied years with a clear link to the climatic conditions, particularly vapour pressure deficit. Compound-specific differences in δ13C values as a response to climate were detected. The δ13C of pinitol, which contributes up to 50% of total soluble carbohydrates, was almost invariant during the whole growing season. Our study provides the first in-depth characterization of compound-specific needle carbohydrate isotope variability, identifies involved mechanisms and shows the potential of such results for linking tree physiological responses to different climatic conditions.

A guide for the laboratory information management system (LIMS) for light stable isotopes--Versions 7 and 8

USGS Publications Warehouse

Coplen, Tyler B.

2000-01-01

The reliability and accuracy of isotopic data can be improved by utilizing database software to (i) store information about samples, (ii) store the results of mass spectrometric isotope-ratio analyses of samples, (iii) calculate analytical results using standardized algorithms stored in a database, (iv) normalize stable isotopic data to international scales using isotopic reference materials, and (v) generate multi-sheet paper templates for convenient sample loading of automated mass-spectrometer sample preparation manifolds. Such a database program, the Laboratory Information Management System (LIMS) for Light Stable Isotopes, is presented herein. Major benefits of this system include (i) a dramatic improvement in quality assurance, (ii) an increase in laboratory efficiency, (iii) a reduction in workload due to the elimination or reduction of retyping of data by laboratory personnel, and (iv) a decrease in errors in data reported to sample submitters. Such a database provides a complete record of when and how often laboratory reference materials have been analyzed and provides a record of what correction factors have been used through time. It provides an audit trail for laboratories. LIMS for Light Stable Isotopes is available for both Microsoft Office 97 Professional and Microsoft Office 2000 Professional as versions 7 and 8, respectively. Both source code (mdb file) and precompiled executable files (mde) are available. Numerous improvements have been made for continuous flow isotopic analysis in this version (specifically 7.13 for Microsoft Access 97 and 8.13 for Microsoft Access 2000). It is much easier to import isotopic results from Finnigan ISODAT worksheets, even worksheets on which corrections for amount of sample (linearity corrections) have been added. The capability to determine blank corrections using isotope mass balance from analyses of elemental analyzer samples has been added. It is now possible to calculate and apply drift corrections to isotopic data based on the time of day of analysis. Whereas Finnigan ISODAT software is confined to using only a single peak for calculating delta values, LIMS now enables one to use the mean of two or more reference injections during a continuous flow analysis to calculate delta values. This is useful with Finnigan?s GasBench II online sample preparation system. Concentrations of carbon, nitrogen, and sulfur can be calculated based one or more isotopic reference materials analyzed with a group of samples. Both sample data and isotopic analysis data can now be exported to Excel files. A calculator for determining the amount of sample needed for isotopic analysis based on a previous amount of sample and continuous flow area is now an integral part of LIMS for Light Stable Isotopes. LIMS for Light Stable Isotopes can now assign an error code to Finnigan elemental analyzer analyses in which one of the electrometers has saturated due to analysis of too much sample material, giving rise to incorrect isotopic abundances. Information on downloading this report and downloading code and databases is provided at the Internet addresses: http://water.usgs.gov/software/geochemical.html or http://www.geogr.uni-jena.de/software/geochemical.html in the Eastern Hemisphere.

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

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

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

2006-12-22

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

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

NASA Astrophysics Data System (ADS)

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

2010-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Noble-gas-rich separates from the Allende meteorite

NASA Technical Reports Server (NTRS)

Ott, U.; Mack, R.; Chang, S.

1981-01-01

Predominantly carbonaceous HF/HCl-resistant residues from the Allende meteorite are studied. Samples are characterized by SEM/EDXA, X-ray diffraction, INAA, C, S, H, N, and noble gas analyses. Isotopic data for carbon show variations no greater than 5%, while isotopic data from noble gases confirm previously established systematics. Noble gas abundances correlate with those of C and N, and concomitant partial loss of C and normal trapped gas occur during treatments with oxidizing acids. HF/HCl demineralization of bulk meteorite results in similar fractional losses of C and trapped noble gases, which leads to the conclusion that various macromolecular carbonaceous substances serve as the main host phase for normal trapped noble gases and anomalous gases in acid-resistant residues, and as the carrier of the major part of trapped noble gases lost during HF/HCl demineralization. Limits on the possible abundances of dense mineralic host phases in the residues are obtained, and considerations of the nucleogenetic origin for CCF-XE indicate that carbonaceous host phases and various forms of organic matter in carbonaceous meteorites may have a presolar origin.

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

Inherited Pb isotopic records in olivine antecryst-hosted melt inclusions from Hawaiian lavas

NASA Astrophysics Data System (ADS)

Sakyi, Patrick Asamoah; Tanaka, Ryoji; Kobayashi, Katsura; Nakamura, Eizo

2012-10-01

Dislocation textures of olivine grains and Pb isotopic compositions (207Pb/206Pb and 208Pb/206Pb) of olivine-hosted melt inclusions in basaltic lavas from three Hawaiian volcanoes (Kilauea, Mauna Loa, and Koolau) were examined. More than 70% of the blocky olivine grains in the studied samples have a regular-shaped dislocation texture with their dislocation densities exceeding 106 cm-2, and can be considered as deformed olivine. The size distribution of blocky olivine grains shows that more than 99% of blocky olivines coarser than 1.2 mm are identified as deformed olivine. These deformed olivine grains are identified as antecrysts, which originally crystallized from previous stages of magmatism in the same shield, followed by plastic deformation prior to entrainment in the erupted host magmas. This study revealed that entrainment of mantle-derived crystallization products by younger batches of magma is an important part of the evolution of magnesium-rich Hawaiian magma. Lead isotopic compositions of melt inclusions hosted in the olivine antecrysts provide information of the evolutionary history of Hawaiian volcanoes which could not have been accessed if only whole rock analyses were carried out. Antecryst-hosted melt inclusions in Kilauea and Koolau lavas demonstrate that the source components in the melting region changed during shield formation. In particular, evidence of interaction of plume-derived melts and upper mantle was observed in the earliest stage of Koolau magmatism.

To what extent do food preferences explain the trophic position of heterotrophic and mixotrophic microbial consumers in a Sphagnum peatland?

PubMed

Jassey, Vincent E J; Meyer, Caroline; Dupuy, Christine; Bernard, Nadine; Mitchell, Edward A D; Toussaint, Marie-Laure; Metian, Marc; Chatelain, Auriel P; Gilbert, Daniel

2013-10-01

Although microorganisms are the primary drivers of biogeochemical cycles, the structure and functioning of microbial food webs are poorly studied. This is the case in Sphagnum peatlands, where microbial communities play a key role in the global carbon cycle. Here, we explored the structure of the microbial food web from a Sphagnum peatland by analyzing (1) the density and biomass of different microbial functional groups, (2) the natural stable isotope (δ(13)C and δ(15)N) signatures of key microbial consumers (testate amoebae), and (3) the digestive vacuole contents of Hyalosphenia papilio, the dominant testate amoeba species in our system. Our results showed that the feeding type of testate amoeba species (bacterivory, algivory, or both) translates into their trophic position as assessed by isotopic signatures. Our study further demonstrates, for H. papilio, the energetic benefits of mixotrophy when the density of its preferential prey is low. Overall, our results show that testate amoebae occupy different trophic levels within the microbial food web, depending on their feeding behavior, the density of their food resources, and their metabolism (i.e., mixotrophy vs. heterotrophy). Combined analyses of predation, community structure, and stable isotopes now allow the structure of microbial food webs to be more completely described, which should lead to improved models of microbial community function.

Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

NASA Technical Reports Server (NTRS)

Jahnke, L. L.; Eder, W.; Huber, Robert; Hinrichs, K-U.; Hayes, J. M.; DesMarais, D. J.; Cady, S. L.; Hope, J. M.; Summons, R. E.

2001-01-01

This paper describes a study of lipid biomarker composition and carbon isotopic fractionation in cultured Aquificales and natural analogues from Yellowstone National Park. Additional information is contained in the original extended abstract.

Elemental and isotopic abundances in the solar wind

NASA Technical Reports Server (NTRS)

Geiss, J.

1972-01-01

The use of collecting foils and lunar material to assay the isotopic composition of the solar wind is reviewed. Arguments are given to show that lunar surface correlated gases are likely to be most useful in studying the history of the solar wind, though the isotopic abundances are thought to give a good approximation to the solar wind composition. The results of the analysis of Surveyor material are also given. The conditions leading to a significant component of the interstellar gas entering the inner solar system are reviewed and suggestions made for experimental searches for this fraction. A critical discussion is given of the different ways in which the basic solar composition could be modified by fractionation taking place between the sun's surface and points of observation such as on the Moon or in interplanetary space. An extended review is made of the relation of isotopic and elemental composition of the interplanetary gas to the dynamic behavior of the solar corona, especially processes leading to fractionation. Lastly, connection is made between the subject of composition, nucleosynthesis and the convective zone of the sun, and processes leading to modification of initial accretion of certain gases on the Earth and Moon.

A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

USGS Publications Warehouse

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

1989-01-01

Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS. ?? 1989.

First-principles theory of anharmonicity and the inverse isotope effect in superconducting palladium-hydride compounds.

PubMed

Errea, Ion; Calandra, Matteo; Mauri, Francesco

2013-10-25

Palladium hydrides display the largest isotope effect anomaly known in the literature. Replacement of hydrogen with the heavier isotopes leads to higher superconducting temperatures, a behavior inconsistent with harmonic theory. Solving the self-consistent harmonic approximation by a stochastic approach, we obtain the anharmonic free energy, the thermal expansion, and the superconducting properties fully ab initio. We find that the phonon spectra are strongly renormalized by anharmonicity far beyond the perturbative regime. Superconductivity is phonon mediated, but the harmonic approximation largely overestimates the superconducting critical temperatures. We explain the inverse isotope effect, obtaining a -0.38 value for the isotope coefficient in good agreement with experiments, hydrogen anharmonicity being mainly responsible for the isotope anomaly.

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

NASA Astrophysics Data System (ADS)

Zurbrick, Cheryl M.

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

Lead in ancient Rome's city waters.

PubMed

Delile, Hugo; Blichert-Toft, Janne; Goiran, Jean-Philippe; Keay, Simon; Albarède, Francis

2014-05-06

It is now universally accepted that utilization of lead for domestic purposes and water distribution presents a major health hazard. The ancient Roman world was unaware of these risks. How far the gigantic network of lead pipes used in ancient Rome compromised public health in the city is unknown. Lead isotopes in sediments from the harbor of Imperial Rome register the presence of a strong anthropogenic component during the beginning of the Common Era and the Early Middle Ages. They demonstrate that the lead pipes of the water distribution system increased Pb contents in drinking water of the capital city by up to two orders of magnitude over the natural background. The Pb isotope record shows that the discontinuities in the pollution of the Tiber by lead are intimately entwined with the major issues affecting Late Antique Rome and its water distribution system.

Stable isotope signatures and trophic-step fractionation factors of fish tissues collected as non-lethal surrogates of dorsal muscle.

PubMed

Busst, Georgina M A; Bašić, Tea; Britton, J Robert

2015-08-30

Dorsal white muscle is the standard tissue analysed in fish trophic studies using stable isotope analyses. As muscle is usually collected destructively, fin tissues and scales are often used as non-lethal surrogates; we examined the utility of scales and fin tissue as muscle surrogates. The muscle, fin and scale δ(15) N and δ(13) C values from 10 cyprinid fish species determined with an elemental analyser coupled with an isotope ratio mass spectrometer were compared. The fish comprised (1) samples from the wild, and (2) samples from tank aquaria, using six species held for 120 days and fed a single food resource. Relationships between muscle, fin and scale isotope ratios were examined for each species and for the entire dataset, with the efficacy of four methods of predicting muscle isotope ratios from fin and scale values being tested. The fractionation factors between the three tissues of the laboratory fishes and their food resource were then calculated and applied to Bayesian mixing models to assess their effect on fish diet predictions. The isotopic data of the three tissues per species were distinct, but were significantly related, enabling estimations of muscle values from the two surrogates. Species-specific equations provided the least erroneous corrections of scale and fin isotope ratios (errors < 0.6‰). The fractionation factors for δ(15) N values were in the range obtained for other species, but were often higher for δ(13) C values. Their application to data from two fish populations in the mixing models resulted in significant alterations in diet predictions. Scales and fin tissue are strong surrogates of dorsal muscle in food web studies as they can provide estimates of muscle values within an acceptable level of error when species-specific methods are used. Their derived fractionation factors can also be applied to models predicting fish diet composition from δ(15) N and δ(13) C values. Copyright © 2015 John Wiley & Sons, Ltd.

Late Quaternary Environmental Changes Inferred from the stable Oxygen Isotope Composition of Aquatic Insects (Chironomidae: Diptera) and Stable Hydrogen Isotope Composition of bulk sediments from Idavain Lake, Southwest Alaska

NASA Astrophysics Data System (ADS)

Wang, Y.; Finney, B.; Wooller, M. J.

2007-12-01

Several techniques are available to examine the isotopic composition of historic lake waters, providing data that can subsequently be used to examine environmental changes. Recently-developed techniques are the stable oxygen isotope analysis of subfossil chironomid (Diptera: Chironomidae) head capsules (mostly chitin) preserved in lake sediments and stable hydrogen isotope analyses directly on bulk sediments. An advantage of using δ18O of chironomids is that the chitinous chironomid headcapsules preserve well in lake sediments, retaining the stable oxygen isotope signature of the lake in which they lived. An advantage of δD analyses of bulk sediments is that a sediment core can be analyzed relatively easily and when the %C (total organic carbon) and %H profiles correlate the data can be used to infer past δD changes of the organics in the sediments. We present results from these analyses of a lake sediment core from Idavain Lake (58°46'N, 155°57'W, 223m above sea level) in southwest Alaska in concert with other paleolimnological proxies, including δ15N, δ13C, LOI, magnetic susceptibility, organic content and opal concentrations for a better understanding of paleolimnological changes since deglaciation for the region. Our preliminilary result shows that downcore shifts of δ18O analyzed from chironomid head capsules coincide well with LOI and pollen changes. The δD of sediments and TOM showed large magnitude changes and reflected the relative lake level changes during the record. This study aim to test the correlation between stable isotope analyese on chiornomid head capsules, lake water, and bulk sediments. In the addition, our study will add to the relatively small database of paleoenvironmental reconstructions from terrestrial sites in Southwest Alaska.

Lead isotopes tracing the life cycle of a catchment: From source rock via weathering to human impact

NASA Astrophysics Data System (ADS)

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

2015-12-01

Chemical weathering of rocks involves consumption of CO2, a greenhouse gas with a strong influence on climate. Among rocks exposed to weathering, basalt plays a major role in the carbon cycle as it is more easily weathered than other crystalline silicate rocks. This means that basalt weathering acts as a major atmospheric CO2 sink. The present study investigated the lead isotopes in rock, soil and sediment for constraining the life cycle of a catchment, covering source rocks, erosion processes and products, and anthropogenic activities. For this, we investigated the Allanche river drainage basin in the Massif Central, the largest volcanic areas in France, that offers opportunities for selected geochemical studies since it drains a single type of virtually unpolluted volcanic rock, with agricultural activity increasing downstream. Soil and sediment are derived exclusively from basalt weathering, and their chemistry, coupled to isotope tracing, should shed light on the behavior of chemical species during weathering from parental bedrock. Bedrock samples of the basin, compared to regional bedrock of the volcanic province, resulted from a complex history and multiple mantle reservoir sources and mixing. Regarding soils and sediments, comparison of Pb and Zr normalized to mobile K shows a linear evolution of weathering processes, whereby lead enrichment from atmospheric deposition is the other major contributor. Lead-isotope ratios showed that most of the lead budget in sediment and soil results from bedrock weathering with an influence of past mining and mineral processing of ores in the Massif Central, and deposition of lead-rich particles from gasoline combustion, but no lead input from agricultural activity. A classic box model was used to investigate the dynamics of sediment transfer at the catchment scale, the lead behavior in the continuum bedrock-soil-sediment and the historical evolution of anthropogenic aerosol emissions.

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

USGS Publications Warehouse

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

1978-01-01

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

Stable isotopes in mineralogy

USGS Publications Warehouse

O'Neil, J.R.

1977-01-01

Stable isotope fractionations between minerals are functions of the fundamental vibrational frequencies of the minerals and therefore bear on several topics of mineralogical interest. Isotopic compositions of the elements H, C, O, Si, and S can now be determined routinely in almost any mineral. A summary has been made of both published and new results of laboratory investigations, analyses of natural materials, and theoretical considerations which bear on the importance of temperature, pressure, chemical composition and crystal structure to the isotopic properties of minerals. It is shown that stable isotope studies can sometimes provide evidence for elucidating details of crystal structure and can be a powerful tool for use in tracing the reaction paths of mineralogical reactions. ?? 1977 Springer-Verlag.

Isotopic Analysis and Evolved Gases

NASA Technical Reports Server (NTRS)

Swindle, Timothy D.; Boynton, William V.; Chutjian, Ara; Hoffman, John H.; Jordan, Jim L.; Kargel, Jeffrey S.; McEntire, Richard W.; Nyquist, Larry

1996-01-01

Precise measurements of the chemical, elemental, and isotopic composition of planetary surface material and gases, and observed variations in these compositions, can contribute significantly to our knowledge of the source(s), ages, and evolution of solar system materials. The analyses discussed in this paper are mostly made by mass spectrometers or some other type of mass analyzer, and address three broad areas of interest: (1) atmospheric composition - isotopic, elemental, and molecular, (2) gases evolved from solids, and (3) solids. Current isotopic data on nine elements, mostly from in situ analysis, but also from meteorites and telescopic observations are summarized. Potential instruments for isotopic analysis of lunar, Martian, Venusian, Mercury, and Pluto surfaces, along with asteroid, cometary and icy satellites, surfaces are discussed.

Lead isotopes and trace metals in dust at Yucca Mountain

USGS Publications Warehouse

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

2008-01-01

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

Transboundary atmospheric lead pollution.

PubMed

Erel, Yigal; Axelrod, Tamar; Veron, Alain; Mahrer, Yitzak; Katsafados, Petros; Dayan, Uri

2002-08-01

A high-temporal resolution collection technique was applied to refine aerosol sampling in Jerusalem, Israel. Using stable lead isotopes, lead concentrations, synoptic data, and atmospheric modeling, we demonstrate that lead detected in the atmosphere of Jerusalem is not only anthropogenic lead of local origin but also lead emitted in other countries. Fifty-seven percent of the collected samples contained a nontrivial fraction of foreign atmospheric lead and had 206Pb/207Pb values which deviated from the local petrol-lead value (206Pb/207Pb = 1.113) by more than two standard deviations (0.016). Foreign 206Pb/207Pb values were recorded in Jerusalem on several occasions. The synoptic conditions on these dates and reported values of the isotopic composition of lead emitted in various countries around Israel suggest that the foreign lead was transported to Jerusalem from Egypt, Turkey, and East Europe. The average concentration of foreign atmospheric lead in Jerusalem was 23 +/- 17 ng/m3, similar to the average concentration of local atmospheric lead, 21 +/- 18 ng/ m3. Hence, the load of foreign atmospheric lead is similar to the load of local atmospheric lead in Jerusalem.

Atomic vapor laser isotope separation of lead-210 isotope

DOEpatents

Scheibner, K.F.; Haynam, C.A.; Johnson, M.A.; Worden, E.F.

1999-08-31

An isotopically selective laser process and apparatus for removal of Pb-210 from natural lead that involves a one-photon near-resonant, two-photon resonant excitation of one or more Rydberg levels, followed by field ionization and then electrostatic extraction. The wavelength to the near-resonant intermediate state is counter propagated with respect to the second wavelength required to populate the final Rydberg state. This scheme takes advantage of the large first excited state cross section, and only modest laser fluences are required. The non-resonant process helps to avoid two problems: first, stimulated Raman Gain due to the nearby F=3/2 hyperfine component of Pb-207 and, second, direct absorption of the first transition process light by Pb-207. 5 figs.

Atomic vapor laser isotope separation of lead-210 isotope

DOEpatents

Scheibner, Karl F.; Haynam, Christopher A.; Johnson, Michael A.; Worden, Earl F.

1999-01-01

An isotopically selective laser process and apparatus for removal of Pb-210 from natural lead that involves a one-photon near-resonant, two-photon resonant excitation of one or more Rydberg levels, followed by field ionization and then electrostatic extraction. The wavelength to the near-resonant intermediate state is counter propagated with respect to the second wavelength required to populate the final Rydberg state. This scheme takes advantage of the large first excited state cross section, and only modest laser fluences are required. The non-resonant process helps to avoid two problems: first, stimulated Raman Gain due to the nearby F=3/2 hyperfine component of Pb-207 and, second, direct absorption of the first transition process light by Pb-207.

Rainfall Type as a Dominant Control of the Isotopic Composition of Precipitation in the South Central United States

NASA Astrophysics Data System (ADS)

Sun, C.; Shanahan, T. M.; Partin, J. W.

2017-12-01

The processes that control the isotopic composition of precipitation in the mid-latitudes are understudied compared to the high and low latitudes, but are critical for interpreting paleo records using isotope proxies. To better understand these processes, we investigated changes of isotopic composition of rainwater in Central Texas using 20 months of event-based rainwater collection. We find that in both the event-based data and the monthly data from the Waco GNIP station, the dominant control on the isotopic composition of precipitation is the proportion that is derived from convective systems. This finding is consistent with previously reported data largely from tropical localities (Aggarwal et al., 2016), where large organized convective systems lead to high rainfall amounts and isotopically depleted precipitation. Although there are seasonal differences in the dominant rainfall types over the South Central US, with winter precipitation almost entirely stratiform, seasonality plays very little role in the net isotopic composition of precipitation because the total contribution during winter is small compared with spring, summer and fall. We also find that changes of source have little effect on the isotopic composition of rainfall, as the majority of the moisture is derived from the Gulf of Mexico with little influence of reevaporation or mixing. The majority of the warm season precipitation in the South Central US occurs in association with mesoscale convective systems (MCSs) and the development of these systems plays a critical role in the overall isotopic signature of precipitation. MCSs are characterized by a combination of intense, organized convection at their leading edges and trailing stratiform precipitation. Larger MCSs tend to contain higher proportions of stratiform rainfall and as a result, have isotopically depleted values. Proxy records from this region displaying more negative isotope values in the past should therefore be interpreted with caution as they could reflect either increases in cool versus warm season precipitation or changes in the intensity of warm season MCSs.

Chromatographic Separation of Cd from Plants via Anion-Exchange Resin for an Isotope Determination by Multiple Collector ICP-MS.

PubMed

Wei, Rongfei; Guo, Qingjun; Wen, Hanjie; Peters, Marc; Yang, Junxing; Tian, Liyan; Han, Xiaokun

2017-01-01

In this study, key factors affecting the chromatographic separation of Cd from plants, such as the resin column, digestion and purification procedures, were experimentally investigated. A technique for separating Cd from plant samples based on single ion-exchange chromatography has been developed, which is suitable for the high-precision analysis of Cd isotopes by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The robustness of the technique was assessed by replicate analyses of Cd standard solutions and plant samples. The Cd yields of the whole separation process were higher than 95%, and the 114/110 Cd values of three Cd second standard solutions (Münster Cd, Spex Cd, Spex-1 Cd solutions) relative to the NIST SRM 3108 were measured accurately, which enabled the comparisons of Cd isotope results obtained in other laboratories. Hence, stable Cd isotope analyses represent a powerful tool for fingerprinting specific Cd sources and/or examining biogeochemical reactions in ecological and environmental systems.

SAS2H Generated Isotopic Concentrations For B&W 15X15 PWR Assembly (SCPB:N/A)

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

J.W. Davis

This analysis is prepared by the Mined Geologic Disposal System (MGDS) Waste Package Development Department (WPDD) to provide pressurized water reactor (PWR) isotopic composition data as a function of time for use in criticality analyses. The objectives of this evaluation are to generate burnup and decay dependant isotopic inventories and to provide these inventories in a form which can easily be utilized in subsequent criticality calculations.

Isotope effect of mercury diffusion in air

PubMed Central

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

2014-01-01

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

Isotope effect of mercury diffusion in air.

PubMed

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

2014-01-01

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

Evaluation of gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) for the quality assessment of citrus liqueurs.

PubMed

Schipilliti, Luisa; Bonaccorsi, Ivana; Cotroneo, Antonella; Dugo, Paola; Mondello, Luigi

2013-02-27

Citrus liqueurs are alcoholic beverages obtained by maceration. The European Parliament protects these alcoholic beverages, forbidding the addition of nature-identical flavoring substances. However, for economical and technological reasons, producers often add natural and/or synthetic flavors to the alcoholic syrup, obtaining artificial spirit drinks. The aim of this study is to investigate the authenticity of Italian liqueurs, of lemon, bergamot, and mandarin (locally known as "limoncello", "bargamino", and "mandarinetto"), comparing the carbon isotope ratios with values determined in genuine cold-pressed peel oils. Authenticity assessment was performed using headspace-solid phase microextraction coupled to gas chromatography-combustion-isotope ratio mass spectrometry. Additional analyses were performed by direct enantioselective gas chromatography to determine the enantiomeric distribution of selected chiral volatiles and by gas chromatography-mass spectrometry for the qualitative analyses of the samples. The method allowed confirmation of genuineness. Enantioselective gas chromatography analyses confirmed the results, demonstrating the reliability of the method.

Isotopic fractionation of volatile species during bubble growth in magmas

NASA Astrophysics Data System (ADS)

Watson, E. B.

2016-12-01

Bubbles grow in decompressing magmas by simple expansion and also by diffusive supply of volatiles to the bubble/melt interface. The latter phenomenon is of significant geochemical interest because diffusion can fractionate isotopes, raising the possibility that the isotopic character of volatile components in bubbles may not reflect that of volatiles dissolved in the host melt over the lifetime of a bubble—even in the complete absence of equilibrium vapor/melt isotopic fractionation. None of the foregoing is conceptually new, but recent experimental studies have established the existence of isotope mass effects on diffusion in silicate melts for several elements (Li, Mg, Ca, Fe), and this finding has now been extended to the volatile (anionic) element chlorine (Fortin et al. 2016; this meeting). Knowledge of isotope mass effects on diffusion of volatile species opens the way for quantitative models of diffusive fractionation during bubble growth. Significantly different effects are anticipated for "passive" volatiles (e.g., noble gases and Cl) that are partitioned into existing bubbles but play little role in nucleation and growth, as opposed to "active" volatiles whose limited solubilities lead to bubble nucleation during magma decompression. Numerical solution of the appropriate diffusion/mass-conservation equations reveals that the isotope effect on passive volatiles partitioned into bubbles growing at a constant rate in a static system depends (predictably) upon R/D, Kd and D1/D2 (R = growth rate; D = diffusivity; Kd = bubble/melt partition coefficient; D1/D2 = diffusivity ratio of the isotopes of interest). Constant R is unrealistic, but other scenarios can be explored by including the solubility and EOS of an "active" volatile (e.g., CO2) in numerical simulations of bubble growth. For plausible decompression paths, R increases exponentially with time—leading, potentially, to larger isotopic fractionation of species partitioned into the growing bubble.

Tracing Carbon Flow from Primary Production to a Gulf Coast Salt Marsh Consumer, the Seaside Sparrow (Ammodramus maritimus)

NASA Astrophysics Data System (ADS)

Johnson, J. J.; Polito, M. J.; Olin, J.

2016-02-01

Determining the relative contributions of primary producers to salt marsh food webs is fundamental to understanding how these systems are structured. Biomarkers such as bulk carbon isotopes (13C/12C) and fatty acids have become popular tracers of trophic dynamics, based on the principle that the composition of biomarkers in consumer tissues is a reflection of the composition of these same biomarkers in a consumer's diet. However, the use of bulk stable isotope and fatty acid analyses to assess carbon flow in food webs is often hampered by confounding factors such as isotopic fractionation and fatty acid modifications that can occur between trophic levels. In contrast, compound-specific stable isotope analysis of amino acids may offer a more precise tracking of carbon flow through complex food webs. This is because the isotopic values of essential amino acids in consumer tissues are assimilated largely unchanged from their primary sources at the base of the food web. The aim of this study was to test the consistency of three different methods (bulk carbon stable isotope, fatty acid and compound-specific stable isotope analyses) while examining the carbon source pool underlying the diet of a common marsh consumer, the seaside sparrow (A. maritimus). This comparison allows us to gain a better idea of the relative merits of these analytical methods and contribute to a clearer model of overall trophic dynamics in a salt marsh food web.

Diet-consumer nitrogen isotope fractionation for prolonged fasting arthropods.

PubMed

Mizota, Chitoshi; Yamanaka, Toshiro

2011-12-01

Nitrogen acquisition for cellular metabolism during diapause is a primary concern for herbivorous arthropods. Analyses of naturally occurring stable isotopes of nitrogen help elucidate the mechanism. Relevant articles have cited (58 times up to mid-June 2011) anomalously elevated δ(15)N (per mil deviation of (15)N/(14)N, relative to atmospheric nitrogen=0 ‰) values (diet-consumer nitrogen isotope fractionation; up to 12 ‰) for a prolonged fasting raspberry beetle (Byturus tomentosus Degeer (Coleoptera: Byturidae)), which feeds on red raspberries (Rubus idaeus: δ(15)N= ~ +2 ‰). Biologists have hypothesised that extensive recycling of amino acid nitrogen is responsible for the prolonged fasting. Since this hypothesis was proposed in 1995, scientists have integrated biochemical and molecular knowledge to support the mechanism of prolonged diapausing of animals. To test the validity of the recycling hypothesis, we analysed tissue nitrogen isotope ratios for four Japanese arthropods: the shield bug Parastrachia japonensis Scott (Hemiptera: Cydnidae), the burrower bug Canthophorus niveimarginatus Scott (Hemiptera: Cydnidae), leaf beetle Gastrophysa atrocyanea Motschulsky (Coleoptera: Chrysomelidae) and the Japanese oak silkworm Antheraea yamamai (Lepidoptera: Saturniidae), all of which fast for more than 6 months as part of their life-history strategy. Resulting diet-consumer nitrogen isotope discrimination during fasting ranged from 0 to 7‰, as in many commonly known terrestrial arthropods. We conclude that prolonged fasting of arthropods does not always result in anomalous diet-consumer nitrogen isotope fractionation, since the recycling process is closed or nearly closed with respect to nitrogen isotopes.

North Pacific Atmospheric Circulation Change and Effective Moisture Variability in the Yukon Territory, Canada

NASA Astrophysics Data System (ADS)

Anderson, L.; Abbott, M. B.; Finney, B. P.; Burns, S. J.

2005-12-01

Analyses of sediment cores from Marcella Lake, a small, hydrologically-closed lake in the semi-arid interior southwest Yukon Territory, provide evaporation information for the last 4500 years at century-scale resolution. Water chemistry and oxygen isotope data from lakes and precipitation in the region indicate that oxygen isotope ratios from Marcella Lake are currently affected by summer evaporation. Past lake water changes were reconstructed from oxygen isotope analyses of sedimentary endogenic calcite. An oxygen isotope record of mean-annual precipitation from Jellybean Lake, a nearby open evaporation-insensitive system, provides simultaneous oxygen isotope ratio variations related to atmospheric circulation and ambient temperature. The difference between the two isotope records represents oxygen-18-enrichment in Marcella Lake water caused by summer evaporation. The oxygen isotope results indicate a prolonged period of lower evaporation between 3000 and 1500 cal BP, a finding that is consistent with independent evidence for higher lake levels during this period (i.e. increased effective moisture). The data indicate that since 1500 cal BP evaporation has increased and that during the last 200 years it has been greater than during the previous ~4000 years. Two prominent increases in evaporation occurred at 1200 and 200 cal BP. These shifts correspond with increases in aridity observed in other records of effective moisture variability in the interior southwest Yukon and with prominent changes in North Pacific atmospheric circulation patterns over the Gulf of Alaska.

Oxygen isotope ranking of late Eocene and Oligocene planktonic foraminifers: Implications for Oligocene sea-surface temperatures and global ice-volume

USGS Publications Warehouse

Poore, R.Z.; Matthews, R.K.

1984-01-01

Oxygen isotope analyses of late Eocene and Oligocene planktonic foraminifers from low and middle latitude sites in the Atlantic Basin show that different species from the same samples can yield significantly different isotopic values. The range of isotopic values observed between species is greatest at low-latitudes and declines poleward. Many planktonic foraminifers exhibit a systematic isotopic ranking with respect to each other and can therefore be grouped on the basis of their isotopic ranking. The isotopic ranking of some taxa, however, appears to vary geographically and/or through time. Isotopic and paleontologic data from DSDP Site 522 indicate that commonly used isotopic temperature scales underestimate Oligocene sea surface temperatures. We suggest these temperature scales require revision to reflect the presence of Oligocene glaciation. Comparison of isotopic and paleontologic data from Sites 522, 511 and 277 suggests cold, low-salinity surface waters were present in high southern latitudes during the early Oligocene. Lowsalinity, high latitude surface waters could be caused by Eocene/Oligocene paleogeography or by the production of warm saline bottom water. ?? 1984.

Stable isotope analysis of Pacific salmon: insight into trophic status and oceanographic conditions over the last 30 years

NASA Astrophysics Data System (ADS)

Satterfield, Franklin R.; Finney, Bruce P.

Food web interactions and the response of Pacific salmon to physical processes in the North Pacific Ocean over interannual and interdecadal timescales are explored using naturally occurring stable isotope ratios of carbon ( 13C/ 12C) and nitrogen ( 15N/ 14N). Stable isotope analyses of five species of sexually mature North Pacific salmon from Alaska ( Oncorhynchus spp.) cluster into three groups: chinook salmon ( O. tshawytscha) have the highest values, followed by coho ( O. kisutch), with chum ( O. keta), sockeye ( O. nerka), and pink ( O. gorbuscha) together having the lowest values. Although detailed isotopic data on salmon prey are lacking, there are limited data on relevant prey items from areas in which they are found in high abundance. These data suggest that the characteristics of the sockeye, pink and chum we have analyzed are compatible with their diets including open ocean squid and zooplankton, which are in general agreement with stomach content analyses. Isotope relationships between muscle and scale show consistent relationships for both δ13C ( R2=0.98) and δ 15N ( R2=0.90). Thus, scales, which have been routinely archived for many systems, can be used for retrospective analyses. Archived sockeye salmon scales spanning 1966-1999 from Red Lake, Kodiak Island, Alaska were analyzed for their stable isotope ratios of carbon and nitrogen. The δ15N record displays a decreasing trend of ~3‰ from 1969-1982 and an increasing trend of ~3‰ from 1982-1992, while the variations in δ13C are relatively minor. These trends may result from factors such as shifts in trophic level of feeding and/or feeding location, or may originate at the base of the food web via changes in processes such as nutrient cycling or primary productivity. Detailed studies on prey isotopic variability and its controls are needed to distinguish between these factors, and thus to improve the use of stable isotope analysis as a tool to learn more about present and past ecosystem change in the North Pacific and its relation to climatic change.

Seasonality of stable isotope composition of atmospheric water input at the southern slopes of Mt. Kilimanjaro, Tanzania

USGS Publications Warehouse

Otte, Insa; Detsch, Florian; Gutlein, Adrian; Scholl, Martha A.; Kiese, Ralf; Appelhans, Tim; Nauss, Thomas

2017-01-01

To understand the moisture regime at the southern slopes of Mt. Kilimanjaro, we analysed the isotopic variability of oxygen (δ18O) and hydrogen (δD) of rainfall, throughfall, and fog from a total of 2,140 samples collected weekly over 2 years at 9 study sites along an elevation transect ranging from 950 to 3,880 m above sea level. Precipitation in the Kilimanjaro tropical rainforests consists of a combination of rainfall, throughfall, and fog. We defined local meteoric water lines for all 3 precipitation types individually and the overall precipitation, δDprec = 7.45 (±0.05) × δ18Oprec + 13.61 (±0.20), n = 2,140, R2 = .91, p < .001. We investigated the precipitation-type-specific stable isotope composition and analysed the effects of amount, altitude, and temperature. Aggregated annual mean values revealed isotope composition of rainfall as most depleted and fog water as most enriched in heavy isotopes at the highest elevation research site. We found an altitude effect of δ18Orain = −0.11‰ × 100 m−1, which varied according to precipitation type and season. The relatively weak isotope or altitude gradient may reveal 2 different moisture sources in the research area: (a) local moisture recycling and (b) regional moisture sources. Generally, the seasonality of δ18Orain values follows the bimodal rainfall distribution under the influences of south- and north-easterly trade winds. These seasonal patterns of isotopic composition were linked to different regional moisture sources by analysing Hybrid Single Particle Lagrangian Integrated Trajectory backward trajectories. Seasonality of dexcess values revealed evidence of enhanced moisture recycling after the onset of the rainy seasons. This comprehensive dataset is essential for further research using stable isotopes as a hydrological tracer of sources of precipitation that contribute to water resources of the Kilimanjaro region.

Detection of bio-signature by microscopy and mass spectrometry

NASA Astrophysics Data System (ADS)

Tulej, M.; Wiesendanger, R.; Neuland, M., B.; Meyer, S.; Wurz, P.; Neubeck, A.; Ivarsson, M.; Riedo, V.; Moreno-Garcia, P.; Riedo, A.; Knopp, G.

2017-09-01

We demonstrate detection of micro-sized fossilized bacteria by means of microscopy and mass spectrometry. The characteristic structures of lifelike forms are visualized with a micrometre spatial resolution and mass spectrometric analyses deliver elemental and isotope composition of host and fossilized materials. Our studies show that high selectivity in isolation of fossilized material from host phase can be achieved while applying a microscope visualization (location), a laser ablation ion source with sufficiently small laser spot size and applying depth profiling method. Our investigations shows that fossilized features can be well isolated from host phase. The mass spectrometric measurements can be conducted with sufficiently high accuracy and precision yielding quantitative elemental and isotope composition of micro-sized objects. The current performance of the instrument allows the measurement of the isotope fractionation in per mill level and yield exclusively definition of the origin of the investigated species by combining optical visualization of investigated samples (morphology and texture), chemical characterization of host and embedded in the host micro-sized structure. Our isotope analyses involved bio-relevant B, C, S, and Ni isotopes which could be measured with sufficiently accuracy to conclude about the nature of the micro-sized objects.

Lead theft--a study of the "uniqueness" of lead from church roofs.

PubMed

Bond, John W; Hainsworth, Sarah V; Lau, Tien L

2013-07-01

In the United Kingdom, theft of lead is common, particularly from churches and other public buildings with lead roofs. To assess the potential to distinguish lead from different sources, 41 samples of lead from 24 church roofs in Northamptonshire, U.K, have been analyzed for relative abundance of trace elements and isotopes of lead using X-ray fluorescence (XRF) and inductively coupled plasma mass spectrometry, respectively. XRF revealed the overall presence of 12 trace elements with the four most abundant, calcium, phosphorus, silicon, and sulfur, showing a large weight percentage standard error of the mean of all samples suggesting variation in the weight percentage of these elements between different church roofs. Multiple samples from the same roofs, but different lead sheets, showed much lower weight percentage standard errors of the mean suggesting similar trace element concentrations. Lead isotope ratios were similar for all samples. Factors likely to affect the occurrence of these trace elements are discussed. © 2013 American Academy of Forensic Sciences.

Scientific Opportunities and Plans for FRIB

NASA Astrophysics Data System (ADS)

Bollen, Georg

2014-09-01

FRIB, the US's ``Facility for Rare Isotope Beams'' under construction at Michigan State University will be a world-leading rare isotope beam facility. FRIB will be based on a 400 kW, 200 MeV/u heavy ion linac and provide a wide variety of high-quality beams of unstable isotopes at unprecedented intensities, opening exciting research perspectives with fast, stopped, and reaccelerated beams. This talk will summarize the scientific opportunities with FRIB in the areas of nuclear science, nuclear astrophysics, and the test of fundamental interaction and symmetries, as well using isotopes from FRIB for societal benefits. Design features of FRIB and the status of the ongoing construction will be presented. FRIB, the US's ``Facility for Rare Isotope Beams'' under construction at Michigan State University will be a world-leading rare isotope beam facility. FRIB will be based on a 400 kW, 200 MeV/u heavy ion linac and provide a wide variety of high-quality beams of unstable isotopes at unprecedented intensities, opening exciting research perspectives with fast, stopped, and reaccelerated beams. This talk will summarize the scientific opportunities with FRIB in the areas of nuclear science, nuclear astrophysics, and the test of fundamental interaction and symmetries, as well using isotopes from FRIB for societal benefits. Design features of FRIB and the status of the ongoing construction will be presented. This material is based upon work supported by the U.S. Department of Energy Office of Science under Cooperative Agreement DE-SC0000661, the State of Michigan and Michigan State University. Michigan State University designs and establishes FRIB as a DOE.

Development of Simultaneous in situ Analysis of Carbon and Nitrogen Isotope Ratios in the Organic Matter by Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Ishida, A.; Kitajima, K.; Williford, K. H.; Kakegawa, T.; Valley, J. W.

2017-12-01

An in-situ analytical method for simultaneous analysis of carbon and nitrogen isotope ratios in organic matter was developed for 12 μm spots by secondary ion mass spectrometry (IMS 1280 at WiscSIMS). Secondary ions of 12C12C-, 12C13C-, 12C14N-, and 12C15N- are simultaneously measured by three Faraday cups and one electron multiplier. Ions of 12C12CH- are measured to monitor hydride interferences. The spot-by-spot reproducibility of δ13C and δ15N values of UWLA-1 anthracite standard (95.7 wt%C and 1.2 wt%N), which was selected as a running reference material, are 0.16‰ and 0.56‰ (2SD), respectively. A negative correlation is observed between the instrumental mass fractionation (mass bias) of carbon and 12C12CH-/12C12C- ratios of examined reference materials. In contrast, there is no correlation of mass bias and hydride cps for nitrogen isotope measurements, suggesting the mass bias of nitrogen can be determined independently of the hydrogen. Values of 22 individual globules of organic matter in a carbonate rock from the 1.9 Ga Gunflint Formation, determined by the new procedure, average δ13C = -33.5 ± 0.25‰ (VPDB) and δ15N = +5.2 ± 0.81‰ (Air). Values of δ13C of both SIMS and bulk kerogen analyses are consistent within analytical error. In contrast, a difference of 1.7‰, which is larger than the 2SD error of each analysis, is observed in δ15N values for in situ vs. bulk kerogen analyses (δ15Nbulk = +6.9 ± 0.6‰). This difference in δ15N might be caused by the preferential removal of low-δ15N components in the organic matter by HCl/HF acid treatment during the bulk kerogen isolation. Simultaneous analyses of carbon and nitrogen in the same micro-volume of organic matter in Precambrian sedimentary rocks will allow correlations with textures and mineralogical occurrences, which will provide more detailed constraints on environments and life of the early Earth. Furthermore, this method is applicable to a wide variety of other research fields, including nutrient distributions in the microstructure of plants and animals, heterogeneous isotope distributions of organic matter in meteorites, maturity of coal, and genesis of diamonds, leading us to understand the evolution of the Earth system.

Measurement of Proton-induced Radiation in Animal Tissue

NASA Astrophysics Data System (ADS)

Sękowski, P.; Skwira-Chalot, I.; Matulewicz, T.

Hadron therapy, because of the dosimetric and radiobiological advantages, is more and more often used in tumour treatment. This treatment method leads also to the radioactive effects induced by energetic protons on nuclei. Nuclear reactions may lead to the production of radioactive isotopes. In the present experiment, two animal (human-like) tissue samples were irradiated with 60 MeV protons. Gamma-ray spectroscopy and lifetime measurements allowed identifying isotopes produced during the irradiation, e.g. $^{18}$F and $^{34m}$Cl.

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

PubMed

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

2015-11-01

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

INCORPORATING CONCENTRATION DEPENDENCE IN STABLE ISOTOPE MIXING MODELS: A REPLY TO ROBBINS, HILDERBRAND AND FARLEY (2002)

EPA Science Inventory

Phillips & Koch (2002) outlined a new stable isotope mixing model which incorporates differences in elemental concentrations in the determinations of source proportions in a mixture. They illustrated their method with sensitivity analyses and two examples from the wildlife ecolog...

A Very Much Faster and More Sensitive In Situ Stable Isotope Analysis Instrument

NASA Astrophysics Data System (ADS)

Coleman, M.; Christensen, L. E.; Kriesel, J. M.; Kelly, J. F.; Moran, J. J.; Vance, S.

2016-10-01

We are developing, Capillary Absorption Spectrometry (CAS) for H and O stable isotope analyses, giving > 4 orders of magnitude improved sensitivity, allowing analysis of 5 nano-moles of water and coupled to laser sampling to free water from hydrated minerals and ice.

CARBOHYDRATE USE AND ASSIMILATION BY LITTER AND SOIL FUNGI ASSESSED BY CARBON ISOTOPES AND BIOLOG ASSAYS

EPA Science Inventory

Soil fungi are integral to decomposition in forests, yet identification of probable functional roles of different taxa is problematic. Here, we compared carbohydrate assimilation patterns derived from stable isotope analyses on cultures with those produced from cultures on Biolo...

Carbon cycle perturbations recorded by δ13C of bulk organic matter: the Carnian Pluvial Event in the Dolomites, northern Italy

NASA Astrophysics Data System (ADS)

Preto, Nereo; Breda, Anna; Dal Corso, Jacopo; Rigo, Manuel; Roghi, Guido; Spötl, Christoph

2015-04-01

A period of increased rainfall occurred in the Carnian (Late Triassic), known as Carnian Pluvial Event (CPE), which is evidenced by major lithological changes in continental and marine successions at tropical latitudes. Increased continental weathering and erosion led to the supply of large amounts of siliciclastics into the marginal basins of the Tethys. Seawater anoxia is also observed locally in semi-restricted basins. Simultaneously, microbial factories on high-relief carbonate platforms were replaced by metazoan factories, forming low-relief carbonate ramps and mixed low-gradient shelves. This environmental change has been shown to be closely associated with a negative carbon isotope excursion. A negative δ13C shift is recorded by bulk organic matter in the Milieres section (central Dolomites) and parallels a coeval excursion in carbon-isotope records of higher plant and marine algal biomarker, thus testifying a global change in the isotopic composition of carbon dioxide in the atmosphere and of dissolved inorganic carbon (DIC) in the ocean. This isotopic excursion was identified in organic carbon records throughout the western Tethys, but so far could not be reproduced convincingly using carbon isotope records from carbonate. A long carbon isotope record was produced from bulk organic matter of the early to late Carnian Milieres - Dibona section in the Dolomites, northern Italy. Carbon isotope analyses of carbonate (limestone and dolomite) were also obtained. This new carbon isotope record illustrates the structure of this complex carbon cycle perturbation related to the CPE. But while sharp carbon isotope oscillations are evident in the bulk organic carbon record, there is no evidence of a similar pattern in carbonate record. It can be shown that the carbon isotope record of carbonates is influenced by fractionation and diagenetic processes that completely obliterated the original δ13C signal. We conclude that the Carnian carbonates of the Dolomites do not record the δ13C of marine DIC. We suggest that the identification of the Carnian carbon isotope excursion in carbonate records may only be possible if the isotopic analyses are coupled with petrographic screening that prove a minimal diagenetic overprint.

Stable Isotope Mapping of Alaskan Grasses and Marijuana

NASA Astrophysics Data System (ADS)

Booth, A. L.; Wooller, M. J.

2008-12-01

The spatial variation of isotope signatures in organic material is a useful forensic tool, particularly when applied to the task of tracking the production and distribution of plant-derived illicit drugs. In order to identify the likely grow-locations of drugs such as marijuana from unknown locations (i.e., confiscated during trafficking), base isotope maps are needed that include measurements of plants from known grow-locations. This task is logistically challenging in remote, large regions such as Alaska. We are therefore investigating the potential of supplementing our base (marijuana) isotope maps with data derived from other plants from known locations and with greater spatial coverage in Alaska. These currently include >150 samples of modern C3 grasses (Poaceae) as well as marijuana samples (n = 18) from known grow-locations across the state. We conducted oxygen, carbon and nitrogen stable isotope analyses of marijuana and grasses (Poaceae). Poaceae samples were obtained from the University of Alaska Fairbanks (UAF) Museum of the North herbarium collection, originally collected by field botanists from around Alaska. Results indicate that the oxygen isotopic composition of these grasses range from 10‰ to 30‰, and broadly mirror the spatial pattern of water isotopes in Alaska. Our marijuana samples were confiscated around the state of Alaska and supplied to us by the UAF Police Department. δ13C, δ15N and δ18O values exhibit geographic patterns similar to the modern grasses, but carbon and nitrogen isotopes of some marijuana plants appear to be influenced by additional factors related to indoor growing conditions (supplementary CO2 sources and the application of organic fertilizer). As well as providing a potential forensic resource, our Poaceae isotope maps could serve additional value by providing resources for studying ecosystem nutrient cycling, for tracing natural ecological processes (i.e., animal migration and food web dynamics) and providing modern data for comparison with isotope analyses conducted on fossil leaf material in paleoecological studies.

A 1000-year record of dry conditions in the eastern Canadian prairies reconstructed from oxygen and carbon isotope measurements on Lake Winnipeg sediment organics

USGS Publications Warehouse

Buhay, W.M.; Simpson, S.; Thorleifson, H.; Lewis, M.; King, J.; Telka, A.; Wilkinson, Philip M.; Babb, J.; Timsic, S.; Bailey, D.

2009-01-01

A short sediment core (162 cm), covering the period AD 920-1999, was sampled from the south basin of Lake Winnipeg for a suite of multi-proxy analyses leading towards a detailed characterisation of the recent millennial lake environment and hydroclimate of southern Manitoba, Canada. Information on the frequency and duration of major dry periods in southern Manitoba, in light of the changes that are likely to occur as a result of an increasingly warming atmosphere, is of specific interest in this study. Intervals of relatively enriched lake sediment cellulose oxygen isotope values (??18Ocellulose) were found to occur from AD 1180 to 1230 (error range: AD 1104-1231 to 1160-1280), 1610-1640 (error range: AD 1571-1634 to 1603-1662), 1670-1720 (error range: AD 1643-1697 to 1692-1738) and 1750-1780 (error range: AD 1724-1766 to 1756-1794). Regional water balance, inferred from calculated Lake Winnipeg water oxygen isotope values (??18Oinf-lw), suggest that the ratio of lake evaporation to catchment input may have been 25-40% higher during these isotopically distinct periods. Associated with the enriched d??18Ocellulose intervals are some depleted carbon isotope values associated with more abundantly preserved sediment organic matter (d??13COM). These suggest reduced microbial oxidation of terrestrially derived organic matter and/or subdued lake productivity during periods of minimised input of nutrients from the catchment area. With reference to other corroborating evidence, it is suggested that the AD 1180-1230, 1610-1640, 1670-1720 and 1750-1780 intervals represent four distinctly drier periods (droughts) in southern Manitoba, Canada. Additionally, lower-magnitude and duration dry periods may have also occurred from 1320 to 1340 (error range: AD 1257-1363), 1530-1540 (error range: AD 1490-1565 to 1498-1572) and 1570-1580 (error range: AD 1531-1599 to 1539-1606). ?? 2009 John Wiley & Sons, Ltd.

Position-specific isotope analysis by on-line pyrolysis coupled to IRMS

NASA Astrophysics Data System (ADS)

Gilbert, A.; Suda, K.; Yamada, K.; Ueno, Y.; Yoshida, N.

2016-12-01

Position-specific isotopic analyses (PSIA) provide unique information regarding the sources, sinks and processes related to natural molecules. For instance, PSIA of short-chain hydrocarbons could lead to temperature of formation and maturity of natural gas reservoirs [1][2]. In the last decade, quantitative Nuclear Magnetic Resonance (NMR) specrometry has been used for PSIA of organic molecules such as glucose or n-alkanes [3][4]. However, due to its low sensitivity, application to low amount geochemical samples remains challenging. In 1997, Corso & Brenna proposed to adapt a pyrolysis furnace to an isotope ratio mass spectrometer, making it possible the thermal degradation of the target molecule and the subsequent analysis of the d13C values of the fragments formed [5]. Starting from fatty acid methyl esters they demonstrated the absence of rearrangement during pyrolytic degradation and could determine the d13C value of carboxyl C-atom position. We adapted the system for the full characterization of position-specific isotope composition of small molecules (ethanol, acetic acid, alanine, propane). Nanomole amount of sample can be analyzed with a precision on intramolecular d13C values of 1‰ or lower [2]. We recently analyzed abiotic and thermogenic propane samples both from the field and from lab simulations. PSIA of propane shows systematic differences of position-specific isotope composition between thermogenic and abiotic samples. While the former show 13C-depletion on the terminal C-atom position - consistent with thermal cracking kinetic models [6] - abiotic samples show little or no preference for terminal or central 13C-isotopomer. These results emphasize the potential of PSIA to trace the the processes associated with organic molecules production. [1] Piasecki et al. 2016 GCA 188, 58 [2] Gilbert et al. 2016 GCA 177, 205 [3] Gilbert et al. 2012 PNAS, 109, 18204 [4] Gilbert et al. 2013 Org. Geochem, 62, 56 [5] Corso & Brenna 1997 PNAS, 94, 1049 [6] Tang et al., 2000 GCA 64, 2673

Environmental lead pollution threatens the children living in the Pearl River Delta region, China.

PubMed

Chen, Jianmin; Tong, Yongpeng; Xu, Jiazhang; Liu, Xiaoli; Li, Yulan; Tan, Mingguang; Li, Yan

2012-09-01

The objective of this study is to determine children's blood lead levels and identify sources of lead exposure. Childhood lead exposure constitutes a major pediatric health problem today in China. A blood lead screening survey program for children in the age group of 2-12 years residing in Pearl River Delta region, south of China, was carried out from Dec 2007 to Jan 2008. Blood lead levels and lead isotope ratios of a total of 761 participants were assessed by inductively coupled plasma mass spectroscopy. Measurements of urban environmental samples for source identification of children lead exposure were also performed. The geometric mean value of the children's blood lead levels was 57.05 μg/L, and 9.6% of them were higher than 100 μg/L. The blood lead levels were still much higher than those in developed countries. Based on the data of environmental lead source inventories, lead isotopic tracing revealed that there is about 6.7% past used gasoline Pb embedded in Shenzhen residential dust and about 15.6% in Guangzhou dust, respectively.

Coupling Meteorology, Metal Concentrations, and Pb Isotopes for Source Attribution in Archived Precipitation Samples

EPA Science Inventory

A technique that couples lead (Pb) isotopes and multi-element concentrations with meteorological analysis was used to assess source contributions to precipitation samples at the Bondville, Illinois USA National Trends Network (NTN) site. Precipitation samples collected over a 16 ...

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

NASA Astrophysics Data System (ADS)

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

2013-07-01

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

Evaluation of Drosophila metabolic labeling strategies for in vivo quantitative proteomic analyses with applications to early pupa formation and amino acid starvation.

PubMed

Chang, Ying-Che; Tang, Hong-Wen; Liang, Suh-Yuen; Pu, Tsung-Hsien; Meng, Tzu-Ching; Khoo, Kay-Hooi; Chen, Guang-Chao

2013-05-03

Although stable isotope labeling by amino acids in cell culture (SILAC)-based quantitative proteomics was first developed as a cell culture-based technique, stable isotope-labeled amino acids have since been successfully introduced in vivo into select multicellular model organisms by manipulating the feeding diets. An earlier study by others has demonstrated that heavy lysine labeled Drosophila melanogaster can be derived by feeding with an exclusive heavy lysine labeled yeast diet. In this work, we have further evaluated the use of heavy lysine and/or arginine for metabolic labeling of fruit flies, with an aim to determine its respective quantification accuracy and versatility. In vivo conversion of heavy lysine and/or heavy arginine to several nonessential amino acids was observed in labeled flies, leading to distorted isotope pattern and underestimated heavy to light ratio. These quantification defects can nonetheless be rectified at protein level using the normalization function. The only caveat is that such a normalization strategy may not be suitable for every biological application, particularly when modified peptides need to be individually quantified at peptide level. In such cases, we showed that peptide ratios calculated from the summed intensities of all isotope peaks are less affected by the heavy amino acid conversion and therefore less sequence-dependent and more reliable. Applying either the single Lys8 or double Lys6/Arg10 metabolic labeling strategy to flies, we quantitatively mapped the proteomic changes during the onset of metamorphosis and upon amino acid deprivation. The expression of a number of steroid hormone 20-hydroxyecdysone regulated proteins was found to be changed significantly during larval-pupa transition, while several subunits of the V-ATPase complex and components regulating actomyosin were up-regulated under starvation-induced autophagy conditions.

Pb-isotopic systematics of lunar highland rocks (>3.9 Ga): Constraints on early lunar evolution

USGS Publications Warehouse

Premo, W.R.; Tatsumoto, M.; Misawa, K.; Nakamuka, N.; Kita, N.I.

1999-01-01

The present lead (Pb)-isotopic database of over 200 analyses from nearly 90 samples of non-mare basalt, lunar highland rocks (>3.9 Ga) delineate at least three isotopically distinct signatures that in some combination can be interpreted to characterize the systematics of the entire database. Two are fairly new sets of lunar data and are typical of Pb data from other solar-system objects, describing nearly linear arrays slightly above the 'geochron' values, with 207Pb/206Pb values 500). Although the age and origin of this exotic Pb is not well constrained, it is interpreted to be related to the entrapment of incompatible-element-rich (U, Th) melts within the lunar upper mantle and crust between 4.36 and 4.46 Ga (urKREEP residuum?). The latest discovered Pb signature is found only in lunar meteorites and is characterized by relatively low source ?? values between 10 and 50 at 3.9 Ga. The fact that most lunar crustal rocks (>3.9 Ga) exhibit high 207Pb/206Pb values requires that they were derived from, mixed with, or contaminated by Pb produced from early-formed, high-?? sources. The ubiquity of these U-Pb characteristics in the sample collection is probably an artifact of Apollo and Luna sampling sites, all located on the near side of the Moon, which was deeply excavated during the basin-forming event(s). However, the newest Pb-isotopic data support the idea that the Moon originally had a ?? value of ~8 to 35, slightly elevated from Earth values, and that progressive U-Pb fractionations occurred within the Moon during later stages of differentiation between 4.36 and 4.46 Ga.

Lead in ancient Rome’s city waters

PubMed Central

Delile, Hugo; Blichert-Toft, Janne; Goiran, Jean-Philippe; Keay, Simon; Albarède, Francis

2014-01-01

It is now universally accepted that utilization of lead for domestic purposes and water distribution presents a major health hazard. The ancient Roman world was unaware of these risks. How far the gigantic network of lead pipes used in ancient Rome compromised public health in the city is unknown. Lead isotopes in sediments from the harbor of Imperial Rome register the presence of a strong anthropogenic component during the beginning of the Common Era and the Early Middle Ages. They demonstrate that the lead pipes of the water distribution system increased Pb contents in drinking water of the capital city by up to two orders of magnitude over the natural background. The Pb isotope record shows that the discontinuities in the pollution of the Tiber by lead are intimately entwined with the major issues affecting Late Antique Rome and its water distribution system. PMID:24753588

Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico

NASA Astrophysics Data System (ADS)

Jimenez, A.

2012-04-01

Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico Abigail Jimenez-Franco1*, Pura Alfonso Abella2, Carles Canet3, Eduardo González-Partida4 1 Posgrado en Ciencias de la Tierra, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 2 Departament d'Enginyeria Minera i Recursos Naturals, Universitat Politècnica de Catalunya, Av de Les Bases de Manresa 61-73, 08242 Manresa. 3Instituto de Geofísica, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 4Centro de Geociencias, Universidad Nacional Autónoma de México, Campus Juriquilla, Boulevard Juriquilla 3001, 76230 Santiago de Querétaro, Qro., Mexico The Velardeña mining district is located in north-eastern part of the state of Durango, in northern of Mexico. The ore deposit is a lead-zinc, garnet-rich skarn developed at the contact between granite porphyry dikes (Eocene) and well-laminated limestones with interbedded chert (Albian-Cenomanian). A study of sulfur isotopes has been carried out in various sulfide minerals of the ores of Velardeña, in order to: (a) constrain the possible sources of sulfur and, therefore, better understand the sulfide mineralizing processes, and (b) to estimate the temperature of the ore-forming stage of the skarn. Sulfur isotope analyses were performed in 21 pure fractions of sulfide minerals of the ore mineralization (pyrite, chalcopyrite, sphalerite and galena). The mineral separation was performed using a series of sieves, and the purity of the samples was verified under a binocular microscope. Isotopic analyses were done on a Finnigan MAT Delta C flow elemental analyzer coupled to a TC-EA, according with the method of Giesemann et al. (1974). The δ34S values of the analyzed sulfides range mostly between -0.6 and +2.6 ‰ (relative to the CDT standard). These values are indicative of a magmatic source of sulfur. A single analysis falls outside the common range of magmatic sulfur; it corresponds to a sphalerite crystal with δ34S of -3.9 ‰. This negative value could be explained by the incorporation of sulfur leached from the sedimentary host rocks. Pyrite and galena in paragenesis were analyzed from one sample (CO-9F); the isotope fractionation equation of Ohmoto and Rye (1979) was applied for geothermometry purposes. This calculation yields a temperature of 346° ±25° C, from fractionation Δpyrite-galena of 2.66 ‰.

Sensitivity and Uncertainty Analysis of Plutonium and Cesium Isotopes in Modeling of BR3 Reactor Spent Fuel

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

Conant, Andrew; Erickson, Anna; Robel, Martin

Nuclear forensics has a broad task to characterize recovered nuclear or radiological material and interpret the results of investigation. One approach to isotopic characterization of nuclear material obtained from a reactor is to chemically separate and perform isotopic measurements on the sample and verify the results with modeling of the sample history, for example, operation of a nuclear reactor. The major actinide plutonium and fission product cesium are commonly measured signatures of the fuel history in a reactor core. This study investigates the uncertainty of the plutonium and cesium isotope ratios of a fuel rod discharged from a research pressurizedmore » water reactor when the location of the sample is not known a priori. A sensitivity analysis showed overpredicted values for the 240Pu/ 239Pu ratio toward the axial center of the rod and revealed a lower probability of the rod of interest (ROI) being on the periphery of the assembly. The uncertainty analysis found the relative errors due to only the rod position and boron concentration to be 17% to 36% and 7% to 15% for the 240Pu/ 239Pu and 137Cs/ 135Cs ratios, respectively. Lastly, this study provides a method for uncertainty quantification of isotope concentrations due to the location of the ROI. Similar analyses can be performed to verify future chemical and isotopic analyses.« less

Sensitivity and Uncertainty Analysis of Plutonium and Cesium Isotopes in Modeling of BR3 Reactor Spent Fuel

DOE PAGES

Conant, Andrew; Erickson, Anna; Robel, Martin; ...

2017-02-03

Nuclear forensics has a broad task to characterize recovered nuclear or radiological material and interpret the results of investigation. One approach to isotopic characterization of nuclear material obtained from a reactor is to chemically separate and perform isotopic measurements on the sample and verify the results with modeling of the sample history, for example, operation of a nuclear reactor. The major actinide plutonium and fission product cesium are commonly measured signatures of the fuel history in a reactor core. This study investigates the uncertainty of the plutonium and cesium isotope ratios of a fuel rod discharged from a research pressurizedmore » water reactor when the location of the sample is not known a priori. A sensitivity analysis showed overpredicted values for the 240Pu/ 239Pu ratio toward the axial center of the rod and revealed a lower probability of the rod of interest (ROI) being on the periphery of the assembly. The uncertainty analysis found the relative errors due to only the rod position and boron concentration to be 17% to 36% and 7% to 15% for the 240Pu/ 239Pu and 137Cs/ 135Cs ratios, respectively. Lastly, this study provides a method for uncertainty quantification of isotope concentrations due to the location of the ROI. Similar analyses can be performed to verify future chemical and isotopic analyses.« less

Pyroxene Homogenization and the Isotopic Systematics of Eucrites

NASA Technical Reports Server (NTRS)

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

1996-01-01

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

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.

A miniature laser ablation mass spectrometer for quantitative in situ chemical composition investigation of lunar surface

NASA Astrophysics Data System (ADS)

Brigitte Neuland, Maike; Grimaudo, Valentine; Mezger, Klaus; Moreno-García, Pavel; Riedo, Andreas; Tulej, Marek; Wurz, Peter

2016-04-01

The chemical composition of planetary bodies, moons, comets and asteroids is a key to understand their origin and evolution [Wurz,2009]. Measurements of the elemental and isotopic composition of rocks yield information about the formation of the planetary body, its evolution and following processes shaping the planetary surface. From the elemental composition, conclusions about modal mineralogy and petrology can be drawn. Isotope ratios are a sensitive indicator for past events on the planetary body and yield information about origin and transformation of the matter, back to events that occurred in the early solar system. Finally, measurements of radiogenic isotopes make it possible to carry out dating analyses. All these topics, particularly in situ dating analyses, quantitative elemental and highly accurate isotopic composition measurements, are top priority scientific questions for future lunar missions. An instrument for precise measurements of chemical composition will be a key element in scientific payloads of future landers or rovers on lunar surface. We present a miniature laser ablation mass spectrometer (LMS) designed for in situ research in planetary and space science and optimised for measurements of the chemical composition of rocks and soils on a planetary surface. By means of measurements of standard reference materials we demonstrate that LMS is a suitable instrument for in situ measurements of elemental and isotopic composition with high precision and accuracy. Measurements of soil standards are used to confirm known sensitivity coefficients of the instrument and to prove the power of LMS for quantitative elemental analyses [Neuland,2016]. For demonstration of the capability of LMS to measure the chemical composition of extraterrestrial material we use a sample of Allende meteorite [Neuland,2014]. Investigations of layered samples confirm the high spatial resolution in vertical direction of LMS [Grimaudo,2015], which allows in situ studying of past surface processes on a planetary surface. Analyses of Pb isotopes show that the statistical uncertainty for the age determination by LMS is about ±100 Myrs, if abundance of 206Pb and 207Pb is 20ppm and 2ppm respectively [Riedo,2013]. These Pb isotopes have abundances of tens to hundreds of ppm in lunar KREEP [Nemchin,2008]. We demonstrate the measurement capabilities of LMS for petrographic and mineralogical analyses, for isotopic studies and dating analyses, which are key topics for future missions to the Moon. Having the LMS instrument installed on a lunar rover would allow measuring the chemical composition of many rock and soil samples, distributed over a certain area, inside the South Pole Aitken Basin for example. LMS measurements would yield valuable conclusions about age and mineralogy. References: [Wurz,2009]Wurz,P. et al. 2009, AIP Conf.Proc., CP1144:70-75. [Grimaudo,2015]Grimaudo, V. et al. 2015, Anal.Chem. 87: 2037-2041. [Neuland,2014]Neuland, M.B. et al. 2014, Planet.Space Sci.101:196-209. [Neuland,2016]Neuland M.B. et al. 2016, Meas. Sci. Technol.,submitted. [Riedo,2013]Riedo A. et al., 2013 Planet. Space Sci. 87: 1-13. [Nemchin,2008]Nemchin et al., 2008 Geochim. Cosmochim.Acta 72:668-689.

Geogenic lead isotope signatures from meat products in Great Britain: Potential for use in food authentication and supply chain traceability.

PubMed

Evans, Jane A; Pashley, Vanessa; Richards, Gemma J; Brereton, Nicola; Knowles, Toby G

2015-12-15

This paper presents lead (Pb) isotope data from samples of farm livestock raised in three areas of Britain that have elevated natural Pb levels: Central Wales, the Mendips and the Derbyshire Peak District. This study highlights three important observations; that the Pb found in modern British meat from these three areas is geogenic and shows no clear evidence of modern tetraethyl anthropogenic Pb contribution; that the generally excellent match between the biological samples and the ore field data, particularly for the Mendip and Welsh data, suggests that this technique might be used to provenance biological products to specific ore sites, under favourable conditions; and that modern systems reflect the same process of biosphere averaging that is analogous to cultural focusing in human archaeological studies that is the process of biological averaging leading to an homogenised isotope signature with increasing Pb concentration. Copyright © 2015. Published by Elsevier B.V.

Stable Chlorine Isotope Study: Application to Early Solar System Materials

NASA Technical Reports Server (NTRS)

Mala,ira. M/; Nyquist, L. E.; Reese, Y.; Shih, C-Y; Fujitani, T.; Okano, O.

2010-01-01

A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the Cl-37/Cl-35 ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For example, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the 37Cl/35Cl ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For eample, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. In order to clarify the stable chlorine isotope features of early solar system materials, we have initiated development of the TIMS technique at NASA JSC applicable to analysis of small amounts of meteoritic and planetary materials. We report here the current status of chlorine isotope analysis at NASA JSC.

Module 5: Applications of Stable Isotope Analyses: Data Interpretation and Data Quality Issues

EPA Science Inventory

When organic contaminants such as benzene, TCE or MTBE are degraded, the ratio of the stable isotopes of carbon in the organic contaminants will often change in a predictable fashion. In the last ten years, advances in analytical chemistry have made it possible to measure these ...

UNCERTAINTY IN SOURCE PARTITIONING USING STABLE ISOTOPES

EPA Science Inventory

Stable isotope analyses are often used to quantify the contribution of multiple sources to a mixture, such as proportions of food sources in an animal's diet, C3 vs. C4 plant inputs to soil organic carbon, etc. Linear mixing models can be used to partition two sources with a sin...

Quantifying plant phenotypes with isotopic labeling and metabolic flux analysis

USDA-ARS?s Scientific Manuscript database

Analyses of metabolic flux using stable isotopes in plants have traditionally been restricted to tissues with presumed homogeneous cell populations such as developing seeds, cell suspensions, or cultured roots and root tips. It is now possible to describe these and other more complex tissues such a...

Optimization Techniques for Improving the Precision of Isotopic Analysis by Thermal Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Wang, G. Q.; Xu, J. F.; Wu-Yang, S. Q.

2016-12-01

Operation of instruments and preparation of samples are also significant factors that can affect the precision of TIMS analyses, in addition to instrument hardware. We have reviewed the isotopic data of several standard materials at our TIMS lab for 5 years. It is suggested that several optimization techniques should be used in order to obtain high-precision isotopic ratio data: (1) It is important to choose a suitable filament material for isotopic measurements. We have established that W filament is likely the most efficient for ionizing Sr when selecting from W, Re, and Ta; meanwhile, Re filament can produce a higher intensity for Nd isotopes than W and Ta filament can. It is concluded that the best TIMS signals are obtained for Sr using W signal-filaments and for Nd using Re double-filaments. (2) The preparation of the activator plays a key role in the analysis of some isotopic ratios. This study indicates that choosing a suitable activator can greatly elevate the precision of 206Pb/204Pb ratios during Pb isotopic measurements. We have suggested a new scheme to make an activator by using a mixture of 10% Si-gel + 7.5% H3PO3 + 82.5% H2O (weight %). (3) It is necessary to re-set the cup configuration to avoid cup degradation when operating for a long period of time (a year or more). We propose a new cup configuration to avoid this disadvantage during Sr isotopic analyses. (4) The contamination of 187Re and 185Re after using Re-filament could be eliminated by cleaning the ion source and baking the source housing.

Sr and Pb isotopic geochemistry of feldspars and implications for the growth of megacrysts in plutonic settings.

NASA Astrophysics Data System (ADS)

Munnikhuis, J.; Glazner, A. F.; Coleman, D. S.; Mills, R. D.

2015-12-01

Why megacrystic textures develop in silicic igneous rocks is still unknown. One hypothesis is that these crystals nucleate early in a magma chamber with a high liquid content. A supportive observation of this hypothesis is areas in plutons with high concentrations of megacrysts suggesting flow sorting. Another group of hypotheses suggest megacrystic textures form during protracted late-stage coarsening in a low-melt, interlocked matrix due to either thermal oscillations from incremental pluton emplacement, or Ostwald ripening. Isotopic analyses of large, euhedral K-feldspar megacrysts from the Cretaceous intrusive suites of the Sierra Nevada batholith (SNB) provide new insight into their origin. Megacrysts from the SNB reach the decimeter scale, are Or rich (85-90%), are perthitic, and host mineral inclusions of nearly all phases in the host rock. In-situ micro-drilling of transects, from core to rim, of the alkali feldspars provides material for Sr and Pb isotopic analyses by thermal ionization mass spectrometry (TIMS). Preliminary 87Sr/86Sr(i) isotopic data from samples from the Cathedral Peak Granodiorite, of the Tuolumne Intrusive Suite range from 0.706337 to 0.706452 (~1.6ɛSr) near the cores, whereas a sawtooth pattern with larger variability, 0.706179 to 0.706533 (~5ɛSr), occurs nears the rims. We interpret these preliminary data to indicate that the late portion of growth (i.e. crystal rim) was dominated by either cannibalism of small K-feldspar crystals with isotopic variability, or by addition of isotopically diverse late components to the magma. By comparing the Sr and Pb isotopic stratigraphy of megacrysts from a variety of rock matrices and different granitoids in the SNB isotopic trends can be evaluated to determine if crystals sizes are dependent on disequilibrium processes or grow at a steady state.

Geographic variation of stable isotopes in African elephant ivory

NASA Astrophysics Data System (ADS)

Ziegler, S.; Merker, S.; Jacob, D.

2012-04-01

In 1989, the international community listed the African elephant in Appendix I of the Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES) thus prohibiting commercial ivory trade. Recent surveillance data show that the illegal trade in ivory has been growing worldwide. Long-term preservation of many of the African elephant populations can be supported with a control mechanism that helps with the implementation of remedial conservation action. Therefore, setting up a reference database that predicts the origin of ivory specimens can assist in determining smuggling routes and the provenance of illegal ivory. Our research builds on earlier work to seek an appropriate method for determining the area of origin for individual tusks. Several researchers have shown that the provenance of elephant ivory can be traced by its isotopic composition, but this is the first attempt to produce an integrated isotopic reference database of elephant ivory provenance. We applied a combination of various routine geochemical analyses to measure the stable isotope ratios of hydrogen, carbon, nitrogen, oxygen, and sulphur. Up to now, we analysed 606 ivory samples of known geographical origin from African range states, museums and private collections, comprising 22 African elephant range states. The isotopic measurements were superimposed with data layers from vegetation, geology and climate. A regression function for the isotope composition of the water isotopes in precipitation and collagen in ivory was developed to overcome the problem of imprecise origin of some of the sampled material. Multivariate statistics, such as nearest neighborhood and discriminate analysis were applied to eventually allow a statistical determination of the provenance for ivory of unknown origin. Our results suggest that the combination of isotopic parameters have the potential to provide predictable and complementary markers for estimating the origin of seized elephant ivory.

Carbon isotope analyses of n-alkanes released from rapid pyrolysis of oil asphaltenes in a closed system.

PubMed

Chen, Shasha; Jia, Wanglu; Peng, Ping'an

2016-08-15

Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ(13) C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oil-source' correlations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

The flow mechanism in the Chalk based on radio-isotope analyses of groundwater in the London Basin

USGS Publications Warehouse

Downing, R.A.; Pearson, F.J.; Smith, D.B.

1979-01-01

14C analyses of groundwaters from the Chalk of the London Basin are re-interpreted and the age of the groundwater is revised. Radio-isotope analyses are used to examine the flow mechanism in the aquifer. The evidence supports the view that a network of micro-fissures and larger intergranular pores in the matrix provides a significant part of the water pumped from Chalk wells and the major fissures distribute the water to the wells. Most of the matrix is fine-grained and contains a very old water. This diffuses into the micro-fissures and larger pores and is carried to the wells by the major fissures. ?? 1979.

Application of stable isotope ratio analysis for biodegradation monitoring in groundwater

USGS Publications Warehouse

Hatzinger, Paul B.; Böhlke, John Karl; Sturchio, Neil C.

2013-01-01

Stable isotope ratio analysis is increasingly being applied as a tool to detect, understand, and quantify biodegradation of organic and inorganic contaminants in groundwater. An important feature of this approach is that it allows degradative losses of contaminants to be distinguished from those caused by non-destructive processes such as dilution, dispersion, and sorption. Recent advances in analytical techniques, and new approaches for interpreting stable isotope data, have expanded the utility of this method while also exposing complications and ambiguities that must be considered in data interpretations. Isotopic analyses of multiple elements in a compound, and multiple compounds in the environment, are being used to distinguish biodegradative pathways by their characteristic isotope effects. Numerical models of contaminant transport, degradation pathways, and isotopic composition are improving quantitative estimates of in situ contaminant degradation rates under realistic environmental conditions.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Isotopic Analysis of Plutonium by Optical Spectroscopy; ANALYSE ISOTOPIQUE DU PLUTONIUM PAR SPECTROSCOPIE OPTIQUE

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

Artaud, J.; Chaput, M.; Gerstenkorn, S.

1961-01-01

Isotopic analyses of mixtures of plutonium-239 and -240 were carried out by means of the photoelectric spectrometer, the source being a hollow cathode cooled by liquid nitrogen. The relative precision is of the order of 2%, for samples containieg 3% of Pu/sup 240/. The study of the reproductibility of the measurements should make it possible to increase the precision; the relative precision which can be expected from the method should be 1% for mixtures containing 1% of Pu/sup 240/. (auth)

Carbon and nitrogen isotope systematics in diamond: Different sensitivities to isotopic fractionation or a decoupled origin?

NASA Astrophysics Data System (ADS)

Hogberg, K.; Stachel, T.; Stern, R. A.

2016-11-01

Using stable isotope data obtained on multiple aliquots of diamonds from worldwide sources, it has been argued that carbon and nitrogen in diamond are decoupled. Here we re-investigate the carbon-nitrogen relationship based on the most comprehensive microbeam data set to date of stable isotopes and nitrogen concentrations in diamonds (n = 94) from a single locality. Our diamond samples, derived from two kimberlites in the Chidliak Field (NE Canada), show large variability in δ13C (- 28.4 ‰ to - 1.1‰, mode at - 5.8‰), δ15N (- 5.8 to + 18.8‰, mode at - 3.0‰) and nitrogen contents ([N]; 3800 to less than 1 at.ppm). In combination, cathodoluminescence imaging and microbeam analyses reveal that the diamonds grew from multiple fluid pulses, with at least one major hiatus documented in some samples that was associated with a resorption event and an abrupt change from low δ13C and [N] to mantle-like δ13C and high [N]. Overall, δ13C appears to be uncorrelated to δ15N and [N] on both the inter- and intra-diamond levels. Co-variations of δ15N-log[N], however, result in at least two parallel, negatively correlated linear arrays, which are also present on the level of the individual diamonds falling on these two trends. These arrays emerge from the two principal data clusters, are characterized by slightly negative and slightly positive δ15N (about - 3 and + 2‰, respectively) and variable but overall high [N]. Using published values for the diamond-fluid nitrogen isotope fractionation factor and nitrogen partition coefficient, these trends are perfectly reproduced by a Rayleigh fractionation model. Overall, three key elements are identified in the formation of the diamond suite studied: (1.) a low δ13C and low [N] component that possibly is directly associated with an eclogitic diamond substrate or introduced during an early stage fluid event. (2.) Repeated influx of a variably nitrogen-rich mantle fluid (mildly negative δ13C and δ15N). (3.) In waning stages of influx, availability of the mantle-type fluid at the site of diamond growth became limited, leading to Rayleigh fractionation. These fractionation trends are clearly depicted by δ15N-[N] but are not detected when examining co-variation diagrams involving δ13C. Also on the level of individual diamonds, large (≥ 5‰) variations in δ15N are associated with δ13C values that typically are constant within analytical uncertainty. The much smaller isotope fractionation factor for carbon (considering carbonate- or methane-rich fluids as possible carbon sources) compared to nitrogen leads to an approximately one order of magnitude lower sensitivity of δ13C values to Rayleigh fractionation processes (i.e. during fractionation, a 1‰ change in δ13C is associated with a 10‰ change in δ15N). As a consequence, even minor heterogeneity in the primary isotopic composition of diamond forming carbon (e.g., due to addition of minor subducted carbon) will completely blur any possible co-variations with δ15N or [N]. We suggest this strong difference in isotope effects for C and N to be the likely cause of observations of an apparently decoupled behaviour of carbon and nitrogen isotopes in diamond.

Electrochemically controlled iron isotope fractionation

NASA Astrophysics Data System (ADS)

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

2010-02-01

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

Preliminary Report on U-Th-Pb Isotope Systematics of the Olivine-Phyric Shergottite Tissint

NASA Technical Reports Server (NTRS)

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

2014-01-01

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-rich reservoir. The former is clearly a depleted mantle source, but there has been a long 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 clearly requires the ancient martian crust to be the enriched source (crustal assimilation), whereas the latter requires 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 U-Th-Pb concentration analyses of the olivine-phyric shergottite Tissint because U-Th-Pb isotope systematics have been intensively used as a powerful radiogenic tracer to characterize old crust/sediment components in mantle- derived, terrestrial oceanic island basalts. The U-Th-Pb analyses are applied to sequential acid leaching fractions obtained from Tissint whole-rock powder in order to search for Pb isotopic source components in Tissint magma. Here we report preliminary results of the U-Th-Pb analyses of acid leachates and a residue, and propose the possibility that Tissint would have experienced minor assimilation of old martian crust.

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

PubMed

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

2015-11-01

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

Tamil Chola Bronzes and Swamimalai Legacy: Metal Sources and Archaeotechnology

NASA Astrophysics Data System (ADS)

Srinivasan, Sharada

2016-08-01

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

Tracing Pleistocene to Holocene meltwater events and provenance of sediments in Baffin Bay using radiogenic isotope signals

NASA Astrophysics Data System (ADS)

Kirillova, Valeriia; Kasemann, Simone A.; Lucassen, Friedrich

2016-04-01

Large meltwater discharge is the principal carrier of detritus from the continent into the ocean and the dispersion of this detritus by ocean currents is a measure for the spatially focused addition of freshwater in the ocean in the high latitude areas. To trace Greenland ice sheet dynamics and freshwater routing during late Pleistocene to Holocene climate transition, we generate strontium (Sr), neodymium (Nd) and lead (Pb) isotope records on sediment cores in the Baffin Bay: GeoTÜ SL 170, covering the last 18.000 years of climate history and GeoTÜ SL 174, covering 40.000 years. Sr, Nd and Pb isotopes are used as proxies for the provenance of continental detritus and seawater sources. Isotope analyses were performed on two separated fractions from the sedimentary core material: the chemically leached fraction and the remaining detritus. Leachates are supposed to represent Fe-Mn coatings formed on the surface of the sediment grains and to reflect the bottom water signal. The detrital fraction acts as a tracer for the meltwater event and weathering regime of the nearby continental masses. For the detrital fraction of the core SL 170, a pronounced shift can be observed in all three isotope systems at ˜ 12 ka, what coincides with the Younger Dryas cold event. For the detrital fraction the 87Sr/86Sr is around ˜0,72 before the event and reaches up to ˜0,74 after. Nd isotope composition (ɛNd) changed from ˜-26 to ˜-32. The shift suggests a change in the continental sources from West and West-South Greenland to the Baffin Island and Canadian Archipelago. It can be explained by the ice sheet melting processes. The 206Pb/204Pb values for the detrital fraction range from ˜17 before the shift to ˜18 after. On the contrary, the leachates show pronounced radiogenic signatures with values changing from ˜21 to ˜23. The reason for such an unusual high values is most likely in the composition of the leached material, which doesn't seem to show the presence of Fe-Mn coatings as was suggested before. The work on the second core SL 174 is in progress. Up to now the results show similar patterns for isotope ratios as in the case of SL 170.

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

USGS Publications Warehouse

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

1984-01-01

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

The medieval metal industry was the cradle of modern large-scale atmospheric lead pollution in northern Europe

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

Braennvall, M.L.; Bindler, R.; Renberg, I.

1999-12-15

There is great concern for contamination of sensitive ecosystems in high latitudes by long-range transport of heavy metals and other pollutants derived from industrial areas in lower latitudes. Atmospheric pollution of heavy metals has a very long history, and since metals accumulate in the environment, understanding of present-day pollution conditions requires knowledge of past atmospheric deposition. The authors use analyses of lead concentrations and stable lead isotopes ({sup 206}Pb/{sup 207}Pb ratios) of annually laminated sediments from four lakes in northern Sweden to provide a decadal record of atmospheric lead pollution for the last 3000 years. There is a clear signalmore » in the sediments of airborne pollution from Greek and Roman cultures 2000 years ago, followed by a period of clean conditions 400--900 A.D. From 900 A.D. there was a conspicuous, permanent increase in atmospheric lead pollution fallout, The sediments reveal peaks in atmospheric lead pollution at 1200 and 1530 A.D. comparable to present-day levels. These peaks match the history of metal production in Europe. This study indicates that the contemporary atmospheric pollution climate in northern Europe was established in Medieval time, rather than in the industrial period. Atmospheric lead pollution deposition did not, when seen in a historical perspective, increase as much as usually assumed with the Industrial Revolution.« less

Mobile mapping of methane emissions and isoscapes

NASA Astrophysics Data System (ADS)

Takriti, Mounir; Ward, Sue; Wynn, Peter; Elias, Dafydd; McNamara, Niall

2017-04-01

Methane (CH4) is a potent greenhouse gas emitted from a variety of natural and anthropogenic sources. It is crucial to accurately and efficiently detect CH4 emissions and identify their sources to improve our understanding of changing emission patterns as well as to identify ways to curtail their release into the atmosphere. However, using established methods this can be challenging as well as time and resource intensive due to the temporal and spatial heterogeneity of many sources. To address this problem, we have developed a vehicle mounted mobile system that combines high precision CH4 measurements with isotopic mapping and dual isotope source characterisation. We here present details of the development and testing of a unique system for the detection and isotopic analysis of CH4 plumes built around a Picarro isotopic (13C/12C) gas analyser and a high precision Los Gatos greenhouse gas analyser. Combined with micrometeorological measurements and a mechanism for collecting discrete samples for high precision dual isotope (13C/12C, 2H/1H) analysis the system enables mapping of concentrations as well as directional and isotope based source verification. We then present findings from our mobile methane surveys around the North West of England. This area includes a variety of natural and anthropogenic methane sources within a relatively small geographical area, including livestock farming, urban and industrial gas infrastructure, landfills and waste water treatment facilities, and wetlands. We show that the system was successfully able to locate leaks from natural gas infrastructure and emissions from agricultural activities and to distinguish isotope signatures from these sources.

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

PubMed

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

2006-10-29

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

Stable isotopic constraints on the tectonic, topographic, and climatic evolution of the northern margin of the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Kent-Corson, Malinda L.; Ritts, Bradley D.; Zhuang, Guangsheng; Bovet, Paul M.; Graham, Stephan A.; Page Chamberlain, C.

2009-05-01

This study presents oxygen and carbon isotopic records from lacustrine, paleosol, alluvial, and fluvial carbonate sampled in thirteen Cenozoic sedimentary sections that span the northern margin of the Tibetan Plateau. Isotopic analyses of 1475 carbonate samples yield δ18O values that range from 13.1 to 38.9‰ (SMOW), and δ13C values range from - 11.5 to 3.7‰ (PDB). Based on these analyses, we see two isotopic trends regionally. We interpret a Paleogene decrease in average oxygen isotope values to result from an increase in the mean elevation of the study region's drainages as they tapped waters from a growing Tibetan Plateau to the south of the study area. We interpret a Neogene increase in both carbon and oxygen isotope values to result from the initiation of local mountain building in the study area and the withdrawal of marine waters, which increased basin isolation, aridity, and temperatures. The timing of inferred initiation of uplift in this region is consistent with structural, thermochronological, and sedimentological evidence for a tectonic transition in the early and middle Miocene from accommodation of India-Eurasia convergence through extrusion along the Altyn Tagh fault to accommodation of convergence through active shortening and mountain building in this region. This study also supports tectonic models for the differential uplift of the Tibetan Plateau, in that mountain building in this study region significantly postdates estimates for the attainment of high elevation from isotopic studies of the central Tibetan Plateau.

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

PubMed Central

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

2006-01-01

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

Small-scale studies of roasted ore waste reveal extreme ranges of stable mercury isotope signatures

NASA Astrophysics Data System (ADS)

Smith, Robin S.; Wiederhold, Jan G.; Jew, Adam D.; Brown, Gordon E.; Bourdon, Bernard; Kretzschmar, Ruben

2014-07-01

Active and closed Hg mines are significant sources of Hg contamination to the environment, mainly due to large volumes of mine waste material disposed of on-site. The application of Hg isotopes as source tracer from such contaminated sites requires knowledge of the Hg isotope signatures of different materials potentially released to the environment. Previous work has shown that calcine, the waste residue of the on-site ore roasting process, can exhibit distinct Hg isotope signatures compared with the primary ore. Here, we report results from a detailed small-scale study of Hg isotope variations in calcine collected from the closed New Idria Hg mine, San Benito County, CA, USA. The calcine samples exhibited different internal layering features which were investigated using optical microscopy, micro X-ray fluorescence, micro X-ray absorption spectroscopy (μ-XAS), and stable Hg isotope analysis. Significant Fe, S, and Hg concentration gradients were found across the different internal layers. Isotopic analyses revealed an extreme variation with pronounced isotopic gradients across the internal layered features. Overall, δ202Hg (±0.10‰, 2 SD) describing mass-dependent fractionation (MDF) ranged from -5.96 to 14.49‰, which is by far the largest range of δ202Hg values reported for any environmental sample. In addition, Δ199Hg (±0.06‰, 2 SD) describing mass-independent fractionation (MIF) ranged from -0.17 to 0.21‰. The μ-XAS analyses suggested that cinnabar and metacinnabar are the dominant Hg-bearing phases in the calcine. Our results demonstrate that the incomplete roasting of HgS ores in Hg mines can cause extreme mass-dependent Hg isotope fractionations at the scale of individual calcine pieces with enrichments in both light and heavy Hg isotopes relative to the primary ore signatures. This finding has important implications for the application of Hg isotopes as potential source tracers for Hg released to the environment from closed Hg mines and highlights the need for detailed source signature identification.

Sediment Tracking Using Carbon and Nitrogen Stable Isotopes

NASA Astrophysics Data System (ADS)

Fox, J. F.; Papanicolaou, A.

2002-12-01

As landscapes are stripped of valuable, nutrient rich topsoils and streams are clouded with habitat degrading fine sediment, it becomes increasingly important to identify and mitigate erosive surfaces. Particle tracking using vegetative derived carbon (C) and nitrogen (N) isotopic signatures and carbon/nitrogen (C/N) atomic ratios offer a promising technique to identify such problematic sources. Consultants and researchers successfully use C, N, and other stable isotopes of water for hydrologic purposes, such as quantifying groundwater vs. surface water contribution to a hydrograph. Recently, C and N isotopes and C/N atomic ratios of sediment were used to determine sediment mass balance within estuarine environments. The current research investigates C and N isotopes and C/N atomic ratios of source sediment for two primary purposes: (1) to establish a blueprint methodology for estimating sediment source and erosion rates within a watershed using this isotopic technology coupled with mineralogy fingerprinting techniques, radionuclide transport monitoring, and erosion-transport models, and (2) to complete field studies of upland erosion processes, such as, solifluction, mass wasting, creep, fluvial erosion, and vegetative induced erosion. Upland and floodplain sediment profiles and riverine suspended sediment were sampled on two occasions, May 2002 and August 2002, in the upper Palouse River watershed of northern Idaho. Over 300 samples were obtained from deep intermountain valley (i.e. forest) and rolling crop field (i.e. agriculture) locations. Preliminary sample treatment was completed at the Washington State University Water Quality Laboratory where samples were dried, removed of organic constituents, and prepared for isotopic analysis. C and N isotope and C/N atomic ratio analyses was performed at the University of Idaho Natural Resources Stable Isotope Laboratory using a Costech 4010 Elemental Combustion System connected with a continuous flow inlet system to the Finnigan MAT Delta Plus isotope ratio mass spectrometer. Results indicate distinct N isotopic signatures and C/N atomic ratios for forest and agriculture sediment sources. In addition, unique C and N isotopic signatures and C/N atomic ratios exist within floodplain and upland surfaces, and within the 10 centimeter profiles of erosion and deposition locations. Suspended sediment analyses are preliminary at this time. Conclusions indicate that sediment C and N isotopic signature and C/N atomic ratio are dependent upon land use and soil moisture conditions, and will serve as a useful technique in quantifying erosive source rates and understanding upland erosion processes.

Isotope Analysis of Uranium by Optical Spectroscopy; ANALYSE ISOTOPIQUE DE L'URANIUM PAR SPECTROSCOPIE OPTIQUE

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

Gerstenkorn, S.

1958-06-01

Isotopic analysis of urarium is made by means of hollow cathode lamp and a Fabry-Perot photoelectric spectrometer. The line U/sup 235/, 5027 A is used. This method allows a deterraination of the isotopic concentrations in U /sup 235/ down to 0.1%. The relative precision is about 2% for amounts of U/sup 235/ over 1%. For weaker amounts this line allows relative measurements of better precision when using standard mixtures. (auth)

Dipole and spin-dipole strength distributions in ^{124,126,128,130} Te isotopes

NASA Astrophysics Data System (ADS)

Cakmak, Necla; Cakmak, Sadiye; Selam, Cevad; Unlu, Serdar

2018-02-01

We try to present the structure of 1- excitations in open-shell ^{124,126,128,130} Te isotopes. Electric dipole states are investigated within a translational and Galilean invariant model. Also, a theoretical description of charge-conserving spin-dipole {1}- excitations is presented for the same isotopes. The energy spectra for both kinds of excitations are analysed in detail. Furthermore, a comparison of the calculated cross-sections and energies with the available experimental data is given.

Lead isotope database of unpublished results from sulfide mineral occurrences-California, Idaho, Oregon, and Washington

USGS Publications Warehouse

Church, S.E.

2010-01-01

The Pb isotope database for sulfide deposits and occurrences in the Western United States was funded by the Mineral Resources Program, U.S. Geological Survey (USGS). Reports on Pb isotope data from Alaska were published in Church and others (1987a) and Gaccetta and Church (1989). The primary objectives of the project were three-fold: * To utilize Pb isotope signatures, in conjunction with the regional mapping, to assess the relative ages and to categorize the types of deposits studied, * To relate the Pb isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and * To use the Pb isotope data to correlate lithotectonic terranes within the northern Cordillera. The report by Church and others (1987b) shows how this fingerprinting methodology can be applied to trace the offset of lithostratigraphic terranes

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.

Isotope Tales: Remaining Problems, Unsolvable Questions, and Gentle Successes

NASA Astrophysics Data System (ADS)

fogel, marilyn; bradley, christina; newsome, seth; filipp, fabian

2014-05-01

Earth's biomes function and adapt today as climate changes and ecosystems and the organisms within them adapt. Stable isotope biogeochemistry has had a major influence in understanding climate perturbations and continues to be an active area of research on many fronts. Banking on the success of compound specific stable isotope analyses of amino acids, nitrogen, carbon, and hydrogen isotopes continue to reveal subtle shifts in oceanic food webs and metabolic changes in microbes, plants, and animals. A biochemical understanding of exactly how organisms process and partition stable isotopes during metabolism remains unsolved, but is required if this field is to move beyond description to quantitation. Although the patterns of carbon and nitrogen isotopes are fairly well established in the common amino acids, we need to consider specifics: How do shifting metabolic pathways (metabolomics) influence the outcome of stable isotope partitioning? What influence does the gut microflora in animals have on isotopic labeling? What are the intramolecular isotope patterns of common amino acids and what do they tell us? What can be learned with other isotope systems, such as hydrogen? Results and ideas of how to move forward in this field will be presented starting at the molecular level and ending with ecosystems.

Oxygen isotope fractionation in the CaCO3-DIC-H2O system

NASA Astrophysics Data System (ADS)

Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

2017-10-01

The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading to a relatively constant foraminifer calcite δ18O-temperature relationship (-0.21 ± 0.01‰/°C). The lower average coral δ18O data relative to foraminifers and other calcifiers is best explained by the precipitation of internal DIC derived from hydrated CO2 in a high-pH calcifying fluid and minimal subsequent DIC-H2O isotopic equilibration. This leads to a reduced and variable coral aragonite δ18O-temperature relationship (-0.11 to -0.22‰/°C). Together, the model presented here reconciles observations of oxygen isotope fractionation over a range of CaCO3-DIC-H2O systems.

Dual isotopic approach for determining groundwater origin and water-rock interactions in over exploited watershed in India

NASA Astrophysics Data System (ADS)

Negrel, Philippe; Pauwels, Hélène; Millot, Romain; Roy, Stéphane; Guerrot, Catherine

2010-05-01

Groundwater flow and storage in hard rock areas is becoming a matter of great interest and importance to researchers and water managers either with regards to the quantity, quality of water as well as delimitation of resources and aquifers. Degradation of groundwater resources by abstraction, contamination, ... has been increasing in many areas and is of growing concern for few decades. In terms of hydrogeology, hard rocks represent a quite heterogeneous and anisotropic media with irregular distribution of pathways of groundwater flow, typically consisting of three vertical zones, upper weathered, middle fractured and lower massive bedrock. Aim of this work is dual and the Maheshwaram watershed (53 km2, Andhra Pradesh, India) representative of watersheds in southern India in terms of geology, overpumping of its hard-rock aquifer (more than 700 classical open end wells in use), its cropping pattern (rice dominating), and its rural socio-economy mainly based on traditional agriculture is investigated through stable isotopes of the water molecule and lead isotopes in groundwater. The overall objective is to incorporate isotopic- and chemical-tracing data and constraints into methods for evaluating groundwater circulation. It divides into fingerprinting the groundwater recharge processes (e.g. the input by the monsoon) and the water use in such agricultural watershed, which is of primary importance in such semi-arid context and investigating the processes of water-rock interactions (e.g. granite-water interaction). In the frame of delimitation of resources and aquifers and long-term sustainability, we monitored the input from monsoon-precipitation over 2 years, and measured spatial and temporal variations in δ18O and δ2H in the groundwater and in precipitation. Individual recharge from the two monsoon periods was identified. This led to identification of periods during which evaporation affects groundwater quality through a higher concentration of salts and stable isotopes in the return flow. In addition, such evaporation is further affected by land use, rice paddies having the strongest evapotranspiration. Lead concentrations span over one or two orders of magnitude up to approximately 20 ?g. L-1. Pb-isotopes, measured in water by MC-ICPMS using an improved new procedure, fluctuate largely as exemplified by the 206Pb/204Pb ratio, reaching values up to 25. Most of the lead in the groundwaters is of geogenic origin, and through the lead isotopic signature in groundwater we have traced and fingerprinted the processes of water-rock interactions considering the granite matrix. Combining a weathering model and field observations, we have defined a two step weathering process that includes a control on the Pb-isotopes ratios by accessory phases and by the main mineral from the granite in a second step of weathering. For future studies, multi-isotope approach will be necessary for the identification of possible flowpaths, in conjunction with the larger exploitation of the groundwater resources. This is also challenging for generalising the use of isotope tools (such as Nd, Sr, Pb and newly developed isotope systematics like Ca, Si...) in many other catchments that may face structural problems of groundwater overdraft.

Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes.

PubMed

Santamaria-Fernandez, Rebeca; Wolff, Jean-Claude

2010-07-30

The potential of high-precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA-MC-ICP-MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in-house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured-corrected Ca isotope ratio values ((43)Ca/(44)Ca and (42)Ca/(44)Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured-corrected Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)-ICP-MS instrument. The use of LA-MC-ICP-MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification. Copyright 2010 John Wiley & Sons, Ltd.

Observation of the 162Dy-164Dy Isotope Shift for the 0 → 16 717.79 cm-1 Optical Transition.

PubMed

Nardin Barreta, Luiz Felipe; Victor, Alessandro Rogério; Bueno, Patrícia; Dos Santos, Jhonatha Ricardo; da Silveira, Carlos Alberto Barbosa; Neri, José Wilson; Neto, Jonas Jakutis; Sbampato, Maria Esther; Destro, Marcelo Geraldo

2017-08-01

In this work, we report a newly observed isotope shift between 162 Dy and 164 Dy isotopes for the 0 → 16 717.79 cm -1 (598.003 nm) optical transition. We compared the newly observed results against two other lines (597.452 nm and 598.859 nm), which we measured in this work, and were already reported in the literature. The newly observed 162-164 Dy isotope shift, shows at least a 20% larger isotope shift than the isotope shifts for the other two lines investigated. The larger 162-164 isotope shift observed for the 598.003 nm line could lead to an increased isotope selectivity for atomic vapor laser isotope separation (AVLIS). Hence, this line could be a good choice for application in AVLIS. Experimental data available in the literature for the 597.452 nm and 598.859 nm lines, enabled us to perform simulations of spectra for both lines, in order to confirm the accuracy of our experimental measurements.

Highly Efficient Quantum Sieving in Porous Graphene-like Carbon Nitride for Light Isotopes Separation

NASA Astrophysics Data System (ADS)

Qu, Yuanyuan; Li, Feng; Zhou, Hongcai; Zhao, Mingwen

2016-01-01

Light isotopes separation, such as 3He/4He, H2/D2, H2/T2, etc., is crucial for various advanced technologies including isotope labeling, nuclear weapons, cryogenics and power generation. However, their nearly identical chemical properties made the separation challenging. The low productivity of the present isotopes separation approaches hinders the relevant applications. An efficient membrane with high performance for isotopes separation is quite appealing. Based on first-principles calculations, we theoretically demonstrated that highly efficient light isotopes separation, such as 3He/4He, can be reached in a porous graphene-like carbon nitride material via quantum sieving effect. Under moderate tensile strain, the quantum sieving of the carbon nitride membrane can be effectively tuned in a continuous way, leading to a temperature window with high 3He/4He selectivity and permeance acceptable for efficient isotopes harvest in industrial application. This mechanism also holds for separation of other light isotopes, such as H2/D2, H2/T2. Such tunable quantum sieving opens a promising avenue for light isotopes separation for industrial application.

Effects of must concentration techniques on wine isotopic parameters.

PubMed

Guyon, Francois; Douet, Christine; Colas, Sebastien; Salagoïty, Marie-Hélène; Medina, Bernard

2006-12-27

Despite the robustness of isotopic methods applied in the field of wine control, isotopic values can be slightly influenced by enological practices. For this reason, must concentration technique effects on wine isotopic parameters were studied. The two studied concentration techniques were reverse osmosis (RO) and high-vacuum evaporation (HVE). Samples (must and extracted water) have been collected in various French vineyards. Musts were microfermented at the laboratory, and isotope parameters were determined on the obtained wine. Deuterium and carbon-13 isotope ratios were studied on distilled ethanol by nuclear magnetic resonance (NMR) and isotope ratio mass spectrometry (IRMS), respectively. The oxygen-18 ratio was determined on extracted and wine water using IRMS apparatus. The study showed that the RO technique has a very low effect on isotopic parameters, indicating that this concentration technique does not create any isotopic fractionation, neither at sugar level nor at water level. The effect is notable for must submitted to HVE concentration: water evaporation leads to a modification of the oxygen-18 ratio of the must and, as a consequence, ethanol deuterium concentration is also modified.

Contribution of bulk mass spectrometry isotopic analysis to characterization of materials in the framework of CMX-4

DOE PAGES

Kuchkin, A.; Stebelkov, V.; Zhizhin, K.; ...

2018-01-30

Seven laboratories used the results of bulk uranium isotopic analysis by either inductively coupled plasma mass spectrometry (ICP-MS) or thermal ionization mass spectrometry (TIMS) for characterization of the samples in the Nuclear Forensic International Technical Working Group fourth international collaborative material exercise, CMX-4. Comparison of the measured isotopic compositions of uranium in three exercise samples is implemented for identifying any differences or similarities between the samples. The role of isotopic analyses in the context of a real nuclear forensic investigation is discussed. Several limitations in carrying out ICP-MS or TIMS analysis in CMX-4 are noted.

The Satellite Telescope Nina for Nuclear and Isotopic Investigations in Space

NASA Astrophysics Data System (ADS)

Circella, M.; Bidoli, V.; Casolino, M.; de Pascale, M. P.; Morselli, A.; Furano, G.; Picozza, P.; Scoscini, A.; Sparvoli, R.; Barbiellini, G.; Bonvicini, W.; Cirami, R.; Schiavon, P.; Vacchi, A.; Zampa, N.; Ambriola, M.; Bellotti, R.; Cafagna, F.; Ciacio, F.; de Marzo, C.; Bartalucci, S.; Giuntoli, S.; Ricci, M.; Papini, P.; Piccardi, S.; Spillantini, P.; Bakaldin, A.; Batishev, A.; Galper, A. M.; Koldashov, S.; Mikhailov, V.; Murashov, A.; Voronov, S.; Boezio, M.

2000-09-01

NINA is a satellite silicon detector designed to perform measurements of the nuclear and isotopic composition of the galactic and anomalous components of cosmic rays, as well as of the energetic particles associated with solar flares. It has been orbiting the Earth onboard the Russian satellite Resource 01 n. 4 since July 1998. It can perform nuclear discrimination from hydrogen to iron as well as isotopic analyses at least up to the beryllium isotopes in a large energy range. NINA is the first step of the wide scientific program WiZard-RIM, which includes the design and deployment of the PAMELA magnet spectrometer.

Development of Tandem, Double-Focusing, Electron Impact, Gas Source Mass Spectrometer for Measurement of Rare Double-Substituted Isotoplogues in Geochemistry

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

Young, Edward D.

This project culminated in construction and delivery of the world’s first large-radius gas-source isotope ratio mass spectrometer that permits unparalleled analyses of the stable isotopic composition of methane gas. The instrument, referred to as the “Panorama” and installed at UCLA in March 2015, can now be used to determine the relative abundances of rare isotopic species of methane that serve as tracers of temperature of formation and/or subsequent processing of gas. With this technology we can begin to delineate different sources and sinks of methane isotopically in ways not possible until now.

Oxygen reservoirs in the early solar nebula inferred from an Allende CAI.

PubMed

Young, E D; Russell, S S

1998-10-16

Ultraviolet laser microprobe analyses of a calcium-aluminum-rich inclusion (CAI) from the Allende meteorite suggest that a line with a slope of exactly 1.00 on a plot of delta (17)O against delta (18)O represents the primitive oxygen isotope reservoir of the early solar nebula. Most meteorites are enriched in (17)O and (18)O relative to this line, and their oxygen isotope ratios can be explained by mass fractionation or isotope exchange initiating from the primitive reservoir. These data establish a link between the oxygen isotopic composition of the abundant ordinary chondrites and the primitive (16)O-rich component of CAIs.

Oxygen reservoirs in the early solar nebula inferred from an allende CAI

PubMed

Young; Russell

1998-10-16

Ultraviolet laser microprobe analyses of a calcium-aluminum-rich inclusion (CAI) from the Allende meteorite suggest that a line with a slope of exactly 1.00 on a plot of delta17O against delta18O represents the primitive oxygen isotope reservoir of the early solar nebula. Most meteorites are enriched in 17O and 18O relative to this line, and their oxygen isotope ratios can be explained by mass fractionation or isotope exchange initiating from the primitive reservoir. These data establish a link between the oxygen isotopic composition of the abundant ordinary chondrites and the primitive 16O-rich component of CAIs.

Contribution of bulk mass spectrometry isotopic analysis to characterization of materials in the framework of CMX-4

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

Kuchkin, A.; Stebelkov, V.; Zhizhin, K.

Seven laboratories used the results of bulk uranium isotopic analysis by either inductively coupled plasma mass spectrometry (ICP-MS) or thermal ionization mass spectrometry (TIMS) for characterization of the samples in the Nuclear Forensic International Technical Working Group fourth international collaborative material exercise, CMX-4. Comparison of the measured isotopic compositions of uranium in three exercise samples is implemented for identifying any differences or similarities between the samples. The role of isotopic analyses in the context of a real nuclear forensic investigation is discussed. Several limitations in carrying out ICP-MS or TIMS analysis in CMX-4 are noted.

Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

PubMed Central

Platzner, Thomas I.; Segal, Irina

2007-01-01

The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment. PMID:17962922

The carbon isotope biogeochemistry of the individual hydrocarbons in bat guano and the ecology of the insectivorous bats in the region of Carlsbad, New Mexico

NASA Technical Reports Server (NTRS)

Des Marais, D. J.; Mitchell, J. M.; Meinschein, W. G.; Hayes, J. M.

1980-01-01

The structures and C-13 contents of individual hydrocarbons extracted from bat guano found in the Carlsbad region of New Mexico are analyzed in order to elucidate details of the carbon flow in the plant-insect-bat ecosystem. Carbon isotopic analyses indicate that equivalent numbers of plants with C3 and C4 photosynthetic pathways occupy the feeding area of the bats, which supports alfalfa and cotton as well as native plants. The molecular composition of the guano is consistent with an origin in two distinct populations of insects with different feeding habits, one of which may graze predominantly on crops. It is also pointed out that isotopic analyses of more ancient guano deposits may be useful in characterizing prevalent vegetation and climate of earlier periods.

Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

NASA Astrophysics Data System (ADS)

Marzouk, E. R.; Chenery, S. R.; Young, S. D.

2013-12-01

The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (<0.22 μm) colloidal particles (SCP-metal). For most soils, the presence of non-labile SCP-metal caused only minor over-estimation of E-values (<2%) but the effect was greater for soils with particularly large humus or carbonate contents. Approximately 80%, 53% and 66% of the variability in Zn, Cd and Pb %E-values (respectively) could be explained by pH, loss on ignition and total metal content. E-values were affected by the presence of ore minerals at high metal contents leading to an inconsistent trend in the relationship between %E-value and soil metal concentration. Metal solubility, in the soil suspensions used to measure E-values, was predicted using the WHAM geochemical speciation model (versions VI and VII). The use of total and isotopically exchangeable metal as alternative input variables was compared; the latter provided significantly better predictions of solubility, especially in the case of Zn. Lead solubility was less well predicted by either version of WHAM, with over-prediction at low pH and under-prediction at high soil pH values. Quantify the isotopically exchangeable fractions of Zn, Cd and Pb (E-values), and assess their local and regional variability, using multi-element stable isotope dilution, in a diverse range of soil ecosystems within the catchment of an old Pb/Zn mining area. Assess the controlling influences of soil properties on metal lability and develop predictive algorithms for metal lability in the contaminated catchment based on simple soil properties (such as pH, organic matter (LOI), and total metal content). Examine the incidence of non-isotopically-exchangeable metal held within suspended colloidal particles (SCP-metal) in filtered soil solutions (<0.22 μm) by comparing E-values from isotopic abundance in solutions equilibrated with soil and in a resin phase equilibrated with the separated solution. Assess the ability of a geochemical speciation model, WHAM(VII), to predict metal solubility using isotopically exchangeable metal as an input variable.

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

USGS Publications Warehouse

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

2014-01-01

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

Tracing geogenic and anthropogenic sources in urban dusts: Insights from lead isotopes

NASA Astrophysics Data System (ADS)

Del Rio-Salas, R.; Ruiz, J.; De la O-Villanueva, M.; Valencia-Moreno, M.; Moreno-Rodríguez, V.; Gómez-Alvarez, A.; Grijalva, T.; Mendivil, H.; Paz-Moreno, F.; Meza-Figueroa, D.

2012-12-01

Tracing the source of metals in the environment is critical to understanding their pollution level and fate. Geologic materials are an important source of airborne particulate matter, but the contribution of contaminated soil to concentrations of Pb in airborne dust is not yet widely documented. To examine the potential significance of this mechanism, surface soil samples were collected, as well as wind-transported dust trapped at 1 and 2 m height at seven different locations including residential, industrial, high-traffic and rural sites. Samples of dust deposited on roofs from 24 schools were also obtained and analyzed for Pb isotope ratios. Spatial distribution of Pb of airborne and sedimented dust suggests a process dominated by re-suspension/sedimentation, which was controlled by erosion, traffic and topography of the urban area. Anthropogenic lead input in the city grades outward the urban zone toward geogenic values. Our results shows that Pb-isotopic signatures of leaded gasoline are imprinted in dust sedimented on roofs. Considering that leaded-gasoline has not been in use in Mexico since two decades ago, this signature shows not only a Pb-legacy in soil, but also a re-suspension process affecting air column below 3 m in height. The combination of the 207Pb/206Pb data of the surrounding rocks and urban dust, reveal three well-defined zones with remarkable anthropogenic influence, which correspond to the oldest urban sectors. This work highlights the importance of spatial characterization of metals in particles suspended below a height of 3 m of the airborne column, a fact that should be considered to identify exposure paths to humans and the potential risks. Lead isotope signatures allowed the identification of geogenic and anthropogenic emission sources for dust, a matter that deserves consideration in the efforts to control airborne metal emissions.

Carbon Isotope Fractionation in Reactions of 1,2-Dibromoethane with FeS and Hydrogen Sulfide

EPA Science Inventory

EDB (1,2-dibromoethane) is frequently detected at sites impacted by leaded gasoline. In reducing environments, EDB is highly susceptible to abiotic degradation. A study was conducted to evaluate the potential of compound-specific isotope analysis (CSIA) in assessing abiotic degr...

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

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

USGS Publications Warehouse

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

2003-01-01

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

Cadmium-isotopic evidence for increasing primary productivity during the Late Permian anoxic event

NASA Astrophysics Data System (ADS)

Georgiev, Svetoslav V.; Horner, Tristan J.; Stein, Holly J.; Hannah, Judith L.; Bingen, Bernard; Rehkämper, Mark

2015-01-01

Earth's most extreme extinction event near the end of the Late Permian decimated more than 90% of all extant marine species. Widespread and intensive oceanic anoxia almost certainly contributed to the catastrophe, though the driving mechanisms that sustained such conditions are still debated. Of particular interest is whether water column anoxia was a consequence of a 'stagnant ocean', or if it was controlled by increases in nutrient supply, primary productivity, and subsequent heterotrophic respiration. Testing these competing hypotheses requires deconvolving sedimentary/bottom water redox conditions from changes in surface water productivity in marine sediments. We address this issue by studying marine shales from East Greenland and the mid-Norwegian shelf and combining sedimentary redox proxies with cadmium-isotopic analyses. Sedimentary nitrogen-isotopic data, pyrite framboid analyses, and organic and inorganic shale geochemistry reveal sulfidic conditions with vigorous upwelling, and increasingly anoxic conditions with a strengthening upwelling in the Greenland and Norwegian sections, respectively. Detailed analysis of sedimentary metal budgets illustrates that Cd is primarily associated with organic carbon and records primary geochemical signatures, thus enabling reconstruction of surface water nutrient utilization. Cadmium-isotopic analyses of the authigenic shale fraction released by inverse aqua regia digestion yield an average δ114Cd110 of + 0.15 ± 0.01 ‰ (2 SE, n = 12; rel. NIST SRM 3108), indicative of incomplete surface water nutrient utilization up-section. The constant degree of nutrient utilization combined with strong upwelling requires increasing primary productivity - and not oceanic stagnation - to balance the larger nutrient fluxes to both study sites during the development of the Late Permian water column anoxia. Overall, our data illustrate that if bottom water redox and upwelling can be adequately constrained, Cd-isotopic analyses of organic-rich sediments can be used to provide valuable information on nutrient utilization and therefore past productivity.

A latitudinal study of oxygen isotopes within horsehair

NASA Astrophysics Data System (ADS)

Thompson, E.; Bronk Ramsey, C.; McConnell, J. R.

2016-12-01

This study aims to explore the hypothesis that 'if oxygen isotope ratios deplete with decreasing temperature then a study of oxygen isotope ratios within horsehair from Oxfordshire to Iceland will show a latitudinal depletion gradient'. By looking at oxygen isotope values at different geographical positions, we can track the relationship with latitude and with different regional climate features. This will provide a firmer understanding of how to compare climate records from different locations. Additionally, a comparison of the horse breeds from this study to those analysed within previous studies will create an even better understanding of the intra-species variation within the δ18O values of horsehair. A total of 24 horses were sampled on the 7th March from Thordale Stud in Shetland, the Icelandic Food And Veterinary Authority in Iceland, the Exmoor Pony Centre in Exmoor and the Pigeon House Equestrian Centre in Oxfordshire. By starting the sampling process from the most recent growth at the follicle, the sampling date becomes a chronological marker, temporally fixing the first sample within a sequential set of data points extending for one year or longer, depending on the length of each individual hair. The samples were analysed for oxygen isotope values using an IRMS coupled within a Sercon HTEA. Preliminary results show a latitudinal gradient is evident on comparison between the locations, consistent with the findings of Darling and Talbot's study of fresh water isotopes in the British Isles (2003). These results support the hypothesis, showing that a study of oxygen isotope ratios within horse hair from Oxfordshire to Iceland showing a latitudinal depletion gradient, consistent with a depletion of oxygen isotope ratios due to decreasing temperatures. Darling, W. and Talbot, J. (2003). The O and H stable isotope composition of freshwaters in the British Isles. 1. Rainfall. Hydrol. Earth System Science, 7(2), pp.163-181.

CORRESPONDENCE OF STABLE ISOTOPE AND GUT CONTENTS ANALYSES IN DETERMINING TROPHIC POSITION OF STREAM FISHES

EPA Science Inventory

It is generally accepted that both stable isotope analysis (SIA) and gut contents analysis (GCA) be used in food web studies; however, few researchers have analyzed these data in concert. We utilized SIA and GCA to determine if longitudinal and seasonal variation in diet affects...

Comparing trophic position of stream fishes using stable isotope and gut contents analyses

EPA Science Inventory

Stable isotope analysis (SIA) and gut content analysis (GCA) are commonly used in food web studies, but few studies analyze these data in concert. We used SIA and GCA to identify diets and trophic position (TP) of six stream fishes and to compare TP estimates between methods. Ord...

PRODUCTION AND TRANSPORT OF CARBON DIOXIDE IN A CONTAMINATED VADOSE ZONE: A STABLE AND RADIOACTIVE CARBON ISOTOPE STUDY

EPA Science Inventory

Analyses of soil gas compositions and stable and radioactive carbon isotopes in the vadose zone above an alluvial aquifer were conducted at an organic solvent disposal site in southeast Phoenix, AZ. The study investigated the source and movement of carbon dioxide above a plume of...

Krypton and xenon in lunar fines

NASA Technical Reports Server (NTRS)

Basford, J. R.; Dragon, J. C.; Pepin, R. O.; Coscio, M. R., Jr.; Murthy, V. R.

1973-01-01

Data from grain-size separates, stepwise-heated fractions, and bulk analyses of 20 samples of fines and breccias from five lunar sites are used to define three-isotope and ordinate intercept correlations in an attempt to resolve the lunar heavy rare gas system in a statistically valid approach. Tables of concentrations and isotope compositions are given.

Stable isotope analysis of stream organisms - a useful tool for monitoring changes in catchment conditions and effects on stream ecosystems?

EPA Science Inventory

Stable isotope analyses of stream organisms usually are performed as discrete site experiments (e.g., to study the effect of a direct manipulation), synoptically (e.g. to illustrate effects of longitudinal variation of influencing factors), or, less frequently, over the course of...

Stable Isotope Analysis of stream organisms -- a potential tool for monitoring changes in catchment conditions and effects on stream ecosystems

EPA Science Inventory

Stable isotope analyses of stream organisms are performed usually as discrete site experiments (e.g., to study the effect of a direct manipulation), synoptically (e.g. to illustrate effects of longitudinal variation of influencing factors), or, less frequently, over the course of...

Hydrological connectivity of perched aquifers and regional aquifers in semi-arid environments: a case study from Namibia

NASA Astrophysics Data System (ADS)

Hamutoko, J. T.; Wanke, H.

2017-12-01

Integrated isotopic and hydrological tracers along with standard hydrological data are used to understand complex dry land hydrological processes on different spatial and temporal scales. The objective of this study is to analyse the relationship between the perched aquifers and the regional aquifer using hydrochemical data and isotopic composition in the Cuvelai-Etosha Basin in Namibia. This relation between the aquifers will aid in understanding groundwater recharge processes and flow dynamics. Perched aquifers are discontinuous shallow aquifers with water level ranging from 0 to 30 meters below ground level. The regional aquifer occurs in semi-consolidated sandstone at depths between about 60 and 160 meters below ground level. Water samples were collected from both aquifers in 10 villages and were analysed for major ions and stable isotopes. The results show overlapping hydrochemistry and isotopic compositions of both aquifers in 8 villages which suggest the possibility of perched aquifer water infiltrating into the regional aquifer. In two villages the hydrochemistry and isotopic composition of the aquifers are totally different and this suggests that there is no interaction between this aquifers. Areas where perched aquifers are connected to regional aquifers maybe recharge zones. These finding have important implications for groundwater resource management.

Global Trophic Position Comparison of Two Dominant Mesopelagic Fish Families (Myctophidae, Stomiidae) Using Amino Acid Nitrogen Isotopic Analyses

PubMed Central

Choy, C. Anela; Davison, Peter C.; Drazen, Jeffrey C.; Flynn, Adrian; Gier, Elizabeth J.; Hoffman, Joel C.; McClain-Counts, Jennifer P.; Miller, Todd W.; Popp, Brian N.; Ross, Steve W.; Sutton, Tracey T.

2012-01-01

The δ15N values of organisms are commonly used across diverse ecosystems to estimate trophic position and infer trophic connectivity. We undertook a novel cross-basin comparison of trophic position in two ecologically well-characterized and different groups of dominant mid-water fish consumers using amino acid nitrogen isotope compositions. We found that trophic positions estimated from the δ15N values of individual amino acids are nearly uniform within both families of these fishes across five global regions despite great variability in bulk tissue δ15N values. Regional differences in the δ15N values of phenylalanine confirmed that bulk tissue δ15N values reflect region-specific water mass biogeochemistry controlling δ15N values at the base of the food web. Trophic positions calculated from amino acid isotopic analyses (AA-TP) for lanternfishes (family Myctophidae) (AA-TP ∼2.9) largely align with expectations from stomach content studies (TP ∼3.2), while AA-TPs for dragonfishes (family Stomiidae) (AA-TP ∼3.2) were lower than TPs derived from stomach content studies (TP∼4.1). We demonstrate that amino acid nitrogen isotope analysis can overcome shortcomings of bulk tissue isotope analysis across biogeochemically distinct systems to provide globally comparative information regarding marine food web structure. PMID:23209656

Global trophic position comparison of two dominant mesopelagic fish families (Myctophidae, Stomiidae) using amino acid nitrogen isotopic analyses

USGS Publications Warehouse

Choy, C. Anela; Davison, Peter C.; Drazen, Jeffrey C.; Flynn, Adrian; Gier, Elizabeth J.; Hoffman, Joel C.; McClain-Counts, Jennifer P.; Miller, Todd W.; Popp, Brian N.; Ross, Steve W.; Sutton, Tracey T.

2012-01-01

The δ15N values of organisms are commonly used across diverse ecosystems to estimate trophic position and infer trophic connectivity. We undertook a novel cross-basin comparison of trophic position in two ecologically well-characterized and different groups of dominant mid-water fish consumers using amino acid nitrogen isotope compositions. We found that trophic positions estimated from the δ15N values of individual amino acids are nearly uniform within both families of these fishes across five global regions despite great variability in bulk tissue δ15N values. Regional differences in the δ15N values of phenylalanine confirmed that bulk tissue δ15N values reflect region-specific water mass biogeochemistry controlling δ15N values at the base of the food web. Trophic positions calculated from amino acid isotopic analyses (AA-TP) for lanternfishes (family Myctophidae) (AA-TP ~2.9) largely align with expectations from stomach content studies (TP ~3.2), while AA-TPs for dragonfishes (family Stomiidae) (AA-TP ~3.2) were lower than TPs derived from stomach content studies (TP~4.1). We demonstrate that amino acid nitrogen isotope analysis can overcome shortcomings of bulk tissue isotope analysis across biogeochemically distinct systems to provide globally comparative information regarding marine food web structure.

Origin of sulfur for elemental sulfur concentration in salt dome cap rocks, Gulf Coast Basin, USA

NASA Astrophysics Data System (ADS)

Hill, J. M.; Kyle, R.; Loyd, S. J.

2017-12-01

Calcite cap rocks of the Boling and Main Pass salt domes contain large elemental sulfur accumulations. Isotopic and petrographic data indicate complex histories of cap rock paragenesis for both domes. Whereas paragenetic complexity is in part due to the open nature of these hydrodynamic systems, a comprehensive understanding of elemental sulfur sources and concentration mechanisms is lacking. Large ranges in traditional sulfur isotope compositions (δ34S) among oxidized and reduced sulfur-bearing phases has led some to infer that microbial sulfate reduction and/or influx of sulfide-rich formation waters occurred during calcite cap rock formation. Ultimately, traditional sulfur isotope analyses alone cannot distinguish among local microbial or exogenous sulfur sources. Recently, multiple sulfur isotope (32S, 33S, 34S, 36S) studies reveal small, but measurable differences in mass-dependent behavior of microbial and abiogenic processes. To distinguish between the proposed sulfur sources, multiple-sulfur-isotope analyses have been performed on native sulfur from the Boling and Main Pass cap rocks. Similarities or deviations from equilibrium relationships indicate which pathways were responsible for native sulfur precipitation. Pathway determination provides insight into Gulf Coast cap rock development and potentially highlights the conditions that led to anomalous sulfur enrichment in Boling and Main Pass Domes.

Chondrule heritage and thermal histories from trace element and oxygen isotope analyses of chondrules and amoeboid olivine aggregates

NASA Astrophysics Data System (ADS)

Jacquet, Emmanuel; Marrocchi, Yves

2017-12-01

We report combined oxygen isotope and mineral-scale trace element analyses of amoeboid olivine aggregates (AOA) and chondrules in ungrouped carbonaceous chondrite, Northwest Africa 5958. The trace element geochemistry of olivine in AOA, for the first time measured by LA-ICP-MS, is consistent with a condensation origin, although the shallow slope of its rare earth element (REE) pattern is yet to be physically explained. Ferromagnesian silicates in type I chondrules resemble those in other carbonaceous chondrites both geochemically and isotopically, and we find a correlation between 16O enrichment and many incompatible elements in olivine. The variation in incompatible element concentrations may relate to varying amounts of olivine crystallization during a subisothermal stage of chondrule-forming events, the duration of which may be anticorrelated with the local solid/gas ratio if this was the determinant of oxygen isotopic ratios as proposed recently. While aqueous alteration has depleted many chondrule mesostases in REE, some chondrules show recognizable subdued group II-like patterns supporting the idea that the immediate precursors of chondrules were nebular condensates.

Climatic changes resulting from mass extinctions at the K-T boundary (and other bio-events)

NASA Technical Reports Server (NTRS)

Rampino, Michael R.; Volk, Tyler

1988-01-01

The mass extinctions at the Cretaceous-Tertiary (K-T) boundary include about 90 percent of marine calcareous nannoplankton (coccoliths), and carbon-isotope data show that marine primary productivity was drastically reduced for about 500,000 years after the boundary event, the so-called Strangelove Ocean effect. One result of the elimination of most marine phytoplankton would have been a severe reduction in production of dimethyl sulfide (DMS), a biogenic gas that is believed to be the major precursor of cloud condensation nuclei (CCN) over the oceans. A drastic reduction in marine CCN should lead to a cloud canopy with significantly lower reflectivity, and hence cause a significant warming at the earth's surface. Calculations suggest that, all other things being held constant, a reduction in CCN of more than 80 percent (a reasonable value for the K-T extinctions) could have produced a rapid global warming of 6 C or more. Oxygen-isotope analyses of marine sediments, and other kinds of paleoclimatic data, have provided for a marked warming, and a general instability of climate coincident with the killoff of marine plankton at the K-T boundary. Similar reductions in phytoplankton abundance at other boundaries, as indicated by marked shifts in carbon-isotope curves, suggest that severe temperature changes may have accompanied other mass extinctions, and raises the intriguing possibility that the extinction events themselves could have contributed to the climatic instabilities at critical bio-events in the geologic record.

Chimpanzee fauna isotopes provide new interpretations of fossil ape and hominin ecologies

PubMed Central

Nelson, Sherry V.

2013-01-01

Carbon and oxygen stable isotopes within modern and fossil tooth enamel record the aspects of an animal's diet and habitat use. This investigation reports the first isotopic analyses of enamel from a large chimpanzee community and associated fauna, thus providing a means of comparing fossil ape and early hominin palaeoecologies with those of a modern ape. Within Kibale National Park forest, oxygen isotopes differentiate primate niches, allowing for the first isotopic reconstructions of degree of frugivory versus folivory as well as use of arboreal versus terrestrial resources. In a comparison of modern and fossil community isotopic profiles, results indicate that Sivapithecus, a Miocene ape from Pakistan, fed in the forest canopy, as do chimpanzees, but inhabited a forest with less continuous canopy or fed more on leaves. Ardipithecus, an early hominin from Ethiopia, fed both arboreally and terrestrially in a more open habitat than inhabited by chimpanzees. PMID:24197413

Difference in the stable isotopic fractionations of Ce, Nd, and Sm during adsorption on iron and manganese oxides and its interpretation based on their local structures

NASA Astrophysics Data System (ADS)

Nakada, Ryoichi; Tanimizu, Masaharu; Takahashi, Yoshio

2013-11-01

Many elements have become targets for studies of stable isotopic fractionation with the development of various analytical techniques. Although several chemical factors that control the isotopic fractionation of heavy elements have been proposed, it remains controversial which properties are most important for the isotopic fractionation of elements. In this study, the stable isotopic fractionation of neodymium (Nd) and samarium (Sm) during adsorption on ferrihydrite and δ-MnO2 was examined. This examination was combined with speciation analyses of these ions adsorbed on the solid phases by extended X-ray absorption fine structure (EXAFS) spectroscopy. Neodymium isotope ratios for Nd on ferrihydrite and δ-MnO2 systems were, on average, 0.166‰ and 0.410‰ heavier than those of the liquid phase, which correspond to mean isotopic fractionation factors between the liquid and solid phases (αLq-So) of Nd on ferrihydrite and δ-MnO2 of 0.999834 (2σ = ±0.000048) and 0.999590 (2σ = ±0.000106), respectively. Similarly, averaged Sm isotope ratios on ferrihydrite and δ-MnO2 were 0.206‰ and 0.424‰ heavier than those of the liquid phase and the corresponding αLq-So values were 0.999794 (±0.000041) and 0.999576 (±0.000134), respectively. These results indicate that the directions of isotopic fractionation in the Nd and Sm systems are in contrast with that recently found for Ce(III) systems despite the similar chemical characteristics of rare earth elements. EXAFS analyses suggest that the bond length of the first coordination sphere (REE-O bond) of Nd and Sm adsorbed on δ-MnO2 is shorter than that of their aqua ions, although this was not clear for the ferrihydrite systems. The shorter bond length relative to the aqua ion is indicative of a stronger bond, suggesting that the equilibrium isotopic fractionation for the Nd and Sm systems can be governed by bond strength as has often been discussed for isotopic fractionation in solid-water adsorption systems. Meanwhile, EXAFS analyses of the Ce/ferrihydrite system showed a distorted structure for the first coordination sphere that was not observed for Ce3+ aqua ions. Such distortion was also observed for La adsorption on ferrihydrite and δ-MnO2. In addition, previous studies have suggested a high stability of the hydrated state for La and Ce in terms of Gibbs free energy change. Thus, we suggest here that the difference in the stable isotopic fractionation for Ce (and predicted for La) vs. Nd and Sm can be explained by (i) the shorter bond lengths of adsorbed relative to dissolved species for Nd and Sm and (ii) the distorted structure of adsorbed Ce (and La) species and high stability of the aqua Ce ion.

87Sr/ 86Sr Concentrations in the Appalachian Basin: A Review

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

Mordensky, Stanley P.; Lieuallen, A. Erin; Verba, Circe

This document reviews 87Sr/ 86Sr isotope data across the Appalachian Basin from existing literature to show spatial and temporal variation. Isotope geochemistry presents a means of understanding the geochemical effects hydraulic fracturing may have on shallow ground substrates. Isotope fractionation is a naturally occurring phenomenon brought about by physical, chemical, and biological processes that partition isotopes between substances; therefore, stable isotope geochemistry allows geoscientists to understand several processes that shape the natural world. Strontium isotopes can be used as a tool to answer an array of geological and environmental inquiries. In some cases, strontium isotopes are sensitive to the introductionmore » of a non-native fluid into a system. This ability allows strontium isotopes to serve as tracers in certain systems. Recently, it has been demonstrated that strontium isotopes can serve as a monitoring tool for groundwater and surface water systems that may be affected by hydraulic fracturing fluids (Chapman et al., 2013; Kolesar Kohl et al., 2014). These studies demonstrated that 87Sr/ 86Sr values have the potential to monitor subsurface fluid migration in regions where extraction of Marcellus Shale gas is occurring. This document reviews publicly available strontium isotope data from 39 sample locations in the Appalachian Basin (Hamel et al., 2010; Chapman et al., 2012; Osborn et al., 2012; Chapman et al., 2013; Capo et al., 2014; Kolesar Kohl et al., 2014). The data is divided into two sets: stratigraphic (Upper Devonian/Lower Mississippi, Middle Devonian, and Silurian) and groundwater. ArcMap™ (ESRI, Inc.) was used to complete inverse distance weighting (IDW) analyses for each dataset to create interpolated surfaces in an attempt to find regional trends or variations in strontium isotopic values across the Appalachian Basin. 87Sr/ 86Sr varies up to ~ 0.011 across the Appalachian Basin, but the current publicly available data is limited in frequency and regional extent, causing artifacts and high uncertainty when interpolating data for locations far from sampling sites. These factors highlight the need for additional strontium isotope sampling across the region. Identifying potential contamination from hydraulic fracturing fluid in Appalachian Basin groundwater using strontium isotopes would require additional sampling. For a more comprehensive strontium isotope database, samples would need to be collected during prefracturing, syn-fracturing, and post-fracturing stages. This would add a temporal component to the spatial data and make tracing of fluid migration with strontium isotopes more accurate. Future research and modeling that incorporates subsurface geology and watershed data would also serve to increase the accuracy and certainty of the interpolations of these analyses. Prospective geospatial Appalachian Basin isotope studies would also benefit from the integration of geologic mapping because surface and subsurface geology influences observed strontium isotope values.« less

Changing carbon isotope ratio of atmospheric carbon dioxide: implications for food authentication.

PubMed

Peck, William H; Tubman, Stephanie C

2010-02-24

Carbon isotopes are often used to detect the addition of foreign sugars to foods. This technique takes advantage of the natural difference in carbon isotope ratio between C(3) and C(4) plants. Many foods are derived from C(3) plants, but the low-cost sweeteners corn and sugar cane are C(4) plants. Most adulteration studies do not take into account the secular shift of the carbon isotope ratio of atmospheric carbon dioxide caused by fossil fuel burning, a shift also seen in plant tissues. As a result statistical tests and threshold values that evaluate authenticity of foods based on carbon isotope ratios may need to be corrected for changing atmospheric isotope values. Literature and new data show that the atmospheric trend in carbon isotopes is seen in a 36-year data set of maple syrup analyses (n = 246), demonstrating that published thresholds for cane or corn sugar adulteration in maple syrup (and other foods) have become progressively more lenient over time.

[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.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Modeling stable isotope transport in metamorphic and hydrothermal systems

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Stable Isotopes, Multidisciplinary Studies, and the Leadership of J.G. Liou in UHP Metamorphism

NASA Astrophysics Data System (ADS)

Rumble, D.

2005-12-01

J.G. Liou has played a crucial role in improving knowledge of UHP metamorphism by leading multi-disciplinary, multi-institutional teams of researchers and by encouraging new investigators and providing them access to samples. Stable isotope geochemistry has made important contributions to understanding UHP metamorphism including: (1) The discovery of O- and H-isotope signatures of meteoric water in UHP rocks from China and Kazakhstan demonstrates that their protoliths originated at or near Earth's surface in a cold climate(a); (2) The mapping of contiguous tracts of outcrops extending over distances of 100 km where both eclogites and their wall rocks retain unusually low d18O and dD is consistent with the subduction and exhumation of UHP slabs as coherent structural units(b); (3) Analysis of samples from the Chinese Continental Scientific Drilling project reveals not only that UHP metamorphic rocks have not exchanged O-isotopes with mantle rocks while they were buried in the upper mantle but also that garnet peridotite slabs from the mantle have not exchanged with crustal wall rocks(c). Recent advances have resulted from multidisciplinary geochemical investigations. The analysis of zircons for both d18O and U-Pb established the age of cold climate, meteoric water alteration of protoliths to be Neoproterozoic for UHP rocks from Dabie and Sulu, China(d). Thus, O-isotopes plus age dating raises the possibility that evidence of snowball Earth conditions has been preserved in an unlikely host: UHP metamorphic rocks. A comparison of U-Pb, Sm-Nd, and Rb-Sr isotope data with analyses for d18O in coexisting minerals shows that discordant age dates correlate with mineral pairs that are not in O-isotope exchange equilibrium(e). It may be seen that multidisciplinary geochemical investigations provide mutually reinforcing data that greatly strengthens interpretations. New discoveries of de novo microdiamonds accompanied by multiphase mineral inclusions in UHP metamorphosed crustal rocks raise exciting possibilities for future stable isotope research on their origin(f). Micron-scale analytical techniques including ion microprobe, "Nano-SIMS", and UV-laser ablation, should be applied to the mineral assemblages to determine whether parent fluids were super-critical C-O-H fluids or carbonate-rich melts. (a) Geochim.Cosmochim.Acta (GCA) 59, 2859; Euro.J.Mineral 8, 317; GCA 61, 1658.(b) GCA 62, 3307.(c) Amer.Mineral. 90, 857.(d) GCA 66, 2299; GCA 68, 4145.(e) GCA 66, 625.(f) J.Metamorph.Geol. 21, 425.

Application of carbon and hydrogen stable isotope analyses to detect exogenous citric acid in Japanese apricot liqueur.

PubMed

Akamatsu, Fumikazu; Oe, Takaaki; Hashiguchi, Tomokazu; Hisatsune, Yuri; Kawao, Takafumi; Fujii, Tsutomu

2017-08-01

Japanese apricot liqueur manufacturers are required to control the quality and authenticity of their liqueur products. Citric acid made from corn is the main acidulant used in commercial liqueurs. In this study, we conducted spiking experiments and carbon and hydrogen stable isotope analyses to detect exogenous citric acid used as an acidulant in Japanese apricot liqueurs. Our results showed that the δ 13 C values detected exogenous citric acid originating from C 4 plants but not from C 3 plants. The δ 2 H values of citric acid decreased as the amount of citric acid added increased, whether the citric acid originated from C 3 or C 4 plants. Commercial liqueurs with declared added acidulant provided higher δ 13 C values and lower δ 2 H values than did authentic liqueurs and commercial liqueurs with no declared added acidulant. Carbon and hydrogen stable isotope analyses are suitable as routine methods for detecting exogenous citric acid in Japanese apricot liqueur. Copyright © 2017 Elsevier Ltd. All rights reserved.

Stable isotope probing to study functional components of complex microbial ecosystems.

PubMed

Mazard, Sophie; Schäfer, Hendrik

2014-01-01

This protocol presents a method of dissecting the DNA or RNA of key organisms involved in a specific biochemical process within a complex ecosystem. Stable isotope probing (SIP) allows the labelling and separation of nucleic acids from community members that are involved in important biochemical transformations, yet are often not the most numerically abundant members of a community. This pure culture-independent technique circumvents limitations of traditional microbial isolation techniques or data mining from large-scale whole-community metagenomic studies to tease out the identities and genomic repertoires of microorganisms participating in biological nutrient cycles. SIP experiments can be applied to virtually any ecosystem and biochemical pathway under investigation provided a suitable stable isotope substrate is available. This versatile methodology allows a wide range of analyses to be performed, from fatty-acid analyses, community structure and ecology studies, and targeted metagenomics involving nucleic acid sequencing. SIP experiments provide an effective alternative to large-scale whole-community metagenomic studies by specifically targeting the organisms or biochemical transformations of interest, thereby reducing the sequencing effort and time-consuming bioinformatics analyses of large datasets.

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

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

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

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.

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.

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

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Messenger, S.

2009-01-01

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

Pico-CSIA: Picomolar Scale Compound-Specific Isotope Analyses

NASA Astrophysics Data System (ADS)

Baczynski, A. A.; Polissar, P. J.; Juchelka, D.; Schwieters, J. B.; Hilkert, A.; Freeman, K. H.

2016-12-01

The basic approach to analyzing molecular isotopes has remained largely unchanged since the late 1990s. Conventional compound-specific isotope analyses (CSIA) are conducted using capillary gas chromatography (GC), a combustion interface, and an isotope-ratio mass spectrometer (IRMS). Commercially available GC-IRMS systems are comprised of components with inner diameters ≥0.25 mm and employ helium flow rates of 1-4 mL/min. These flow rates are an order of magnitude larger than what the IRMS can accept. Consequently, ≥90% of the sample is lost through the open split, and 1-10s of nanomoles of carbon are required for analysis. These sample requirements are prohibitive for many biomarkers, which are often present in picomolar concentrations. We utilize the resolving power and low flows of narrow-bore capillary GC to improve the sensitivity of CSIA. Narrow bore capillary columns (<0.25 mm ID) allow low helium flow rates of ≤0.5mL/min for more efficient sample transfer to the ion source of the IRMS while maintaining the high linear flow rates necessary to preserve narrow peak widths ( 250 ms). The IRMS has been fitted with collector amplifiers configured to 25 ms response times for rapid data acquisition across narrow peaks. Previous authors (e.g., Sacks et al., 2007) successfully demonstrated improved sensitivity afforded by narrow-bore GC columns. They reported an accuracy and precision of 1.4‰ for peaks with an average width at half maximum of 720 ms for 100 picomoles of carbon on column. Our method builds on their advances and further reduces peak widths ( 600 ms) and the amount of sample lost prior to isotopic analysis. Preliminary experiments with 100 picomoles of carbon on column show an accuracy and standard deviation <1‰. With further improvement, we hope to demonstrate robust isotopic analysis of 10s of picomoles of carbon, more than 2 orders of magnitude lower than commercial systems. The pico-CSIA method affords high-precision isotopic analyses for picomoles of carbon in organic biomarkers, which significantly lowers sample size requirements and broadens analytical windows in paleoclimate, astrobiological, and biogeochemical research.

Investigation of the quasi-simultaneous arrival (QSA) effect on a CAMECA IMS 7f-GEO.

PubMed

Jones, Clive; Fike, David A; Peres, Paula

2017-04-15

IMS 7f-GEO isotope ratio applications increasingly involve analyses (e.g., S - or O - isotopes, coupled with primary ion currents <30 pA) for which quasi-simultaneous arrival (QSA) could compromise precision and accuracy of data. QSA and associated correction have been widely investigated for the CAMECA NanoSIMS instruments, but not for the IMS series. Sulfur and oxygen isotopic ratio experiments were performed using an electron multiplier (EM) detector, employing Cs + primary ion currents of 1, 2, 5 and 11.5 pA (nominal) and a variety of secondary ion transmissions to vary QSA probability. An experiment to distinguish between QSA undercounting and purported aperture-related mass fractionation was performed using an EM for 16 O - and 18 O - plus an additional 16 O - measurement using a Faraday cup (FC) detector. An experiment to investigate the accuracy of the QSA correction was performed by comparing S isotopic ratios obtained using an EM with those obtained on the same sample using dual FCs. The QSA effect was observed on the IMS-7f-GEO, and QSA coefficients (β) of ~0.66 were determined, in agreement with reported NanoSIMS measurements, but different from the value (0.5) predicted using Poisson statistics. Aperture-related fractionation was not sufficient to explain the difference but uncertainties in primary ion flux measurement could play a role. When QSA corrected, the isotope ratio data obtained using the EM agreed with the dual FC data, within statistical error. QSA undercounting could compromise isotope ratio analyses requiring ~1 × 10 5 counts per second for the major isotope and primary currents <20 pA. The error could be >8‰ for a 1 pA primary current. However, correction can be accurately applied. For instrumental mass fractionation (IMF)-corrected data, the magnitude of the error resulting from not correcting for QSA is dependent on the difference in secondary ion count rate between the unknown and standard analyses. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Zinc isotope ratio imaging of rat brain thin sections from stable isotope tracer studies by LA-MC-ICP-MS.

PubMed

Urgast, Dagmar S; Hill, Sarah; Kwun, In-Sook; Beattie, John H; Goenaga-Infante, Heidi; Feldmann, Jörg

2012-10-01

Zinc stable isotope tracers (⁶⁷Zn and ⁷⁰Zn) were injected into rats at two different time points to investigate the feasibility of using tracers to study zinc kinetics at the microscale within distinct tissue features. Laser ablation coupled to multi-collector ICP-MS was used to analyse average isotope ratios in liver thin sections and to generate bio-images showing zinc isotope ratio distribution in brain thin sections. Average isotope ratios of all samples from treated animals were found to be statistically different (P < 0.05) from samples from untreated control animals. Furthermore, differing isotope ratios in physiological features of the brain, namely hippocampus, amygdala, cortex and hypothalamus, were identified. This indicates that these regions differ in their zinc metabolism kinetics. While cortex and hypothalamus contain more tracer two days after injection than 14 days after injection, the opposite is true for hippocampus and amygdala. This study showed that stable isotope tracer experiments can be combined with laser ablation MC-ICP-MS to measure trace element kinetics in tissues at a microscale level.

A program for mass spectrometer control and data processing analyses in isotope geology; written in BASIC for an 8K Nova 1120 computer

USGS Publications Warehouse

Stacey, J.S.; Hope, J.

1975-01-01

A system is described which uses a minicomputer to control a surface ionization mass spectrometer in the peak switching mode, with the object of computing isotopic abundance ratios of elements of geologic interest. The program uses the BASIC language and is sufficiently flexible to be used for multiblock analyses of any spectrum containing from two to five peaks. In the case of strontium analyses, ratios are corrected for rubidium content and normalized for mass spectrometer fractionation. Although almost any minicomputer would be suitable, the model used was the Data General Nova 1210 with 8K memory. Assembly language driver program and interface hardware-descriptions for the Nova 1210 are included.

Fukushima Daiichi reactor source term attribution using cesium isotope ratios from contaminated environmental samples

DOE PAGES

Snow, Mathew S.; Snyder, Darin C.; Delmore, James E.

2016-01-18

Source term attribution of environmental contamination following the Fukushima Daiichi Nuclear Power Plant (FDNPP) disaster is complicated by a large number of possible similar emission source terms (e.g. FDNPP reactor cores 1–3 and spent fuel ponds 1–4). Cesium isotopic analyses can be utilized to discriminate between environmental contamination from different FDNPP source terms and, if samples are sufficiently temporally resolved, potentially provide insights into the extent of reactor core damage at a given time. Rice, soil, mushroom, and soybean samples taken 100–250 km from the FDNPP site were dissolved using microwave digestion. Radiocesium was extracted and purified using two sequentialmore » ammonium molybdophosphate-polyacrylonitrile columns, following which 135Cs/ 137Cs isotope ratios were measured using thermal ionization mass spectrometry (TIMS). Results were compared with data reported previously from locations to the northwest of FDNPP and 30 km to the south of FDNPP. 135Cs/ 137Cs isotope ratios from samples 100–250 km to the southwest of the FDNPP site show a consistent value of 0.376 ± 0.008. 135Cs/ 137Cs versus 134Cs/ 137Cs correlation plots suggest that radiocesium to the southwest is derived from a mixture of FDNPP reactor cores 1, 2, and 3. Conclusions from the cesium isotopic data are in agreement with those derived independently based upon the event chronology combined with meteorological conditions at the time of the disaster. In conclusion, cesium isotopic analyses provide a powerful tool for source term discrimination of environmental radiocesium contamination at the FDNPP site. For higher precision source term attribution and forensic determination of the FDNPP core conditions based upon cesium, analyses of a larger number of samples from locations to the north and south of the FDNPP site (particularly time-resolved air filter samples) are needed. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.« less

Isotopic and elemental chemistry of sedimentary pyrite: A combined analytical and statistical approach to a novel planetary biosignature

NASA Astrophysics Data System (ADS)

Figueroa, M. C.; Gregory, D. D.; Lyons, T. W.; Williford, K. H.

2017-12-01

Life processes affect trace element abundances in pyrite such that sedimentary and hydrothermal pyrite have significantly different trace element signatures. Thus, we propose that these biogeochemical data could be used to identify pyrite that formed biogenetically either early in our planet's history or on other planets, particularly Mars. The potential for this approach is elevated because pyrite is common in diverse sedimentary settings, and its trace element content can be preserved despite secondary overprints up to greenschist facies, thus minimizing the concerns about remobilization that can plague traditional whole rock studies. We are also including in-situ sulfur isotope analysis to further refine our understanding of the complex signatures of ancient pyrite. Sulfur isotope data can point straightforwardly to the involvement of life, because pyrite in sediments is inextricably linked to bacterial sulfate reduction and its diagnostic isotopic expressions. In addition to analyzing pyrite of known biological origin formed in the modern and ancient oceans under a range of conditions, we are building a data set for pyrite formed by hydrothermal and metamorphic processes to minimize the risk of false positives in life detection. We have used Random Forests (RF), a machine learning statistical technique with proven efficiency for classifying large geological datasets, to classify pyrite into biotic and abiotic end members. Coupling the trace element and sulfur isotope data from our analyses with a large existing dataset from diverse settings has yielded 4500 analyses with 18 different variables. Our initial results reveal the promise of the RF approach, correctly identifying biogenic pyrite 97 percent of the time. We will continue to couple new in-situ S-isotope and trace element analyses of biogenic pyrite grains from modern and ancient environments, using cutting-edge microanalytical techniques, with new data from high temperature settings. Our ultimately goal is a refined search tool with straightforward application in the search for early life on Earth and distant life recorded in meteorites, returned samples, and in situ measurements.

Fukushima Daiichi reactor source term attribution using cesium isotope ratios from contaminated environmental samples

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

Snow, Mathew S.; Snyder, Darin C.; Delmore, James E.

Source term attribution of environmental contamination following the Fukushima Daiichi Nuclear Power Plant (FDNPP) disaster is complicated by a large number of possible similar emission source terms (e.g. FDNPP reactor cores 1–3 and spent fuel ponds 1–4). Cesium isotopic analyses can be utilized to discriminate between environmental contamination from different FDNPP source terms and, if samples are sufficiently temporally resolved, potentially provide insights into the extent of reactor core damage at a given time. Rice, soil, mushroom, and soybean samples taken 100–250 km from the FDNPP site were dissolved using microwave digestion. Radiocesium was extracted and purified using two sequentialmore » ammonium molybdophosphate-polyacrylonitrile columns, following which 135Cs/ 137Cs isotope ratios were measured using thermal ionization mass spectrometry (TIMS). Results were compared with data reported previously from locations to the northwest of FDNPP and 30 km to the south of FDNPP. 135Cs/ 137Cs isotope ratios from samples 100–250 km to the southwest of the FDNPP site show a consistent value of 0.376 ± 0.008. 135Cs/ 137Cs versus 134Cs/ 137Cs correlation plots suggest that radiocesium to the southwest is derived from a mixture of FDNPP reactor cores 1, 2, and 3. Conclusions from the cesium isotopic data are in agreement with those derived independently based upon the event chronology combined with meteorological conditions at the time of the disaster. In conclusion, cesium isotopic analyses provide a powerful tool for source term discrimination of environmental radiocesium contamination at the FDNPP site. For higher precision source term attribution and forensic determination of the FDNPP core conditions based upon cesium, analyses of a larger number of samples from locations to the north and south of the FDNPP site (particularly time-resolved air filter samples) are needed. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.« less