Rapid ultra-trace analysis of sucralose in multiple-origin aqueous samples by online solid-phase extraction coupled to high-resolution mass spectrometry.

PubMed

Batchu, Sudha Rani; Ramirez, Cesar E; Gardinali, Piero R

2015-05-01

Because of its widespread consumption and its persistence during wastewater treatment, the artificial sweetener sucralose has gained considerable interest as a proxy to detect wastewater intrusion into usable water resources. The molecular resilience of this compound dictates that coastal and oceanic waters are the final recipient of this compound with unknown effects on ecosystems. Furthermore, no suitable methodologies have been reported for routine, ultra-trace detection of sucralose in seawater as the sensitivity of traditional liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis is limited by a low yield of product ions upon collision-induced dissociation (CID). In this work, we report the development and field test of an alternative analysis tool for sucralose in environmental waters, with enough sensitivity for the proper quantitation and confirmation of this analyte in seawater. The methodology is based on automated online solid-phase extraction (SPE) and high-resolving-power orbitrap MS detection. Operating in full scan (no CID), detection of the unique isotopic pattern (100:96:31 for [M-H](-), [M-H+2](-), and [M-H+4](-), respectively) was used for ultra-trace quantitation and analyte identification. The method offers fast analysis (14 min per run) and low sample consumption (10 mL per sample) with method detection and confirmation limits (MDLs and MCLs) of 1.4 and 5.7 ng/L in seawater, respectively. The methodology involves low operating costs due to virtually no sample preparation steps or consumables. As an application example, samples were collected from 17 oceanic and estuarine sites in Broward County, FL, with varying salinity (6-40 PSU). Samples included the ocean outfall of the Southern Regional Wastewater Treatment Plant (WWTP) that serves Hollywood, FL. Sucralose was detected above MCL in 78% of the samples at concentrations ranging from 8 to 148 ng/L, with the exception of the WWTP ocean outfall (at pipe end, 28 m below the surface) where the measured concentration was 8418 ± 3813 ng/L. These results demonstrate the applicability of this monitoring tool for the trace-level detection of this wastewater marker in very dilute environmental waters.

Biological forcing controls the chemistry of the coral exoskeleton

NASA Astrophysics Data System (ADS)

Meibom, A.; Mostefaoui, S.; Cuif, J.; Yurimoto, H.; Dauphin, Y.; Houlbreque, F.; Dunbar, R.; Constantz, B.

2006-12-01

A multitude of marine organisms produce calcium carbonate skeletons that are used extensively to reconstruct water temperature variability of the tropical and subtropical oceans - a key parameter in global climate-change models. Such paleo-climate reconstructions are based on the notion that skeletal oxygen isotopic composition and certain trace-element abundances (e.g., Sr/Ca and Mg/Ca ratios) vary in response to changes in the water temperature. However, it is a fundamental problem that poorly understood biological processes introduce large compositional deviations from thermodynamic equilibrium and hinder precise calibrations of many paleo-climate proxies. Indeed, the role of water temperature in controlling the composition of the skeleton is far from understood. We have studied trace-element abundances as well as oxygen and carbon isotopic compositions of individual skeletal components in the zooxanthellate and non-zooxanthellate corals at ultra-structural, i.e. micrometer to sub-micrometer length scales. From this body of work we draw the following, generalized conclusions: 1) Centers of calcification (COC) are not in equilibrium with seawater. Notably, the Sr/Ca ratio is higher than expected for aragonite equilibrium with seawater at the temperature at which the skeleton was formed. Furthermore, the COC are further away from equilibrium with seawater than fibrous skeleton in terms of stable isotope composition. 2) COC are dramatically different from the fibrous aragonite skeleton in terms of trace element composition. 3) Neither trace element nor stable isotope variations in the fibrous (bulk) part of the skeleton are directly related to changes in SST. In fact, changes in SST can have very little to do with the observed compositional variations. 4) Trace element variations in the fibrous (bulk) part of the skeleton are not related to the activity of zooxanthellae. These observations are directly relevant to the issue of biological versus non-biological control over skeleton composition and will be discussed.

Detection of the actinides and cesium from environmental samples

NASA Astrophysics Data System (ADS)

Snow, Mathew Spencer

Detection of the actinides and cesium in the environment is important for a variety of applications ranging from environmental remediation to safeguards and nuclear forensics. The utilization of multiple different elemental concentrations and isotopic ratios together can significantly improve the ability to attribute contamination to a unique source term and/or generation process; however, the utilization of multiple elemental "signatures" together from environmental samples requires knowledge of the impact of chemical fractionation for various elements under a variety of environmental conditions (including predominantly aqueous versus arid conditions). The research reported in this dissertation focuses on three major areas: 1. Improving the understanding of actinide-mineral interactions at ultra-low concentrations. Chapter 2 reports a batch sorption and modeling study of Np(V) sorption to the mineral goethite from attomolar to micromolar concentrations. 2. Improving the detection capabilities for Thermal Ionization Mass Spectrometry (TIMS) analyses of ultra-trace cesium from environmental samples. Chapter 4 reports a new method which significantly improves the chemical yields, purification, sample processing time, and ultimately, the detection limits for TIMS analyses of femtogram quantities of cesium from a variety of environmental sample matrices. 3. Demonstrating how actinide and cesium concentrations and isotopic ratios from environmental samples can be utilized together to determine a wealth of information including environmental transport mechanisms (e.g. aqueous versus arid transport) and information on the processes which generated the original material. Chapters1, 3 and 5 demonstrate these principles using Pu, Am, Np, and Cs concentrations and isotopic ratios from contaminated soils taken near the Subsurface Disposal Area (SDA) of Idaho National Laboratory (INL) (a low level radioactive waste disposal site in southeastern Idaho).

Trace element and stable isotope analysis of fourteen species of marine invertebrates from the Bay of Fundy, Canada.

PubMed

English, Matthew D; Robertson, Gregory J; Mallory, Mark L

2015-12-15

The Bay of Fundy, Canada, is a macrotidal bay with a highly productive intertidal zone, hosting a large abundance and diversity of marine invertebrates. We analysed trace element concentrations and stable isotopic values of δ(15)N and δ(13)C in 14 species of benthic marine invertebrates from the Bay of Fundy's intertidal zone to investigate bioaccumulation or biodilution of trace elements in the lower level of this marine food web. Barnacles (Balanus balanus) consistently had significantly greater concentrations of trace elements compared to the other species studied, but otherwise we found low concentrations of non-essential trace elements. In the range of trophic levels that we studied, we found limited evidence of bioaccumulation or biodilution of trace elements across species, likely due to the species examined occupying similar trophic levels in different food chains. Copyright © 2015 Elsevier Ltd. All rights reserved.

Trace Elements and Carbon and Nitrogen Stable Isotopes in Organisms from a Tropical Coastal Lagoon

PubMed Central

van Hattum, B.; de Boer, J.; van Bodegom, P. M.; Rezende, C. E.; Salomons, W.

2010-01-01

Trace elements (Fe, Mn, Al, Zn, Cr, Cu, Ni, Pb, Cd, Hg, and As) and stable isotope ratios (δ13C and δ15N) were analyzed in sediments, invertebrates, and fishes from a tropical coastal lagoon influenced by iron ore mining and processing activities to assess the differences in trace element accumulation patterns among species and to investigate relations with trophic levels of the organisms involved. Overall significant negative relations between trophic level (given by 15N) and trace element concentrations in gastropods and crustaceans showed differences in internal controls of trace element accumulation among the species of different trophic positions, leading to trace element dilution. Generally, no significant relation between δ15N and trace element concentrations was observed among fish species, probably due to omnivory in a number of species as well as fast growth. Trace element accumulation was observed in the fish tissues, with higher levels of most trace elements found in liver compared with muscle and gill. Levels of Fe, Mn, Al, and Hg in invertebrates, and Fe and Cu in fish livers, were comparable with levels in organisms and tissues from other contaminated areas. Trace element levels in fish muscle were below the international safety baseline standards for human consumption. PMID:20217062

Trace elements and carbon and nitrogen stable isotopes in organisms from a tropical coastal lagoon.

PubMed

Pereira, A A; van Hattum, B; de Boer, J; van Bodegom, P M; Rezende, C E; Salomons, W

2010-10-01

Trace elements (Fe, Mn, Al, Zn, Cr, Cu, Ni, Pb, Cd, Hg, and As) and stable isotope ratios (delta(13)C and delta(15)N) were analyzed in sediments, invertebrates, and fishes from a tropical coastal lagoon influenced by iron ore mining and processing activities to assess the differences in trace element accumulation patterns among species and to investigate relations with trophic levels of the organisms involved. Overall significant negative relations between trophic level (given by (15)N) and trace element concentrations in gastropods and crustaceans showed differences in internal controls of trace element accumulation among the species of different trophic positions, leading to trace element dilution. Generally, no significant relation between delta(15)N and trace element concentrations was observed among fish species, probably due to omnivory in a number of species as well as fast growth. Trace element accumulation was observed in the fish tissues, with higher levels of most trace elements found in liver compared with muscle and gill. Levels of Fe, Mn, Al, and Hg in invertebrates, and Fe and Cu in fish livers, were comparable with levels in organisms and tissues from other contaminated areas. Trace element levels in fish muscle were below the international safety baseline standards for human consumption.

Parent Body Influences on Amino Acids in the Tagish Lake Meteorite

NASA Technical Reports Server (NTRS)

Glavin, D. P.; Callahan, M. P.; Dworkin, J. P.; Elsila, J. E.; Herd, C. D. K.

2010-01-01

The Tagish Lake meteorite is a primitive C2 carbonaceous chondrite with a mineralogy, oxygen isotope, and bulk chemical. However, in contrast to many CI and CM carbonaceous chondrites, the Tagish Lake meteorite was reported to have only trace levels of indigenous amino acids, with evidence for terrestrial L-amino acid contamination from the Tagish Lake meltwater. The lack of indigenous amino acids in Tagish Lake suggested that they were either destroyed during parent body alteration processes and/or the Tagish Lake meteorite originated on a chemically distinct parent body from CI and CM meteorites where formation of amino acids was less favorable. We recently measured the amino acid composition of three different lithologies (11h, 5b, and 11i) of pristine Tagish Lake meteorite fragments that represent a range of progressive aqueous alteration in order 11h < 5b < 11i as inferred from the mineralogy, petrology, bulk isotopes, and insoluble organic matter structure. The distribution and enantiomeric abundances of the one- to six-carbon aliphatic amino acids found in hot-water extracts of the Tagish Lake fragments were determined by ultra performance liquid chromatography fluorescence detection and time of flight mass spectrometry coupled with OPA/NAC derivatization. Stable carbon isotope analyses of the most abundant amino acids in 11h were measured with gas chromatography coupled with quadrupole mass spectrometry and isotope ratio mass spectrometry.

Ar39 Detection at the 10-16 Isotopic Abundance Level with Atom Trap Trace Analysis

NASA Astrophysics Data System (ADS)

Jiang, W.; Williams, W.; Bailey, K.; Davis, A. M.; Hu, S.-M.; Lu, Z.-T.; O'Connor, T. P.; Purtschert, R.; Sturchio, N. C.; Sun, Y. R.; Mueller, P.

2011-03-01

Atom trap trace analysis, a laser-based atom counting method, has been applied to analyze atmospheric Ar39 (half-life=269yr), a cosmogenic isotope with an isotopic abundance of 8×10-16. In addition to the superior selectivity demonstrated in this work, the counting rate and efficiency of atom trap trace analysis have been improved by 2 orders of magnitude over prior results. The significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors.

Simultaneous measurement of tritium and radiocarbon by ultra-low-background proportional counting

DOE PAGES

Mace, Emily; Aalseth, Craig; Alexander, Tom; ...

2016-12-21

Use of ultra-low-background capabilities at Pacific Northwest National Laboratory provide enhanced sensitivity for measurement of low-activity sources of tritium and radiocarbon using proportional counters. Tritium levels are nearly back to pre-nuclear test backgrounds (~2-8 TU in rainwater), which can complicate their dual measurement with radiocarbon due to overlap in the beta decay spectra. In this paper, we present results of single-isotope proportional counter measurements used to analyze a dual-isotope methane sample synthesized from ~120 mg of H 2O and present sensitivity results.

Development of new method of δ13C measurement for trace hydrocarbons in natural gas using solid phase micro-extraction coupled to gas chromatography isotope ratio mass spectrometry.

PubMed

Li, Zhongping; Wang, Xibin; Li, Liwu; Zhang, Mingjie; Tao, Mingxin; Xing, Lantian; Cao, Chunhui; Xia, Yanqing

2014-11-01

Compound specific isotope analysis (CSIA) of normal-level hydrocarbons (C 1 -C 4 ) in natural gas is often successfully used in natural gas origin identification and classification, but little progress so far has been made for trace level hydrocarbons (C 5 -C 14 ) in natural gas. In this study, we developed a method for rapid analysis of carbon isotopic ratios for trace hydrocarbons in natural gas samples. This method can be described as a combined approach characterized by solid phase micro-extraction (SPME) technique coupled to gas chromatography isotope ratio mass spectrometry (GC/IRMS). In this study, the CAR-PDMS fiber was chosen as the SPME adsorptive material after comparative experiments with other four fibers, and the parameters, including equilibration time, extraction temperature and desorption time, for efficient extraction of trace hydrocarbons were systematically optimized. The results showed the carbon isotopic fractionation was not observed as a function of equilibration time and extraction temperature. And the δ 13 C signatures determined by SPME-GC/IRMS were in good agreement with the known δ 13 C values of C 5 -C 14 measured by GC-IRMS, and the accuracy is generally within ±0.5‰. Five natural gas samples were analyzed using this method, and the δ 13 C values for C 5 -C 14 components were obtained with satisfied repeatability. The SPME-GC/IRMS approach fitted with CAR-PDMS fiber is well suited for the preconcentration of trace hydrocarbons and provides so far the most reliable carbon isotopic analysis for trace compounds in natural gas. Published by Elsevier B.V.

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

First results of a simultaneous measurement of tritium and 14C in an ultra-low-background proportional counter for environmental sources of methane

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

Mace, Emily K.; Aalseth, Craig E.; Day, Anthony R.

Abstract Simultaneous measurement of tritium and 14C would provide an added tool for tracing organic compounds through environmental systems and is possible via beta energy spectroscopy of sample-derived methane in internal-source gas proportional counters. Since the mid-1960’s atmospheric tritium and 14C have fallen dramatically as the isotopic injections from above-ground nuclear testing have been diluted into the ocean and biosphere. In this work, the feasibility of simultaneous tritium and 14C measurements via proportional counters is revisited in light of significant changes in both the atmospheric and biosphere isotopics and the development of new ultra-low-background gas proportional counting capabilities for smallmore » samples (roughly 50 cc methane). A Geant4 Monte Carlo model of a Pacific Northwest National Laboratory (PNNL) proportional counter response to tritium and 14C is used to analyze small samples of two different methane sources to illustrate the range of applicability of contemporary simultaneous measurements and their limitations. Because the two methane sources examined were not sample size limited, we could compare the small-sample measurements performed at PNNL with analysis of larger samples performed at a commercial laboratory. The dual-isotope simultaneous measurement is well matched for methane samples that are atmospheric or have an elevated source of tritium (i.e. landfill gas). For samples with low/modern tritium isotopics (rainwater), commercial separation and counting is a better fit.« less

Simultaneous measurement of tritium and radiocarbon by ultra-low-background proportional counting.

PubMed

Mace, Emily; Aalseth, Craig; Alexander, Tom; Back, Henning; Day, Anthony; Hoppe, Eric; Keillor, Martin; Moran, Jim; Overman, Cory; Panisko, Mark; Seifert, Allen

2017-08-01

Use of ultra-low-background capabilities at Pacific Northwest National Laboratory provide enhanced sensitivity for measurement of low-activity sources of tritium and radiocarbon using proportional counters. Tritium levels are nearly back to pre-nuclear test backgrounds (~2-8 TU in rainwater), which can complicate their dual measurement with radiocarbon due to overlap in the beta decay spectra. We present results of single-isotope proportional counter measurements used to analyze a dual-isotope methane sample synthesized from ~120mg of H 2 O and present sensitivity results. Copyright © 2017 Elsevier Ltd. All rights reserved.

Uranium beam characterization at CIRCE for background and contamination determinations.

PubMed

De Cesare, M; De Cesare, N; D'Onofrio, A; Fifield, L K; Gialanella, L; Terrasi, F

2015-09-01

The Accelerator Mass Spectrometry (AMS) is the most sensitive technique, compared either to the Inductively Coupled Plasma (ICP-MS) or Thermal Ionization (TI-MS) mass spectrometer, for the actinide (e.g. (236)U, (x)Pu isotopes) measurements. They are present in environmental samples at the ultra trace level since atmospheric tests of Nuclear Weapons (NWs) performed in the past, deliberate dumping of nuclear waste, nuclear fuel reprocessing, on a large scale, and operation of Nuclear Power Plants (NPPs), on a small scale, have led to the release of a wide range of radioactive nuclides in the environment. At the Center for Isotopic Research on Cultural and Environmental heritage (CIRCE) in Caserta, Italy, an upgraded actinide AMS system, based on a 3-MV pelletron tandem accelerator, has been developed and routinely operated. At CIRCE a charge state distribution as a function of terminal voltage, the beam emittance, measured in the 20° actinides dedicated beam line, as well as the energy and position validation of the U ions were performed in order to determine the best measurement conditions. A (236)U/(238)U isotopic ratio background level of about 5×10(-12) or 3×10(-13), depending on the Time of Flight-Energy (TOF-E) configurations, as well as the spatial distribution of the (235)U, (238)U interferences ions and a (236)U contamination mass of about 0.5 fg have been determined. Copyright © 2015 Elsevier Ltd. All rights reserved.

A METHOD TO IMPROVE DOSE ASSESSMENT BY RECONSTRUCTION OF THE COMPLETE ISOTOPES INVENTORY.

PubMed

Bonin, Alice; Tsilanizara, Aimé

2017-06-01

Radiation shielding assessments may underestimate the expected dose if some isotopes at trace level are not considered in the isotopes inventory of the shielded radioactive materials. Indeed, information about traces is not often available. Nevertheless, the activation of some minor isotopic traces may significantly contribute to the dose build-up. This paper presents a new method (Isotopes Inventory Reconstruction-IIR) estimating the concentration of the minor isotopes in the irradiated material at the beginning of the cooling period. The method requires the solution of the inverse problem describing the irradiated material's decay. In a mixture of an irradiated uranium-plutonium oxide shielded by a set-up made of stainless-steel, porous polyethylene plaster and lead methyl methacrylate, the comparison between different methods proves that the IIR-method allows better assessment of the dose than other approximate methods. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Determination of ultra-low level plutonium isotopes (239Pu, 240Pu) in environmental samples with high uranium.

PubMed

Xing, Shan; Zhang, Weichao; Qiao, Jixin; Hou, Xiaolin

2018-09-01

In order to measure trace plutonium and its isotopes ratio ( 240 Pu/ 239 Pu) in environmental samples with a high uranium, an analytical method was developed using radiochemical separation for separation of plutonium from matrix and interfering elements including most of uranium and ICP-MS for measurement of plutonium isotopes. A novel measurement method was established for extensively removing the isobaric interference from uranium ( 238 U 1 H and 238 UH 2 + ) and tailing of 238 U, but significantly improving the measurement sensitivity of plutonium isotopes by employing NH 3 /He as collision/reaction cell gases and MS/MS system in the triple quadrupole ICP-MS instrument. The results show that removal efficiency of uranium interference was improved by more than 15 times, and the sensitivity of plutonium isotopes was increased by a factor of more than 3 compared to the conventional ICP-MS. The mechanism on the effective suppress of 238 U interference for 239 Pu measurement using NH 3 -He reaction gases was explored to be the formation of UNH + and UNH 2 + in the reactions of UH + and U + with NH 3 , while no reaction between NH 3 and Pu + . The detection limits of this method were estimated to be 0.55 fg mL -1 for 239 Pu, 0.09 fg mL -1 for 240 Pu. The analytical precision and accuracy of the method for Pu isotopes concentration and 240 Pu/ 239 Pu atomic ratio were evaluated by analysis of sediment reference materials (IAEA-385 and IAEA-412) with different levels of plutonium and uranium. The developed method were successfully applied to determine 239 Pu and 240 Pu concentrations and 240 Pu/ 239 Pu atomic ratios in soil samples collected in coastal areas of eastern China. Copyright © 2018 Elsevier B.V. All rights reserved.

Comparison between lead levels in dandelions grown in an ultra-clean lab environment (baseline) and those collected from the San Francisco Bay Area

NASA Astrophysics Data System (ADS)

Rojero, J.; Odigie, K. O.; Hibdon, S.; Flegal, A. R.

2011-12-01

This study is aimed at establishing the baseline (natural) levels of lead in dandelions (Taraxacum officinale) grown in an ultra-clean environment. Dandelions have been used extensively as biomonitors of environmental lead levels since their distribution is global and they can be easily collected. However, industrial lead contamination is so pervasive that even dandelions from the most remote areas in the world may be contaminated with industrial lead. Therefore, this work will test the hypothesis that "natural" lead levels in dandelions are lower than any previously published values - by growing them in a HEPA filtered air (Class 100) trace metal clean room with high purity (18 MΩ cm) water. Concentrations and isotopic compositions of lead in the clean-room grown dandelions will be compared to values in literature and to those of lead in dandelions collected from San Francisco Bay Area. Lead is a dense, ductile, and highly malleable metal that is found naturally in our environment. Due to its properties it is currently highly used in building construction, in ceramic glazes, lead chromate and in PVC plastic used to coat electrical cords. The uses of lead have included paint, leather tanning, and being used as an additive to gasoline prior to the mid 1970's, as well as others. Due to its many uses, humans are susceptible to lead regularly through various means of exposure from air, water and soil, often leading to lead toxicity.

Chemical sensing thresholds for mine detection dogs

NASA Astrophysics Data System (ADS)

Phelan, James M.; Barnett, James L.

2002-08-01

Mine detection dogs have been found to be an effective method to locate buried landmines. The capabilities of the canine olfaction method are from a complex combination of training and inherent capacity of the dog for odor detection. The purpose of this effort was to explore the detection thresholds of a limited group of dogs that were trained specifically for landmine detection. Soils were contaminated with TNT and 2,4-DNT to develop chemical vapor standards to present to the dogs. Soils contained ultra trace levels of TNT and DNT, which produce extremely low vapor levels. Three groups of dogs were presented the headspace vapors from the contaminated soils in work environments for each dog group. One positive sample was placed among several that contained clean soils and, the location and vapor source (strength, type) was frequently changed. The detection thresholds for the dogs were determined from measured and extrapolated dilution of soil chemical residues and, estimated soil vapor values using phase partitioning relationships. The results showed significant variances in dog sensing thresholds, where some dogs could sense the lowest levels and others had trouble with even the highest source. The remarkable ultra-trace levels detectable by the dogs are consistent with the ultra-trace chemical residues derived from buried landmines; however, poor performance may go unnoticed without periodic challenge tests at levels consistent with performance requirements.

Surface Cleaning Techniques: Ultra-Trace ICP-MS Sample Preparation and Assay of HDPE

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

Overman, Nicole R.; Hoppe, Eric W.; Addleman, Raymond S.

2013-06-01

The world’s most sensitive radiation detection and assay systems depend upon ultra-low background (ULB) materials to reduce unwanted radiological backgrounds. Herein, we evaluate methods to clean HDPE, a material of interest to ULB systems and the means to provide rapid assay of surface and bulk contamination. ULB level material and ultra-trace level detection of actinide elements is difficult to attain, due to the introduction of contamination from sample preparation equipment such as pipette tips, sample vials, forceps, etc. and airborne particulate. To date, literature available on the cleaning of such polymeric materials and equipment for ULB applications and ultra-trace analysesmore » is limited. For these reasons, a study has been performed to identify an effective way to remove surface contamination from polymers in an effort to provide improved instrumental detection limits. Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) was utilized to assess the effectiveness of a variety of leachate solutions for removal of inorganic uranium and thorium surface contamination from polymers, specifically high density polyethylene (HDPE). HDPE leaching procedures were tested to optimize contaminant removal of thorium and uranium. Calibration curves for thorium and uranium ranged from 15 ppq (fg/mL) to 1 ppt (pg/mL). Detection limits were calculated at 6 ppq for uranium and 7 ppq for thorium. Results showed the most effective leaching reagent to be clean 6 M nitric acid for 72 hour exposures. Contamination levels for uranium and thorium found in the leachate solutions were significant for ultralow level radiation detection applications.« less

Recent developments on field gas extraction and sample preparation methods for radiokrypton dating of groundwater

NASA Astrophysics Data System (ADS)

Yokochi, Reika

2016-09-01

Current and foreseen population growths will lead to an increased demand in freshwater, large quantities of which is stored as groundwater. The ventilation age is crucial to the assessment of groundwater resources, complementing the hydrological model approach based on hydrogeological parameters. Ultra-trace radioactive isotopes of Kr (81 Kr and 85 Kr) possess the ideal physical and chemical properties for groundwater dating. The recent advent of atom trap trace analyses (ATTA) has enabled determination of ultra-trace noble gas radioisotope abundances using 5-10 μ L of pure Kr. Anticipated developments will enable ATTA to analyze radiokrypton isotope abundances at high sample throughput, which necessitates simple and efficient sample preparation techniques that are adaptable to various sample chemistries. Recent developments of field gas extraction devices and simple and rapid Kr separation method at the University of Chicago are presented herein. Two field gas extraction devices optimized for different sampling conditions were recently designed and constructed, aiming at operational simplicity and portability. A newly developed Kr purification system enriches Kr by flowing a sample gas through a moderately cooled (138 K) activated charcoal column, followed by a gentle fractionating desorption. This simple process uses a single adsorbent and separates 99% of the bulk atmospheric gases from Kr without significant loss. The subsequent two stages of gas chromatographic separation and a hot Ti sponge getter further purify the Kr-enriched gas. Abundant CH4 necessitates multiple passages through one of the gas chromatographic separation columns. The presented Kr separation system has a demonstrated capability of extracting Kr with > 90% yield and 99% purity within 75 min from 1.2 to 26.8 L STP of atmospheric air with various concentrations of CH4. The apparatuses have successfully been deployed for sampling in the field and purification of groundwater samples.

The new high-resolution IRMS MAT253 ULTRA at Utrecht University

NASA Astrophysics Data System (ADS)

Röckmann, Thomas; Hofmann, Magdalena; Paul, Dipayan; Popa, Elena; Adnew, Getachew

2017-04-01

In 2016, the new high-resolution, multi-collector isotope ratio mass spectrometer MAT253 ULTRA [1] was installed at Utrecht University. This instrument is designed to reach a mass resolving power of 20,000 to 40,000 (M/ΔM). The ion currents are detected with a variable multi-collector unit that allows to register up to 9 ion currents simultaneously with Faraday cups and ion counters. The width of the entrance slit can be varied between 5 and 250μm so that the instrument can be operated under low, medium and high mass resolution, and an optimum balance between resolution and sensitivity can be selected for the respective applications. The central field of application of the new IRMS at Utrecht University is the measurement of multiply substituted isotopologues (clumped isotopes) in atmospheric trace compounds (e.g. 13CDH3, 13C18O16O, 18O18O, 15N14N18O) [1-7]. It is known from thermodynamics that the zero point energy of a chemical bond usually decreases when multiple heavy isotopes clump together in a molecule, and this effect depends on temperature [7]. Therefore, the abundance of clumped isotopes can be used as temperature indicator under thermodynamical equilibrium conditions. However, in the atmosphere, many reactions are controlled kinetically. It has been shown recently for a few examples that negative clumping signatures (anti-clumping) can be produced under non-equilibrium conditions [3,4]. In addition, based on purely statistical reasons, anti-clumping signatures will be produced in any molecule that contains indistinguishable atoms, which originate from isotopically distinct reservoir [5,6]. Thus, the investigation of multiply substituted isotopologues is expected to generate novel isotope signatures that can complement conventional stable isotope analysis in atmospheric science. We will present data on the performance of the MAT 253 ULTRA instrument and first scientific applications to atmospheric research. 1. Eiler, J.M., et al., A high-resolution gas-source isotope ratio mass spectrometer, Int. J. Mass Spect., 2013. 335: 45- 56. 2. Young, E.D., et al., A large-radius high-mass-resolution multiple-collector isotope ratio mass spectrometer for analysis of rare isotopologues of O2, N2, CH4 and other gases, Int. J. Mass Spect., 2016. 401: 1-10. 3. Wang, D.T., et al., Nonequilibrium clumped isotope signals in microbial methane, Science, 2015. 348: 428-431. 4. Yeung, L.Y., et al., Biological signatures in clumped isotopes of O2, Science, 2015. 348: 431-434. 5. Yeung, L.Y., Combinatorial effects on clumped isotopes and their significance in biogeochemistry, Geochim. Cosmochim. Act., 2016: doi:10.1016/j.gca.2015.09.020. 6. Röckmann, T., et al., Statistical clumped isotope signatures Scientific reports, 2016. 6: 31947; doi: 10.1038/srep31947. 7. Wang, Z.G., et al., Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases, Geochim. Cosmochim. Act., 2004. 68: 4779-4797.

An automated multidimensional preparative gas chromatographic system for isolation and enrichment of trace amounts of xenon from ambient air.

PubMed

Larson, Tuula; Östman, Conny; Colmsjö, Anders

2011-04-01

The monitoring of radioactive xenon isotopes is one of the principal methods for the detection of nuclear explosions in order to identify clandestine nuclear testing. In this work, a miniaturized, multiple-oven, six-column, preparative gas chromatograph was constructed in order to isolate trace quantities of radioactive xenon isotopes from ambient air, utilizing nitrogen as the carrier gas. The multidimensional chromatograph comprised preparative stainless steel columns packed with molecular sieves, activated carbon, and synthetic carbon adsorbents (e.g., Anasorb®-747 and Carbosphere®). A combination of purification techniques--ambient adsorption, thermal desorption, back-flushing, thermal focusing, and heart cutting--was selectively optimized to produce a well-defined xenon peak that facilitated reproducible heart cutting and accurate quantification. The chromatographic purification of a sample requires approximately 4 h and provides complete separation of xenon from potentially interfering components (such as water vapor, methane, carbon dioxide, and radon) with recovery and accuracy close to 100%. The preparative enrichment process isolates and concentrates a highly purified xenon gas fraction that is suitable for subsequent ultra-low-level γ-, ß/γ-spectroscopic or high-resolution mass spectrometric measurement (e.g., to monitor the gaseous fission products of nuclear explosions at remote locations). The Xenon Processing Unit is a free-standing, relatively lightweight, and transportable system that can be interfaced to a variety of sampling and detection systems. It has a relatively inexpensive, rugged, and compact modular (19-inch rack) design that provides easy access to all parts for maintenance and has a low power requirement.

The ATTA-Hefei Instrument for Radioactive Noble-gas Dating

NASA Astrophysics Data System (ADS)

Hu, S.; Cheng, C.; Cheng, G.; Sun, Y. R.; Tu, L.; Yang, G.

2013-12-01

Long-lived noble-gas isotopes 85Kr (10.8 y), 39Ar (269 y) and 81Kr (229 ky) are ideal tracers for dating environmental samples such as groundwater and ice. Together with 14C, these nuclides can be used to cover the whole range of 100-106 y. Atom Trap Trace Analysis (ATTA) is an emerging method for the analysis of these isotopes at an isotopic abundance level as low as 10^-16 [1,2]. The ATTA instrument built in Hefei, China, can determine the isotopic abundances of 85Kr and 81Kr with typically 5-10% accuracy using krypton gas samples of a few micro-liters (STP) krypton gas [3]. The krypton gas sample can be extracted from several liters of air using a distillation-chromatograph setup with a typical efficiency of 85%, while the air sample can be extracted from groundwater or ices. The typical sample size for ATTA measurement is 100L groundwater or 40Kg ices. One such ATTA beamline can handle about 100 samples per year. [1] Chen, C. Y. et al. Ultrasensitive isotope trace analyses with a magneto-optical trap. Science 286, 1139-1141 (1999). [2] Jiang, W. et al. 39Ar detection at the 10-16 isotopic abundance level with atom trap trace analysis. Phys. Rev. Lett. 106, 103001 (2011). [3] Yang, G. -M. et al. Analysis of 85Kr: a comparison at the 10-14 level using micro-liter samples, Sci. Rep. 3, 1596 (2013). Relative uncertainty of the determined 85Kr abundance by the ATTA-Hefei instrument.

Stable isotope and trace element studies of black bear hair, Big Bend ecosystem, Texas and Mexico

USGS Publications Warehouse

Shanks, W.C. Pat; Hellgren, Eric C.; Stricker, Craig A.; Gemery-Hill, Pamela A.; Onorato, David P.

2008-01-01

Hair from black bears (Ursus americanus), collected from four areas in the Big Bend ecosystem, has been analyzed for stable isotopes of carbon, nitrogen, and sulfur to determine major food sources and for trace metals to infer possible effects of environmental contaminants. Results indicate that black bears are largely vegetarian, feeding on desert plants, nuts, and berries. Mercury concentrations in bear hair are below safe level standards (

Isotope-Labeled Composition B for Tracing Detonation Signatures

NASA Astrophysics Data System (ADS)

Manner, Virginia; Podlesak, David; Huber, Rachel; Amato, Ronald; Giambra, Anna; Bowden, Patrick; Hartline, Ernest; Dattelbaum, Dana

2017-06-01

To better understand how solid carbon forms and evolves during detonation, we have prepared Composition B with 13 C and 15 N-labeled 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and 2,4,6-trinitrotoluene (TNT) in order to trace the formation of soot from the carbon and nitrogen atoms in these explosives. Isotope-labeling of explosives has been performed in the recent past for a variety of reasons, including environmental remediation and reaction mechanism studies. Because it is expensive and time consuming to prepare these materials, and our detection equipment only requires trace amounts of isotopes, we have prepared fully-labeled materials and substituted them into unlabeled RDX and TNT at less than the 1% level. We will discuss the preparation and full characterization of this labeled Composition B, the detonation tests performed, along with the results of the post-detonation soot analysis. Various detonation models predict differing amounts and forms of carbon and nitrogen; these isotopically-labeled precursors have allowed these models to be tested.

Gamma-ray spectrometry of ultra low levels of radioactivity within the material screening program for the GERDA experiment.

PubMed

Budjás, D; Gangapshev, A M; Gasparro, J; Hampel, W; Heisel, M; Heusser, G; Hult, M; Klimenko, A A; Kuzminov, V V; Laubenstein, M; Maneschg, W; Simgen, H; Smolnikov, A A; Tomei, C; Vasiliev, S I

2009-05-01

In present and future experiments in the field of rare events physics a background index of 10(-3) counts/(keV kg a) or better in the region of interest is envisaged. A thorough material screening is mandatory in order to achieve this goal. The results of a systematic study of radioactive trace impurities in selected materials using ultra low-level gamma-ray spectrometry in the framework of the GERDA experiment are reported.

Ultra-trace analysis of 41Ca in urine by accelerator mass spectrometry: an inter-laboratory comparison

PubMed Central

Jackson, George S.; Hillegonds, Darren J.; Muzikar, Paul; Goehring, Brent

2013-01-01

A 41Ca interlaboratory comparison between Lawrence Livermore National Laboratory (LLNL) and the Purdue Rare Isotope Laboratory (PRIME Lab) has been completed. Analysis of the ratios assayed by accelerator mass spectrometry (AMS) shows that there is no statistically significant difference in the ratios. Further, Bayesian analysis shows that the uncertainties reported by both facilities are correct with the possibility of a slight under-estimation by one laboratory. Finally, the chemistry procedures used by the two facilities to produce CaF2 for the cesium sputter ion source are robust and don't yield any significant differences in the final result. PMID:24179312

Carbon and Hydrogen Isotope Measurements of Alcohols and Organic Acids by Online Pyroprobe-GC-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.

2012-01-01

The detection of methane in the atmosphere of Mars, combined with evidence showing widespread water-rock interaction during martian history, suggests that the production of methane on Mars may be the result of mineral surface-catalyzed CO2 and or CO reduction during Fisher-Tropsch Type (FTT) reactions. A better understanding of these reaction pathways and corresponding C and H isotope fractionations is critical to deciphering the synthesis of organic compounds produced under abiotic hydrothermal conditions. Described here is a technique for the extraction and analysis of both C and H isotopes from alcohols (C1-C4) and organic acids (C1-C6). This work is meant to provide a "proof of concept" for making meaningful isotope measurements on complex mixtures of solid-phase hydrocarbons and other intermediary products produced during high-temperature and high-pressure synthesis on mineral-catalyzed surfaces. These analyses are conducted entirely "on-line" utilizing a CDS model 5000 Pyroprobe connected to a Thermo Trace GC Ultra that is interfaced with a Thermo MAT 253 isotope ratio mass spectrometer operating in continuous flow mode. Also, this technique is designed to carry a split of the GC-separated product to a DSQ II quadrupole mass spectrometer as a means of making semi-quantitative compositional measurements. Therefore, both chemical and isotopic measurements can be carried out on the same sample.

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

Massively parallel sensing of trace molecules and their isotopologues with broadband subharmonic mid-infrared frequency combs

NASA Astrophysics Data System (ADS)

Muraviev, A. V.; Smolski, V. O.; Loparo, Z. E.; Vodopyanov, K. L.

2018-04-01

Mid-infrared spectroscopy offers supreme sensitivity for the detection of trace gases, solids and liquids based on tell-tale vibrational bands specific to this spectral region. Here, we present a new platform for mid-infrared dual-comb Fourier-transform spectroscopy based on a pair of ultra-broadband subharmonic optical parametric oscillators pumped by two phase-locked thulium-fibre combs. Our system provides fast (7 ms for a single interferogram), moving-parts-free, simultaneous acquisition of 350,000 spectral data points, spaced by a 115 MHz intermodal interval over the 3.1-5.5 µm spectral range. Parallel detection of 22 trace molecular species in a gas mixture, including isotopologues containing isotopes such as 13C, 18O, 17O, 15N, 34S, 33S and deuterium, with part-per-billion sensitivity and sub-Doppler resolution is demonstrated. The technique also features absolute optical frequency referencing to an atomic clock, a high degree of mutual coherence between the two mid-infrared combs with a relative comb-tooth linewidth of 25 mHz, coherent averaging and feasibility for kilohertz-scale spectral resolution.

ICP MS selection of radiopure materials for the GERDA experiment

NASA Astrophysics Data System (ADS)

di Vacri, M. L.; Nisi, S.; Cattadori, C.; Janicsko, J.; Lubashevskiy, A.; Smolnikov, A.; Walter, M.

2015-08-01

The GERDA (GERmanium Detector Array) experiment, located in the Gran Sasso Underground Laboratory (LNGS, Italy) aims to search for neutrinoless double beta (0νββ) decay of the 76Ge isotope. Both an ultra-low radioactivity background environment and active techniques to abate the residual background are required to reach the background index (of 10-3 counts/keV kg y) at the Qββ. In order to veto and suppress those events that partially deposit energy in Ge detectors, the readout of liquid argon (LAr) scintillation light (SL) has been implemented for the second GERDA experimental Phase. A double veto system has been designed and constructed using highly radiopure materials (scintillating fibers, wavelength shifters, polymeric foils, reflective foils). This work describes the study of lead, thorium and uranium ultra-trace content, performed at the LNGS Chemistry Laboratory by High Resolution Mass Spectrometry (HR ICP MS), for the selection of all materials involved in the construction of the veto system

Boninite-like intraplate magmas from Manihiki Plateau require ultra-depleted and enriched source components

PubMed Central

Golowin, Roman; Portnyagin, Maxim; Hoernle, Kaj; Hauff, Folkmar; Gurenko, Andrey; Garbe-Schönberg, Dieter; Werner, Reinhard; Turner, Simon

2017-01-01

The Ontong Java and Manihiki oceanic plateaus are believed to have formed through high-degree melting of a mantle plume head. Boninite-like, low-Ti basement rocks at Manihiki, however, imply a more complex magma genesis compared with Ontong Java basement lavas that can be generated by ∼30% melting of a primitive mantle source. Here we show that the trace element and isotope compositions of low-Ti Manihiki rocks can best be explained by re-melting of an ultra-depleted source (possibly a common mantle component in the Ontong Java and Manihiki plume sources) re-enriched by ≤1% of an ocean-island-basalt-like melt component. Unlike boninites formed via hydrous flux melting of refractory mantle at subduction zones, these boninite-like intraplate rocks formed through adiabatic decompression melting of refractory plume material that has been metasomatized by ocean-island-basalt-like melts. Our results suggest that caution is required before assuming all Archaean boninites were formed in association with subduction processes. PMID:28181497

ICP MS selection of radiopure materials for the GERDA experiment

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

Di Vacri, M. L., E-mail: divacrim@lngs.infn.it; Dipartimento di Scienze Fisiche e Chimiche, University of L’Aquila, via Vetoio, 67100 L’Aquila; Nisi, S., E-mail: nisi@lngs.infn.it

2015-08-17

The GERDA (GERmanium Detector Array) experiment, located in the Gran Sasso Underground Laboratory (LNGS, Italy) aims to search for neutrinoless double beta (0νββ) decay of the {sup 76}Ge isotope. Both an ultra-low radioactivity background environment and active techniques to abate the residual background are required to reach the background index (of 10{sup −3} counts/keV kg y) at the Q{sub ββ}. In order to veto and suppress those events that partially deposit energy in Ge detectors, the readout of liquid argon (LAr) scintillation light (SL) has been implemented for the second GERDA experimental Phase. A double veto system has been designedmore » and constructed using highly radiopure materials (scintillating fibers, wavelength shifters, polymeric foils, reflective foils). This work describes the study of lead, thorium and uranium ultra-trace content, performed at the LNGS Chemistry Laboratory by High Resolution Mass Spectrometry (HR ICP MS), for the selection of all materials involved in the construction of the veto system.« less

Desorption electrospray ionization mass spectrometry for trace analysis of agrochemicals in food.

PubMed

García-Reyes, Juan F; Jackson, Ayanna U; Molina-Díaz, Antonio; Cooks, R Graham

2009-01-15

Desorption electrospray ionization (DESI) is applied to the rapid, in situ, direct qualitative and quantitative (ultra)trace analysis of agrochemicals in foodstuffs. To evaluate the potential of DESI mass spectrometry (MS) in toxic residue testing in food, 16 representative multiclass agricultural chemicals (pesticides, insecticides, herbicides, and fungicides) were selected (namely, ametryn, amitraz, azoxystrobin, bitertanol, buprofezin, imazalil, imazalil metabolite, isofenphos-methyl, malathion, nitenpyram, prochloraz, spinosad, terbuthylazine, thiabendazole, and thiacloprid). The DESI-MS experiments were performed using 3 microL of solution spotted onto conventional smooth poly(tetrafluoroethylene) (PTFE) surfaces, with examination by MS and tandem mass spectrometry (MS/MS) using an ion trap mass spectrometer. Optimization of the spray solvent led to the use of acetonitrile/water (80:20) (v/v), with 1% formic acid. Most of the compounds tested showed remarkable sensitivity in the positive ion mode, approaching that attainable with conventional direct infusion electrospray mass spectrometry. To evaluate the potential of the proposed approach in real samples, different experiments were performed including the direct DESI-MS/MS analysis of fruit peels and also of fruit/vegetable extracts. The results proved that DESI allows the detection and confirmation of traces of agrochemicals in actual market-purchased samples. In addition, MS/MS confirmation of selected pesticides in spiked vegetable extracts was obtained at absolute levels as low as 1 pg for ametryn. Quantitation of imazalil residues was also undertaken using an isotopically labeled standard. The data obtained were in agreement with those from the liquid chromatography mass spectrometry (LC-MS) reference method, with relative standard deviation (RSD) values consistently below 15%. The results obtained demonstrate the sensitivity of DESI as they meet the stringent European Union pesticide regulation requirements (maximum residue levels) for a large percentage of the studied compounds.

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

Mace, Emily; Aalseth, Craig; Alexander, Tom

Use of ultra-low-background capabilities at Pacific Northwest National Laboratory provide enhanced sensitivity for measurement of low-activity sources of tritium and radiocarbon using proportional counters. Tritium levels are nearly back to pre-nuclear test backgrounds (~2-8 TU in rainwater), which can complicate their dual measurement with radiocarbon due to overlap in the isotope’s respective energy spectra. This activity makes direct dual-isotope measurements challenging without additional chemistry to concentrate the tritium in a sample. We present results of single-isotope proportional counter measurements used to analyze a dual-isotope methane sample synthesized from ~120 mg of H2O and present sensitivity results.

Analysis of trace halocarbon contaminants in ultra high purity helium

NASA Technical Reports Server (NTRS)

Fewell, Larry L.

1994-01-01

This study describes the analysis of ultra high purity helium. Purification studies were conducted and containment removal was effected by the utilization of solid adsorbent purge-trap systems at cryogenic temperatures. Volatile organic compounds in ultra high purity helium were adsorbed on a solid adsorbent-cryogenic trap, and thermally desorbed trace halocarbon and other contaminants were analyzed by combined gas chromatography-mass spectrometry.

An Industry-Scale Mass Marking Technique for Tracing Farmed Fish Escapees

PubMed Central

Warren-Myers, Fletcher; Dempster, Tim; Fjelldal, Per Gunnar; Hansen, Tom; Swearer, Stephen E.

2015-01-01

Farmed fish escape and enter the environment with subsequent effects on wild populations. Reducing escapes requires the ability to trace individuals back to the point of escape, so that escape causes can be identified and technical standards improved. Here, we tested if stable isotope otolith fingerprint marks delivered during routine vaccination could be an accurate, feasible and cost effective marking method, suitable for industrial-scale application. We tested seven stable isotopes, 134Ba, 135Ba, 136Ba, 137Ba, 86Sr, 87Sr and 26Mg, on farmed Atlantic salmon reared in freshwater, in experimental conditions designed to reflect commercial practice. Marking was 100% successful with individual Ba isotopes at concentrations as low as 0.001 µg. g-1 fish and for Sr isotopes at 1 µg. g-1 fish. Our results suggest that 63 unique fingerprint marks can be made at low cost using Ba (0.0002 – 0.02 $US per mark) and Sr (0.46 – 0.82 $US per mark) isotopes. Stable isotope fingerprinting during vaccination is feasible for commercial application if applied at a company level within the world’s largest salmon producing nations. Introducing a mass marking scheme would enable tracing of escapees back to point of origin, which could drive greater compliance, better farm design and improved management practices to reduce escapes. PMID:25738955

Same-sample determination of ultratrace levels of polybromodiphenylethers, polybromodibenzo-p-dioxins/furans, and polychlorodibenzo-p-dioxins/furans from combustion flue gas

EPA Science Inventory

The analytical method used for determination of polychlorinated dibenzo-p-dioxins and -furans (PCDDs/Fs) emissions from municipal waste combustors and other stationary sources was modified and validated to enable simultaneous analysis of ultra trace levels of polybrominated diphe...

Purification of lanthanides for double beta decay experiments

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

Polischuk, O. G.; Barabash, A. S.; Belli, P.

2013-08-08

There are several potentially double beta active isotopes among the lanthanide elements. However, even high purity grade lanthanide compounds contain {sup 238}U, {sup 226}Ra and {sup 232,228}Th typically on the level of ∼ (0.1 - 1) Bq/kg. The liquid-liquid extraction technique was used to remove traces of U, Ra and Th from CeO{sub 2}, Nd{sub 2}O{sub 3} and Gd{sub 2}O{sub 3}. The radioactive contamination of the samples before and after the purification was tested by using ultra-low-background HPGe γ spectrometry at the underground Gran Sasso National Laboratories of the INFN (Italy). After the purification the radioactive contamination of gadolinium oxidemore » by Ra and Th was decreased at least one order of magnitude. The efficiency of the approach to purify cerium oxide from Ra was on same level, while the radioactive contamination of neodymium sample before and after the purification is below the sensitivity of analytical methods. The purification method is much less efficient for chemically very similar radioactive elements like lanthanum, lutetium and actinium. R and D of the methods to remove the pollutions with improved efficiency is in progress.« less

Anatomy of a cluster IDP. Part 2: Noble gas abundances, trace element geochemistry, isotopic abundances, and trace organic chemistry of several fragments from L2008#5

NASA Technical Reports Server (NTRS)

Thomas, K. L.; Clemett, S. J.; Flynn, G. J.; Keller, L. P.; Mckay, David S.; Messenger, S.; Nier, A. O.; Schlutter, D. J.; Sutton, S. R.; Walker, R. M.

1994-01-01

The topics discussed include the following: noble gas content and release temperatures; trace element abundances; heating summary of cluster fragments; isotopic measurements; and trace organic chemistry.

Neutral Mass Spectrometry for Venus Atmosphere and Surface

NASA Technical Reports Server (NTRS)

Mahaffy, Paul

2005-01-01

The assignment is to make precise (better than 1 %) measurements of isotope ratios and accurate (5-10%) measurements of abundances of noble gas and to obtain vertical profiles of trace chemically active gases from above the clouds all the way down to the surface. Science measurement objectives are as follows: 1) Determine the composition of Venus atmosphere, including trace gas species and light stable isotopes; 2) Accurately measure noble-gas isotopic abundance in the atmosphere; 3) Provide descent, surface, and ascent meteorological data; 4) Measure zonal cloud-level winds over several Earth days; 5) Obtain near-IR descent images of the surface from 10-km altitude to the surface; 6) Accurately measure elemental abundances & mineralogy of a core from the surface; and 7) Evaluate the texture of surface materials to constrain weathering environment.

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

Bürger, Stefan; Riciputi, Lee R; Bostick, Debra A

A ThermoFisher 'Triton' multi-collector thermal ionization mass spectrometer (MC-TIMS) was evaluated for trace and ultra-trace level isotoperatioanalysis of actinides (uranium, plutonium, and americium), fission products and geolocators (strontium, cesium, and neodymium). Total efficiencies (atoms loaded to ions detected) of up to 0.5-2% for U, Pu, and Am, and 1-30% for Sr, Cs, and Nd can be reported employing resin bead load techniques onto flat ribbon Re filaments or resin beads loaded into a millimeter-sized cavity drilled into a Re rod. This results in detection limits of <0.1 fg (10{sup 4} atoms to 10{sup 5} atoms) for {sup 239-242+244}Pu, {sup 233+236}U,more » {sup 241-243}Am, {sup 89,90}Sr, and {sup 134,135,137}Cs, and {le} 1 pg for natural Nd isotopes (limited by the chemical processing blank) using a secondary electron multiplier (SEM) or multiple-ion counters (MICs). Relative standard deviations (RSD) as small as 0.1% and abundance sensitivities of 1 x 10{sup 6} or better using a SEM are reported here. Precisions of RSD {approx} 0.01-0.001% using a multi-collector Faraday cup array can be achieved at sub-nanogram concentrations for strontium and neodymium and are suitable to gain crucial geolocation information. The analytical protocols reported herein are of particular value for nuclear forensic and nuclear safeguard applications.« less

Ochratoxin A determination in swine muscle and liver from French conventional or organic farming production systems.

PubMed

Hort, Vincent; Nicolas, Marina; Minvielle, Brice; Maleix, Corentin; Desbourdes, Caroline; Hommet, Frédéric; Dragacci, Sylviane; Dervilly-Pinel, Gaud; Engel, Erwan; Guérin, Thierry

2018-05-28

Consumers generally considered organic products to be healthier and safer but data regarding the contamination of organic products are scarce. This study evaluated the impact of the farming system on the levels of ochratoxin A (OTA) in the tissues of French pigs (muscle and liver) reared following three different types of production (organic, Label Rouge and conventional). Because OTA is present at trace levels in animal products, a sensitive ultra-high performance liquid chromatography-tandem mass spectrometry method using stable isotope dilution assay was developed and validated. OTA was detected or quantified (LOQ of 0.10 μg kg -1 ) in 67% (n = 47) of the 70 pig liver samples analysed, with concentrations ranging from <0.10 to 3.65 μg kg -1 . The maximum concentration was found in a sample from organic production but there were no significant differences in the content of OTA between farming systems. OTA was above the LOQ in four out of 25 samples of the pork muscles. A good agreement was found between OTA levels in muscle and liver (liver concentration = 2.9 × OTA muscle concentration, r = 0.981). Copyright © 2018 Elsevier B.V. All rights reserved.

Existing and emerging technologies for measuring stable isotope labelled retinol in biological samples: isotope dilution analysis of body retinol stores.

PubMed

Preston, Tom

2014-01-01

This paper discusses some of the recent improvements in instrumentation used for stable isotope tracer measurements in the context of measuring retinol stores, in vivo. Tracer costs, together with concerns that larger tracer doses may perturb the parameter under study, demand that ever more sensitive mass spectrometric techniques are developed. GCMS is the most widely used technique. It has high sensitivity in terms of sample amount and uses high resolution GC, yet its ability to detect low isotope ratios is limited by background noise. LCMSMS may become more accessible for tracer studies. Its ability to measure low level stable isotope tracers may prove superior to GCMS, but it is isotope ratio MS (IRMS) that has been designed specifically for low level stable isotope analysis through accurate analysis of tracer:tracee ratios (the tracee being the unlabelled species). Compound-specific isotope analysis, where GC is interfaced to IRMS, is gaining popularity. Here, individual 13C-labelled compounds are separated by GC, combusted to CO2 and transferred on-line for ratiometric analysis by IRMS at the ppm level. However, commercially-available 13C-labelled retinol tracers are 2 - 4 times more expensive than deuterated tracers. For 2H-labelled compounds, GC-pyrolysis-IRMS has now become more generally available as an operating mode on the same IRMS instrument. Here, individual compounds are separated by GC and pyrolysed to H2 at high temperature for analysis by IRMS. It is predicted that GC-pyrolysis-IRMS will facilitate low level tracer procedures to measure body retinol stores, as has been accomplished in the case of fatty acids and amino acids. Sample size requirements for GC-P-IRMS may exceed those of GCMS, but this paper discusses sample preparation procedures and predicts improvements, particularly in the efficiency of sample introduction.

Ultra-sensitive speciation analysis of mercury by CE-ICP-MS together with field-amplified sample stacking injection and dispersive solid-phase extraction.

PubMed

Chen, YiQuan; Cheng, Xian; Mo, Fan; Huang, LiMei; Wu, Zujian; Wu, Yongning; Xu, LiangJun; Fu, FengFu

2016-04-01

A simple dispersive solid-phase extraction (DSPE) used to extract and preconcentrate ultra-trace MeHg, EtHg and Hg(2+) from water sample, and a sensitive method for the simultaneous analysis of MeHg, EtHg and Hg(2+) by using capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) with field-amplified sample stacking injection (FASI) were first reported in this study. The DSPE used thiol cotton particles as adsorbent, and is simple and effective. It can be used to extract and preconcentrate ultra-trace mercury compounds in water samples within 30 min with a satisfied recovery and no mercury species alteration during the process. The FASI enhanced the sensitivity of CE-ICP-MS with 25-fold, 29-fold and 27-fold for MeHg, EtHg and Hg(2+) , respectively. Using FASI-CE-ICP-MS together with DSPE, we have successfully determined ultra-trace MeHg, EtHg and Hg(2+) in tap water with a limits of quantification (LOQs) of 0.26-0.45 pg/mL, an RSD (n = 3) < 6% and a recovery of 92-108%. Ultra-high sensitivity, as well as much less sample and reagent consumption and low operating cost, make our method a valuable technique to the speciation analysis of ultra-trace mercury. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of Trace Level Iodine in Biological and Botanical Reference Materials by Isotope Dilution Mass Spectrometry

PubMed Central

Gramlich, John W.; Murphy, Thomas J.

1989-01-01

A method has been developed for the determination of trace level iodine in biological and botanical materials. The method consists of spiking a sample with 129I, equilibration of the spike with the natural iodine, wet ashing under carefully controlled conditions, and separation of the iodine by co-precipitation with silver chloride. Measurement of the 129I/127I ratio is accomplished by negative thermal ionization mass spectrometry using LaB6 for ionization enhancement. The application of the method to the certification of trace iodine in two Standard Reference Materials is described. PMID:28053411

Seasonal Cyclicity in Trace Elements and Stable Isotopes of Modern Horse Enamel.

PubMed

de Winter, Niels J; Snoeck, Christophe; Claeys, Philippe

2016-01-01

The study of stable isotopes in fossil bioapatite has yielded useful results and has shown that bioapatites are able to faithfully record paleo-environmental and paleo-climatic parameters from archeological to geological timescales. In an effort to establish new proxies for the study of bioapatites, intra-tooth records of enamel carbonate stable isotope ratios from a modern horse are compared with trace element profiles measured using laboratory micro X-Ray Fluorescence scanning. Using known patterns of tooth eruption and the relationship between stable oxygen isotopes and local temperature seasonality, an age model is constructed that links records from six cheek upper right teeth from the second premolar to the third molar. When plotted on this age model, the trace element ratios from horse tooth enamel show a seasonal pattern with a small shift in phase compared to stable oxygen isotope ratios. While stable oxygen and carbon isotopes in tooth enamel are forced respectively by the state of the hydrological cycle and the animal's diet, we argue that the seasonal signal in trace elements reflects seasonal changes in dust intake and diet of the animal. The latter explanation is in agreement with seasonal changes observed in carbon isotopes of the same teeth. This external forcing of trace element composition in mammal tooth enamel implies that trace element ratios may be used as proxies for seasonal changes in paleo-environment and paleo-diet.

Seasonal Cyclicity in Trace Elements and Stable Isotopes of Modern Horse Enamel

PubMed Central

Snoeck, Christophe; Claeys, Philippe

2016-01-01

The study of stable isotopes in fossil bioapatite has yielded useful results and has shown that bioapatites are able to faithfully record paleo-environmental and paleo-climatic parameters from archeological to geological timescales. In an effort to establish new proxies for the study of bioapatites, intra-tooth records of enamel carbonate stable isotope ratios from a modern horse are compared with trace element profiles measured using laboratory micro X-Ray Fluorescence scanning. Using known patterns of tooth eruption and the relationship between stable oxygen isotopes and local temperature seasonality, an age model is constructed that links records from six cheek upper right teeth from the second premolar to the third molar. When plotted on this age model, the trace element ratios from horse tooth enamel show a seasonal pattern with a small shift in phase compared to stable oxygen isotope ratios. While stable oxygen and carbon isotopes in tooth enamel are forced respectively by the state of the hydrological cycle and the animal’s diet, we argue that the seasonal signal in trace elements reflects seasonal changes in dust intake and diet of the animal. The latter explanation is in agreement with seasonal changes observed in carbon isotopes of the same teeth. This external forcing of trace element composition in mammal tooth enamel implies that trace element ratios may be used as proxies for seasonal changes in paleo-environment and paleo-diet. PMID:27875538

Natural Transmutation of Actinides via the Fission Reaction in the Closed Thorium-Uranium-Plutonium Fuel Cycle

NASA Astrophysics Data System (ADS)

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

2017-12-01

It is shown for a closed thorium-uranium-plutonium fuel cycle that, upon processing of one metric ton of irradiated fuel after each four-year campaign, the radioactive wastes contain 54 kg of fission products, 0.8 kg of thorium, 0.10 kg of uranium isotopes, 0.005 kg of plutonium isotopes, 0.002 kg of neptunium, and "trace" amounts of americium and curium isotopes. This qualitatively simplifies the handling of high-level wastes in nuclear power engineering.

Measurement of trace impurities in ultra pure hydrogen and deuterium at the parts-per-billion level using gas chromatography

NASA Astrophysics Data System (ADS)

Ganzha, V.; Ivshin, K.; Kammel, P.; Kravchenko, P.; Kravtsov, P.; Petitjean, C.; Trofimov, V.; Vasilyev, A.; Vorobyov, A.; Vznuzdaev, M.; Wauters, F.

2018-02-01

A series of muon experiments at the Paul Scherrer Institute in Switzerland deploy ultra-pure hydrogen active targets. A new gas impurity analysis technique was developed, based on conventional gas chromatography, with the capability to measure part-per-billion (ppb) traces of nitrogen and oxygen in hydrogen and deuterium. Key ingredients are a cryogenic admixture accumulation, a directly connected sampling system and a dedicated calibration setup. The dependence of the measured concentration on the sample volume was investigated, confirming that all impurities from the sample gas are collected in the accumulation column and measured with the gas chromatograph. The system was calibrated utilizing dynamic dilution of admixtures into the gas flow down to sub-ppb level concentrations. The total amount of impurities accumulated in the purification system during a three month long experimental run was measured and agreed well with the calculated amount based on the measured concentrations in the flow.

Analysis of Endocrine Disrupting Pesticides by Capillary GC with Mass Spectrometric Detection

PubMed Central

Matisová, Eva; Hrouzková, Svetlana

2012-01-01

Endocrine disrupting chemicals, among them many pesticides, alter the normal functioning of the endocrine system of both wildlife and humans at very low concentration levels. Therefore, the importance of method development for their analysis in food and the environment is increasing. This also covers contributions in the field of ultra-trace analysis of multicomponent mixtures of organic pollutants in complex matrices. With this fact conventional capillary gas chromatography (CGC) and fast CGC with mass spectrometric detection (MS) has acquired a real importance in the analysis of endocrine disrupting pesticide (EDP) residues. This paper provides an overview of GC methods, including sample preparation steps, for analysis of EDPs in a variety of matrices at ultra-trace concentration levels. Emphasis is put on separation method, mode of MS detection and ionization and obtained limits of detection and quantification. Analysis time is one of the most important aspects that should be considered in the choice of analytical methods for routine analysis. Therefore, the benefits of developed fast GC methods are important. PMID:23202677

Mo isotopes as redox indicators for the Southern Tethys during the PETM

NASA Astrophysics Data System (ADS)

Wouters, H.; Dickson, A.; Porcelli, D.; Hesselbo, S. P.; van den Boorn, S.; Gomez, V. G.; Mutterlose, J.

2014-12-01

As several ocean and climate models predict a decline in dissolved ocean oxygen concentrations associated with future global warming [1], recent research is increasingly focusing on past episodes of low ocean oxygen levels. Trace metals are generally enriched in organic-rich sediments deposited under such low oxygen conditions, and the concentration and isotopic signatures of several of these elements (e.g. Mo, U, Cr) may be applied as proxies to reconstruct the processes involved in these redox changes [2,3]. This project investigates the use of the molybdenum isotope system as a proxy for redox changes during an interval of abrupt environmental change spanning the Paleocene/Eocene boundary (the Paleocene/Eocene Thermal Maximum, PETM, ~56 Ma). The PETM is characterized by global warming and environmental and ecological changes including decreased ocean oxygen levels [4]. Study of the PETM can therefore offer us a valuable insight into how marine ecosystems and biogeochemical cycles may respond to future climate changes, and the predicted decrease of oxygen concentrations in seawater. The molybdenum concentrations and isotope compositions of organic-rich sediments spanning the PETM have been obtained from a Jordan oil shale drill core (OS-28). The obtained δ98/95Mo isotopic ratios range between -0.12‰ and 1.59‰ and coincide with significant fluctuations in trace metal abundances. The data together demonstrate that the global environmental changes associated with the PETM were manifest in the Jordanian basin as significant changes in basin hydrography and dissolved oxygen levels.

1300930

NASA Image and Video Library

2013-08-15

DR. BINAYAK PANDA LOADS A SAMPLE IN THE IMS-6F SECONDARY ION MASS SPECTROSCOPE’S ULTRA HIGH VACUUM CHAMBER. IT IS CAPABLE OF ANALYZING VERY LIGHT ELEMENTS SUCH AS HYDROGEN AND LITHIUM IN ALLOYS. IT CAN ALSO ANALYZE VERY SMALL QUANTITIES OF IMPURITIES IN MATERIALS AT PARTS PER MILLION LEVELS, AND DETERMINE ISOTOPE RATIOS OF ELEMENTS, ALL IN SOLID SAMPLES.

Extraction of CO2 from air samples for isotopic analysis and limits to ultra high precision delta18O determination in CO2 gas.

PubMed

Werner, R A; Rothe, M; Brand, W A

2001-01-01

The determination of delta18O values in CO2 at a precision level of +/-0.02 per thousand (delta-notation) has always been a challenging, if not impossible, analytical task. Here, we demonstrate that beyond the usually assumed major cause of uncertainty - water contamination - there are other, hitherto underestimated sources of contamination and processes which can alter the oxygen isotope composition of CO2. Active surfaces in the preparation line with which CO2 comes into contact, as well as traces of air in the sample, can alter the apparent delta18O value both temporarily and permanently. We investigated the effects of different surface materials including electropolished stainless steel, Duran glass, gold and quartz, the latter both untreated and silanized. CO2 frozen with liquid nitrogen showed a transient alteration of the 18O/16O ratio on all surfaces tested. The time to recover from the alteration as well as the size of the alteration varied with surface type. Quartz that had been ultrasonically cleaned for several hours with high purity water (0.05 microS) exhibited the smallest effect on the measured oxygen isotopic composition of CO2 before and after freezing. However, quartz proved to be mechanically unstable with time when subjected to repeated large temperature changes during operation. After several days of operation the gas released from the freezing step contained progressively increasing trace amounts of O2 probably originating from inclusions within the quartz, which precludes the use of quartz for cryogenically trapping CO2. Stainless steel or gold proved to be suitable materials after proper pre-treatment. To ensure a high trapping efficiency of CO2 from a flow of gas, a cold trap design was chosen comprising a thin wall 1/4" outer tube and a 1/8" inner tube, made respectively from electropolished stainless steel and gold. Due to a considerable 18O specific isotope effect during the release of CO2 from the cold surface, the thawing time had to be as long as 20 min for high precision delta18O measurements. The presence of traces of air in almost all CO2 gases that we analyzed was another major source of error. Nitrogen and oxygen in the ion source of our mass spectrometer (MAT 252, Finnigan MAT, Bremen, Germany) give rise to the production of NO2 at the hot tungsten filament. NO2+ is isobaric with C16O18O+ (m/z 46) and interferes with the delta18O measurement. Trace amounts of air are present in CO2 extracted cryogenically from air at -196 degrees C. This air, trapped at the cold surface, cannot be pumped away quantitatively. The amount of air present depends on the surface structure and, hence, the alteration of the measured delta18O value varies with the surface conditions. For automated high precision measurement of the isotopic composition of CO2 of air samples stored in glass flasks an extraction interface ('BGC-AirTrap') was developed which allows 18 analyses (including standards) per day to be made. For our reference CO2-in-air, stored in high pressure cylinders, the long term (>9 months) single sample precision was 0.012 per thousand for delta13C and 0.019 per thousand for delta18O. Copyright 2001 John Wiley & Sons, Ltd.

Tracing environmental aetiological factors of chronic kidney diseases in the dry zone of Sri Lanka-A hydrogeochemical and isotope approach.

PubMed

Wickramarathna, Sudeera; Balasooriya, Shyamalie; Diyabalanage, Saranga; Chandrajith, Rohana

2017-12-01

Chronic kidney disease of unknown aetiologies (CKDu) is increasingly recognized in tropical regions and is now considered a global health problem. A detailed hydrogeochemical investigation has been performed in three CKDu hotspots in Sri Lanka to assess the geo-environmental aetiological factors influencing this disease. A total of 71 ground- and 26 surface water samples were collected from Girandurukotte, Wilgamuwa and Nikawewa regions and analysed for major constituents and trace elements. The affected regions are dominated by Ca-Mg-HCO 3 facies groundwater that is mainly controlled by silicate weathering. Higher levels of fluoride associated with higher hardness is the main feature of groundwater from CKDu regions compared to non-CKDu regions. Results showed that 65% of the wells in the affected regions exceeded the fluoride concentration of 0.5mg/L. Environmental isotopes of groundwater in the CKDu regions are represented by the regression line of δ 2 H=5.42δ 18 O-3.59 (r 2 =0.916) with a clear isotopic differentiation between local precipitation and groundwater. None of the trace elements exceeded the recommended scales and in most cases levels are negligible in both surface and groundwater in study areas. Therefore, the involvement of trace elements such as Cd, As and Pb can be ignored as causative factors for CKDu. This study highlights the synergistic influence of fluoride and hardness that could enhance the disease, and thereby refute earlier theories that attribute trace elements as causative factors for CKDu. Higher hardness in drinking water also restricts sufficient water uptake, particularly by farmers and which affects the physiological, biochemical and nutritional requirements. Copyright © 2017 Elsevier GmbH. All rights reserved.

Trace gas detection in hyperspectral imagery using the wavelet packet subspace

NASA Astrophysics Data System (ADS)

Salvador, Mark A. Z.

This dissertation describes research into a new remote sensing method to detect trace gases in hyperspectral and ultra-spectral data. This new method is based on the wavelet packet transform. It attempts to improve both the computational tractability and the detection of trace gases in airborne and spaceborne spectral imagery. Atmospheric trace gas research supports various Earth science disciplines to include climatology, vulcanology, pollution monitoring, natural disasters, and intelligence and military applications. Hyperspectral and ultra-spectral data significantly increases the data glut of existing Earth science data sets. Spaceborne spectral data in particular significantly increases spectral resolution while performing daily global collections of the earth. Application of the wavelet packet transform to the spectral space of hyperspectral and ultra-spectral imagery data potentially improves remote sensing detection algorithms. It also facilities the parallelization of these methods for high performance computing. This research seeks two science goals, (1) developing a new spectral imagery detection algorithm, and (2) facilitating the parallelization of trace gas detection in spectral imagery data.

Development and application of mass spectrometric techniques for ultra-trace determination of 236U in environmental samples-A review.

PubMed

Bu, Wenting; Zheng, Jian; Ketterer, Michael E; Hu, Sheng; Uchida, Shigeo; Wang, Xiaolin

2017-12-01

Measurements of the long-lived radionuclide 236 U are an important endeavor, not only in nuclear safeguards work, but also in terms of using this emerging nuclide as a tracer in chemical oceanography, hydrology, and actinide sourcing. Depending on the properties of a sample and its neutron irradiation history, 236 U/ 238 U ratios from different sources vary significantly. Therefore, this ratio can be treated as an important fingerprint for radioactive source identification, and in particular, affords a definitive means of discriminating between naturally occurring U and specific types of anthropogenic U. The development of mass spectrometric techniques makes it possible to determine ultra-trace levels of 236 U in environmental samples. In this paper, we review the current status of mass spectrometric approaches for determination of 236 U in environmental samples. Various sample preparation methods are summarized and compared. The mass spectrometric techniques emphasized herein are thermal ionization mass spectrometry (TIMS), inductively coupled plasma mass spectrometry (ICP-MS) and accelerator mass spectrometry (AMS). The strategies or principles used by each technique for the analysis of 236 U are described. The performances of these techniques in terms of abundance sensitivity and detection limit are discussed in detail. To date, AMS exhibits the best capability for ultra-trace determinations of 236 U. The levels and behaviors of 236 U in various environmental media are summarized and discussed as well. Results suggest that 236 U has an important, emerging role as a tracer for geochemical studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Application of isotope-dilution laser ablation ICP-MS for direct determination of Pu concentrations in soils at pg g(-1) levels.

PubMed

Boulyga, Sergei F; Tibi, Markus; Heumann, Klaus G

2004-01-01

The methods available for determination of environmental contamination by plutonium at ultra-trace levels require labor-consuming sample preparation including matrix removal and plutonium extraction in both nuclear spectroscopy and mass spectrometry. In this work, laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for direct analysis of Pu in soil and sediment samples. Application of a LINA-Spark-Atomizer system (a modified laser ablation system providing high ablation rates) coupled with a sector-field ICP-MS resulted in detection limits as low as 3x10(-13) g g(-1) for Pu isotopes in soil samples containing uranium at a concentration of a few microg g(-1). The isotope dilution (ID) technique was used for quantification, which compensated for matrix effects in LA-ICP-MS. Interferences by UH+ and PbO2+ ions and by the peak tail of 238U+ ions were reduced or separated by use of dry plasma conditions and a mass resolution of 4000, respectively. No other effects affecting measurement accuracy, except sample inhomogeneity, were revealed. Comparison of results obtained for three contaminated soil samples by use of alpha-spectrometry, ICP-MS with sample decomposition, and LA-ICP-IDMS showed, in general, satisfactory agreement of the different methods. The specific activity of (239+240)Pu (9.8 +/- 3.0 mBq g(-1)) calculated from LA-ICP-IDMS analysis of SRM NIST 4357 coincided well with the certified value of 10.4 +/- 0.2 mBq g(-1). However, the precision of LA-ICP-MS for determination of plutonium in inhomogeneous samples, i.e. if "hot" particles are present, is limited. As far as we are aware this paper reports the lowest detection limits and element concentrations yet measured in direct LA-ICP-MS analysis of environmental samples.

Mantle End-Members: The Trace Element Perspective

NASA Astrophysics Data System (ADS)

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

2004-12-01

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

Use of an ultra-clean sampling technique with inductively coupled plasma-mass spectrometry to determine trace-element concentrations in water from the Kirkwood-Cohansey Aquifer system, coastal plain, New Jersey

USGS Publications Warehouse

Ivahnenko, Tamara; Szabo, Zoltan; Hall, G.S.

1996-01-01

Water samples were collected during 1993 from 22 public supply wells screened in the Kirkwood-Cohansey aquifer system; concentrations of 18 trace elements were determined primarily by using inductively coupled plasma-mass spectrometry (ICP-MS) techniques, though graphite furnace atomic adsorption, hydride generation, and cold- vapor flameless atomic adsorption techniques were used for thallium, arsenic, and mercury, respectively, at the U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL). In addition, laboratory measurements of alkalinity and turbidity were made. The ground-water samples were collected by using ultra-clean sampling protocols developed by the USGS for collecting ground-water samples in areas with water containing low concentrations of trace elements. This technique is based on recently gained experience in sampling surface water for these elements. Field parameters (water temperature, specific conductance, pH, and dissolved-oxygen concentration) were monitored prior to sample collection. Three equipment blanks were collected to ensure that low-level trace-element contamination did not occur during sample collection. One split sample and a commercially- prepared reference standard were submitted to the NWQL o evaluate laboratory precision and accuracy, respectively. Trace-element concentrations in 10 sample splits and one equipment blank were also determined at the Rutgers University Chemistry Department laboratory. Results of the ICP-MS analyses and cold vapor flameless atomic absorption indicated that five trace elements-- cobalt, copper, lead, mercury, and nickel--were detectable in low concentrations (<0.1-29 mg/L) in most of the samples from the 22 wells, and four elements--aluminum, barium, manganese and zinc--were detected in higher concentrations than the other elements (30-710 mg/L for aluminum; 4-180 mg/L for barium, manganese, and zinc). The remaining nine trace elements were present in concentrations consistently lower than the minimum reporting limit. Turbidity was low (less than 1 nephelometric turbidity unit (NTU)), indicating that the trace-element concentrations were present in the dissolved phase and ideally would be reproducible in the absence of highly variable concentrations of particulates. The concentration of lead in one sample exceeded the U.S. Environmental Protection Agency (USEPA) action level of 15 mg/L; concentrations ranged from <1 to 16 mg/L. Mercury was frequently detected; concentrations ranged from <0.1 to 1.1 mg/L but did not exceed the USEPA maximum contaminant level. Results of analyses of the equipment blanks indicated that samples collected by using the new ultra-clean sampling protocols were free of low-level (< 1mg/L) trace-element contamination. The analysis of the split sample sent to the NWQL had a difference of 5 percent or less for all constituents except aluminum, for which the analysis had a difference of 10 percent. Results of ICP-MS analyses of split water samples sent to the Rutgers University Chemistry Department laboratory were, in general, in good agreement (within 10 percent) with those of the NWQL. Results of the analysis of the commercial standard agreed (within 5 percent) with the known concentrations of the trace elements. The quality-assurance data (three blanks, one split sample, and one standard), although not statistically evaluated because of the small data set, indicate that the measured trace-element concentrations are precise and accurate and that the samples were free of contamination at the microgram-per-liter level of contamination.

Spatio-Temporal Variability of Recent Snow Accumulation Across the West Antarctic Ice Sheet Divide Using Ultra-High Frequency Radar and Shallow Firn Cores

NASA Astrophysics Data System (ADS)

Keeler, D. G.; Rupper, S.; Forster, R. R.; Miège, C.; Brewer, S.; Koenig, L.

2017-12-01

The West Antarctic Ice Sheet (WAIS) could be a substantial source of future sea level rise, with 3+ meters of potential increase stored in the ice sheet. Adequate predictions of WAIS contributions, however, depend on well-constrained surface mass balance estimates for the region. Given the sparsity of available data, such estimates are tenuous. Although new data are periodically added, further research (both to collect more data and better utilize existing data) is critical to addressing these issues. Here we present accumulation data from 9 shallow firn cores and 600 km of Ku band radar traces collected as part of the Satellite Era Antarctic Traverse (SEAT) 2011/2012 field season. Using these data, combined with similar data collected during the SEAT 2010/2011 field season, we investigate the spatial variability in accumulation across the WAIS Divide and surrounding regions. We utilize seismic interpretation and 3D visualization tools to investigate the extent and variations of laterally continuous internal horizons in the radar profiles, and compare the results to nearby firn cores. Previous results show that clearly visible, laterally continuous horizons in radar returns in this area do not always represent annual accumulation isochrones, but can instead represent multi-year or sub-annual events. The automated application of Bayesian inference techniques to averaged estimates of multiple adjacent radar traces, however, can estimate annually-resolved independent age-depth scales for these radar data. We use these same automated techniques on firn core isotopic records to infer past snow accumulation rates, allowing a direct comparison with the radar-derived results. Age-depth scales based on manual annual-layer counting of geochemical and isotopic species from these same cores provide validation for the automated approaches. Such techniques could theoretically be applied to additional radar/core data sets in polar regions (e.g. Operation IceBridge), thereby increasing the number of high resolution accumulation records available in these data-sparse regions. An increased understanding of the variability in magnitude and past rates of surface mass balance can provide better constraints on sea level projections and more precise context for present-day and future observations in these regions.

[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.

Use of stable carbon and nitrogen isotopes to trace the larval striped bass food chain in the Sacramento-San Joaquin Estuary, California, April to September 1985

USGS Publications Warehouse

Rast, Walter; Sutton, J.E.

1989-01-01

To assess one potential cause for the decline of the striped bass fishery in the Sacramento-San Joaquin Estuary, stable carbon and nitrogen isotope ratios were used to examine the trophic structures of the larval striped bass food chain, and to trace the flux of these elements through the food chain components. Study results generally confirm a food chain consisting of the elements, phytoplankton/detritus-->zooplankton/Neomysis shrimp-->larval striped bass. The stable isotope ratios generally become more positive as one progresses from the lower to the higher trophic level food chain components, and no unusual trophic structure was found in the food chain. However, the data indicate an unidentified consumer organism occupying an intermediate position between the lower and higher trophic levels of the larval striped bass food chain. Based on expected trophic interactions, this unidentified consumer would have a stable carbon isotope ratio of about 28/mil and a stable nitrogen isotope ratio of about 8/mi. Three possible feeding stages for larval striped bass also were identified, based on their lengths. The smallest length fish seem to subsist on their yolk sac remnants, and the largest length fish subsist on Neomysis shrimp and zooplankton. The intermediate-length fish represent a transition stage between primary food sources and/or use of a mixture of food sources. (USGS)

Tracing contamination sources in soils with Cu and Zn isotopic ratios.

PubMed

Fekiacova, Z; Cornu, S; Pichat, S

2015-06-01

Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrochemical Sample Matrix Elimination for Trace Level Potentiometric Detection with Polymeric Membrane Ion-Selective Electrodes

PubMed Central

Chumbimuni-Torres, Karin Y.; Calvo-Marzal, Percy; Wang, Joseph; Bakker, Eric

2008-01-01

Potentiometric sensors are today sufficiently well understood and optimized to reach ultra-trace level (sub-nanomolar) detection limits for numerous ions. In many cases of practical relevance, however, a high electrolyte background hampers the attainable detection limits. A particularly difficult sample matrix for potentiometric detection is seawater, where the high saline concentration forms a major interfering background and reduces the activity of most trace metals by complexation. This paper describes for the first time a hyphenated system for the online electrochemically modulated preconcentration and matrix elimination (EMPM) of trace metals, combined with a downstream potentiometric detection with solid contact polymeric membrane ion-selective microelectrodes. Following the preconcentration at the bismuth coated electrodes, the deposited metals are oxidized and released to a medium favorable to potentiometric detection, in this case calcium nitrate. Matrix interferences arising from the saline sample medium are thus circumvented. This concept is successfully evaluated with cadmium as a model trace element and offers potentiometric detection down to low parts per billion levels in samples containing 0.5 M NaCl background electrolyte. PMID:18570385

Using Tidal Fluctuation-Induced Dynamics of Radium Isotopes (224Ra, 223Ra, and 228Ra) to Trace the Hydrodynamics and Geochemical Reactions in a Coastal Groundwater Mixing Zone

NASA Astrophysics Data System (ADS)

Liu, Yi; Jiao, Jiu Jimmy; Liang, Wenzhao; Luo, Xin

2018-04-01

The reactive transport of radium isotopes (224Ra, 223Ra, and 228Ra) in coastal groundwater mixing zones (CGMZs) is sensitive to shifts of redox conditions and geochemical reactions induced by tidal fluctuation. This study presents a spatial distribution and temporal variation of radium isotopes in the CGMZ for the first time. Results show that the activity of radium isotopes in the upper saline plume (USP) is comparatively low due to a short residence time and mixing loss induced by the infiltration of low radium seawater whereas the activity of radium isotopes in the salt wedge (SW) is comparatively high due to a long residence time in the aquifer. The spatial distribution of radium isotopes is determined by the partitioning of radium isotopes, groundwater residence time, and relative ingrowth rates of radium isotopes. In addition, the variation of radium isotopes in the USP lags slightly (˜0 h) whereas the fluctuation of radium isotopes in the SW lags significantly (˜12 h) behind sea level oscillation. Tidal fluctuation affects the partitioning of radium isotopes through controlling seawater infiltration and subsequently influences the dynamics of radium isotopes in the USP. Concurrently, seawater infiltration significantly affects geochemical processes such as the production of nutrients and total alkalinity. Therefore, radium dynamics in the USP have implications for these geochemical processes. The variation of radium isotopes in the USP also has potential implications for transformation of trace metals such as iron and manganese because of the close affinity of radium isotopes to manganese and iron oxides.

Simultaneous visualization of the subfemtomolar expression of microRNA and microRNA target gene using HILO microscopy.

PubMed

Lin, Yi-Zhen; Ou, Da-Liang; Chang, Hsin-Yuan; Lin, Wei-Yu; Hsu, Chiun; Chang, Po-Ling

2017-09-01

The family of microRNAs (miRNAs) not only plays an important role in gene regulation but is also useful for the diagnosis of diseases. A reliable method with high sensitivity may allow researchers to detect slight fluctuations in ultra-trace amounts of miRNA. In this study, we propose a sensitive imaging method for the direct probing of miR-10b (miR-10b-3p, also called miR-10b*) and its target ( HOXD10 mRNA) in fixed cells based on the specific recognition of molecular beacons combined with highly inclined and laminated optical sheet (HILO) fluorescence microscopy. The designed dye-quencher-labelled molecular beacons offer excellent efficiencies of fluorescence resonance energy transfer that allow us to detect miRNA and the target mRNA simultaneously in hepatocellular carcinoma cells using HILO fluorescence microscopy. Not only can the basal trace amount of miRNA be observed in each individual cell, but the obtained images also indicate that this method is useful for monitoring the fluctuations in ultra-trace amounts of miRNA when the cells are transfected with a miRNA precursor or a miRNA inhibitor (anti-miR). Furthermore, a reasonable causal relation between the miR-10b and HOXD10 expression levels was observed in miR-10b* precursor-transfected cells and miR-10b* inhibitor-transfected cells. The trends of the miRNA alterations obtained using HILO microscopy completely matched the RT-qPCR data and showed remarkable reproducibility (the coefficient of variation [CV] = 0.86%) and sensitivity (<1.0 fM). This proposed imaging method appears to be useful for the simultaneous visualisation of ultra-trace amounts of miRNA and target mRNA and excludes the procedures for RNA extraction and amplification. Therefore, the visualisation of miRNA and the target mRNA should facilitate the exploration of the functions of ultra-trace amounts of miRNA in fixed cells in biological studies and may serve as a powerful tool for diagnoses based on circulating cancer cells.

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.

Determination of 241Am in sediments by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS).

PubMed

Agarande, M; Benzoubir, S; Bouisset, P; Calmet, D

2001-08-01

Trace levels (pg kg(-1)) of 241Am in sediments were determined by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS) using a microconcentric nebulizer. 241Am was isolated from major elements like Ca and Fe by different selective precipitations. In further steps. Am was first separated from other transuranic elements and purified by anion exchange and extraction chromatography prior to the mass spectrometric measurements. The ID HR ICP-MS results are compared with isotope dilution alpha spectrometry.

High-Resolution Triple Resonance Autoionization of Uranium Isotopes

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

Schumann, Philipp G.; Wendt, K; Bushaw, Bruce A.

2005-11-01

The near-threshold autoionization (AI) spectrum of uranium has been investigated by triple-resonance excitation with single-mode continuous lasers. Spectra were recorded over the first {approx}30 cm-1 above the first ionization limit at a resolution of 3x10-4 cm 1 using intermediate states with different J values (6, 7, 8) to assign AI level total angular momentum JAI = 5 to 9. Resonances with widths ranging from 8 MHz to 30 GHz were observed; the strongest ones have JAI = 9 and widths of {approx} 60 MHz. Hyperfine structures for 235U and isotope shifts for 234,235U have been measured in the two intermediatemore » levels and in the final AI level for the most favorable excitation path. These measurements were performed using aqueous samples containing sub-milligram quantities of uranium at natural isotopic abundances, indicating the potential of this approach for trace isotope ratio determinations.« less

Evaluating the cave carbonate chemical signal as a proxy for rain patterns in Mallorca Island

NASA Astrophysics Data System (ADS)

Cacho, Isabel; Cisneros, Mercé; Torner, Judit; Català, Albert; Moreno, Ana; Stoll, Heather; Iglesias, Miguel; Bladé, Ileana; Fornos, Joan

2017-04-01

Mallorca's climate is marked by a strong seasonal cycle in both temperatures and precipitations which is likely to be recorded in the carbonate precipitates formed in its extended karst systems. Here we present isotopes and trace elements measured in dripwaters collected at weakly and/or seasonal bases since spring 2013 in three caves from Mallorca that represent the eastern and S-eastern sector of the island. This information is complemented with isotopic composition of rain events in the same region, other cave environmental parameters and chemistry of seasonal farmed carbonates in the same caves. Drip water results are very consistent between the different studied caves and indicate an important attenuation of the rainfall isotopic signal in the epikarst and only extreme climate conditions such as the severe dry conditions in summer 2015. Farmed carbonates present a clear seasonal cycle with low values, in both carbon and oxygen isotopes, in summer and autumn and high values in winter and spring. This cyclicity can not be attributed to amount effect or rain composition and we propose a close relation to cave environmental conditions. High CO2 concentrations in summer and autumn would avoid degasification reducing the PCP process and resulting in more negative isotopic relationships in both oxygen and carbon isotopes. Coherently, this CO2 cycles are in phase with those of temperature since both reflect ventilation rates in the cave. Nevertheless, ultra-high resolution profiles of Mg/Ca ratios measured by laser ablation on last century carbonate precipitates in the same caves, reveal a inter-annual variability with a persistent cyclicity which show coherent patterns with the instrumental rain records from Mallorca. This comparison reveals the potential of the Mallorca carbonates to reveal the long-term precipitation evolution of the island.

Laser-Induced Ionization Efficiency Enhancement On A Filament For Thermal Ionization Mass Spectrometry

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

Siegfried, M.

2015-10-14

The evaluation of trace Uranium and Plutonium isotope ratios for nanogram to femtogram material quantities is a vital tool for nuclear counter-proliferation and safeguard activities. Thermal Ionization Mass Spectrometry (TIMS) is generally accepted as the state of the art technology for highly accurate and ultra-trace measurements of these actinide ratios. However, the very low TIMS ionization yield (typically less than 1%) leaves much room for improvement. Enhanced ionization of Nd and Sm from a TIMS filament was demonstrated using wavelength resonance with a nanosecond (pulse width) laser operating at 10 Hz when light was directed toward the filament.1 For thismore » study, femtosecond and picosecond laser capabilities were to be employed to study the dissociation and ionization mechanisms of actinides/lanthanides and measure the enhanced ionization of the metal of interest. Since the underlying chemistry of the actinide/lanthanide carbides produced and dissociated on a TIMS filament is not well understood, the experimental parameters affecting the photodissociation and photoionization with one and two laser beams were to be investigated.« less

Atmospheric trace elements and Pb isotopes at an offshore site, Ieodo Ocean Research Station, in the East China Sea from June to October 2015

NASA Astrophysics Data System (ADS)

Lee, S.; Han, C.; Shin, D.; Hur, S. D.; Jun, S. J.; Kim, Y. T.; Hong, S.

2016-12-01

East Asia, especially China, has become a major anthropogenic source region of trace elements due to the rapid industrialization and urbanization in the past decades. Numerous studies reported that anthropogenic pollutants from East Asia are transported by westerly winds during winter to spring across the Pacific to North America and beyond. Here we report elemental concentrations and Pb isotope ratios in airborne particles from Ieodo Ocean Research Station (IORS) located in the middle of the East China Sea (32.07o N, 125.10o E). A total of 30 aerosol samples (PM2.5-10) were collected between 18 June and 30 October 2015 and analyzed for trace elements (Zn, As, Mo, Cd, Sb, Ba, Tl, and Pb) and Pb isotopes using ICP-SFMS and TIMS, respectively. The mean concentrations of trace elements ranged from 0.06 ng m-3 for Tl to 10.1 ng m-3 for Zn. These values are much lower (up to several orders) than those at unban sites in East Asia, confirming a low level of air pollution at IORS due to the remoteness of the site from major sources of anthropogenic pollutants. On the other hand, the mean crustal enrichment factors, calculated using Ba as a conservative crustal element, are much higher than unity (84 for Tl, 100 for Mo, 140 for Pb, 166 for Zn, 262 for As, 526 for Cd, and 570 for Sb, respectively), indicating that these elements are of anthropogenic origin. Combining the Pb isotope ratios and the HYSPLIT model 5-day backward trajectory analysis, we have identified episodic long-range transport of air pollutants from diverse source regions of China, Korea, Japan and Taiwan to the site in summer (June to August). By comparison, an increasing long-range transport of pollution from China was observed in autumn (September and October). Finally, our study shows that IORS is an ideal background site for monitoring levels of concentrations and source origins of atmospheric trace elements in East Asia.

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...

A portable fluorescence detector for fast ultra trace detection of explosive vapors

NASA Astrophysics Data System (ADS)

Xin, Yunhong; He, Gang; Wang, Qi; Fang, Yu

2011-10-01

This paper developed a portable detector based on a specific material-based fluorescent sensing film for an ultra trace detection of explosives, such as 2,4,6-trinitrotoluene (TNT) or its derivate 2,4-dinitrotoluene (DNT), in ambient air or on objects tainted by explosives. The fluorescent sensing films are based on single-layer chemistry and the signal amplification effect of conjugated polymers, which exhibited higher sensitivity and shorter response time to TNT or DNT at their vapor pressures. Due to application of the light emitting diode and the solid state photomultiplier and the cross-correlation-based circuit design technology, the device has the advantages of low-power, low-cost, small size, and an improved signal to noise ratio. The results of the experiments showed that the detector can real-time detect and identify of explosive vapors at extremely low levels; it is suitable for the identification of suspect luggage, forensic analyses, or battlefields clearing.

A portable fluorescence detector for fast ultra trace detection of explosive vapors.

PubMed

Xin, Yunhong; He, Gang; Wang, Qi; Fang, Yu

2011-10-01

This paper developed a portable detector based on a specific material-based fluorescent sensing film for an ultra trace detection of explosives, such as 2,4,6-trinitrotoluene (TNT) or its derivate 2,4-dinitrotoluene (DNT), in ambient air or on objects tainted by explosives. The fluorescent sensing films are based on single-layer chemistry and the signal amplification effect of conjugated polymers, which exhibited higher sensitivity and shorter response time to TNT or DNT at their vapor pressures. Due to application of the light emitting diode and the solid state photomultiplier and the cross-correlation-based circuit design technology, the device has the advantages of low-power, low-cost, small size, and an improved signal to noise ratio. The results of the experiments showed that the detector can real-time detect and identify of explosive vapors at extremely low levels; it is suitable for the identification of suspect luggage, forensic analyses, or battlefields clearing.

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

PubMed

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

2016-10-01

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

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

PubMed

Müller, M; Heumann, K G

2000-09-01

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

Isotope tracing of Hg pollution from artisanal small scale gold mining in an aquatic ecosystem of Amapá, Brazil

NASA Astrophysics Data System (ADS)

Adler Miserendino, R.; Silbergeld, E. K.; Guimarães, J. D.; Ghosh, S.; Bergquist, B. A.

2010-12-01

Artisinal small scale gold mining (ASGM) is a central economic activity throughout the developing world. It is both a poverty driven and poverty alleviating process; however, ASGM leads to extensive pollution of waterways through the use of Hg to extract gold from deposits. There have been many studies conducted in the Amazon showing elevated levels of Hg in fish and sediment downstream of ASGM sites; however, the debate continues about the contribution of Hg from ASGM versus other potential sources of Hg. In this study, we investigate whether Hg stable isotope analysis can be used to trace mercury pollution from an ASGM site through an aquatic ecosystem in Amapá, Brazil. We measured the Hg isotopic composition of sediment cores from two lakes, only one of which was heavily impacted by the use of elemental Hg in ASGM, as well as from grab samples at the AGSM site and upstream and downstream from the AGSM site along the river which connects the polluted lake to the ASGM site. Hg from all samples were trapped via combustion using the Leeman Labs Hydra-C mercury analyzer and analyzed for both mass-independent and mass-dependent signatures using cold vapor multi-collector inductively coupled plasma mass spectrometry (CV-MC-ICP-MS). Detectable variations in the Hg isotopic signatures were apparent across our field sites, suggesting stable isotopic analysis has great potential to trace contamination pathways in waterways. Preliminary data demonstrate Hg from the ASGM site has unique isotopic signatures that are seen downstream. However, the impacted lake sediments do not have the mining signature despite having three times more Hg than the non-impacted lake. Based on this data, it may be possible to trace Hg from ASGM and assess whether it is impacting local ecosystems and food webs. Hair and soil samples will also be discussed. This demonstration is essential for the broader application of these tools for understanding and applying Hg isotopic analysis in other contexts. This information may also be useful to help reduce Hg exposure of highly vulnerable populations exposed to Hg from ASGM through these aquatic networks in Amapá, Brazil.

Following Carbon Isotopes from Methane to Molecules

NASA Astrophysics Data System (ADS)

Freeman, K. H.

2017-12-01

Continuous-flow methods introduced by Hayes (Matthews and Hayes, 1978; Freeman et al., 1990; Hayes et al., 1990) for compound-specific isotope analyses (CSIA) transformed how we study the origins and fates of organic compounds. This analytical revolution launched several decades of research in which researchers connect individual molecular structures to diverse environmental and climate processes affecting their isotopic profiles. Among the first applications, and one of the more dramatic isotopically, was tracing the flow of natural methane into cellular carbon and cellular biochemical constituents. Microbial oxidation of methane can be tracked by strongly 13C-depleted organic carbon in early Earth sedimentary environments, in marine and lake-derived biomarkers in oils, and in modern organisms and their environments. These signatures constrain microbial carbon cycling and inform our understanding of ocean redox. The measurement of molecular isotopes has jumped forward once again, and it is now possible to determine isotope abundances at specific positions within increasingly complex organic structures. In addition, recent analytical developments have lowered sample sensitivity limits of CSIA to picomole levels. These new tools have opened new ways to measure methane carbon in the natural environment and within biochemical pathways. This talk will highlight how molecular isotope methods enable us to follow the fate of methane carbon in complex environments and along diverse metabolic pathways, from trace fluids to specific carbon positions within microbial biomarkers.

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

PubMed Central

2017-01-01

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

Using combinations of metal isotopes as tracers of tailings pond discharges to subsurface aquifers in the Athabasca Oil Sands area, Canada.

NASA Astrophysics Data System (ADS)

Gammon, P. R.; Savard, M. M.; Ahad, J. M.; Girard, I.

2016-12-01

The Athabasca Oil Sands (AOS) industry in Alberta, Canada deposits voluminous waste streams in Earth's largest tailings ponds (TPs). Detecting and tracing contaminant discharge from TPs to subsurface aquifers has proven difficult because tailings have the same composition as the surrounding environment of unmined oil sand. To trace pond discharge to the subsurface therefore relies on the waste stream hosting additions or alterations induced by mining or industrial processes. Inorganic element or contaminant concentration data have proven ineffective at tracing because there is insufficient alteration of the chemical constituents or their ratios. Metal isotopes have not generally been applied to tracing emissions even though isotopic fractionation is likely induced via the high temperature and pH industrial process. We have generated Mg, Li, Pb and Zn isotopic data for a range of groundwater wells and TPs. Mg isotopes are excellent for distinguishing deep saline brines that are pumped into the waste stream during mine dewatering. Li isotopes appear to be heavily fractionated during processing, which produces a heavy isotopic signature that is an excellent tracer of production water. Pb isotopes discriminate Pb derived from oil-sand versus bedrock carbonate. Juxtapositions of TPs, carbonates and near-surface aquifers are common and of significant regulatory concern, making Pb isotopes particularly useful. Zn isotopic data indicates similarities to Pb isotopes, but are difficult to obtain due to low concentrations. Combining the isotopic data with concentration data and hydrologic models will assist in determining the fluxes of discharges from the TPs to near-surface aquifers. The range of environmental contexts of AOS TPs is limited and thus monitoring discharges to nearby aquifers from TPs could feasibly be accomplished using tailored suites of metal isotopes.

Trace elements (Cu, Zn, and Hg) and δ13C/δ15N in seabird subfossils from three islands of the South China Sea and its implications.

PubMed

Xu, Liqiang; Liu, Xiaodong; Nie, Yaguang

2016-05-01

Seabird subfossils were collected on three islands of the Xisha Archipelago, South China Sea. Via elemental analysis, we identified that bird guano was a significant source for heavy metals Cu, Zn, and Hg. Cu and Zn levels in these guano samples are comparable to their levels in wildbird feces, but guano Hg was lower than previously reported. Trophic positions significantly impacted transfer efficiency of heavy metals by seabirds. Despite of a common source, trace elements, as well as stable isotopes (i.e., guano δ(13)C and collagen δ(15)N), showed island-specific characteristics. Bird subfossils on larger island had relatively greater metal concentrations and revealed higher trophic positions. Partition of element and isotope levels among the islands suggested that transfer efficacy of seabirds on different islands was different, and bird species were probably unevenly distributed among the islets. Island area is possibly a driving factor for distributions of seabird species.

Genesis of Ultra-High Pressure Garnet Pyroxenite in Orogenic Peridotites and its bearing on the Isotopic Chemical Heterogeneity in the Mantle Source of Oceanic Basalts

NASA Astrophysics Data System (ADS)

Varas Reus, María Isabel; Garrido, Carlos J.; Marchesi, Claudio; Bosch, Delphine; Hidas, Károly

2017-04-01

The genesis of ultra-high pressure (UHP) garnet pyroxenites in orogenic peridotite massifs and its implications on the formation of chemical heterogeneities in the mantle and on basalt petrogenesis are still not fully understood. Some UHP (diamond-bearing) garnet pyroxenites have isotopic, and major and trace element compositions similar to the recycled oceanic crustal component observed in oceanic basalts [1-6]. These pyroxenites hence provide an exceptional opportunity to investigate in situ the nature and scale of the Earth's mantle chemical heterogeneities. Here, we present an integrated geochemical study of UHP garnet pyroxenites from the Ronda (Betic Belt, S. Spain) and Beni Bousera (Rif Belt, N. Morocco) peridotite massifs. This investigation encompasses, in the same sample, bulk rock major and trace elements, as well as Sr-Nd-Pb-Hf isotopic analyses. According to their Al2O3 content, we classify UHP garnet pyroxenites into three groups that have distinct trace elements and Sr-Nd-Pb-Hf isotopic signatures. Group A pyroxenites (Al2O3: 15 - 17.5 wt. %) are characterized by low initial 87Sr/86Sr, relatively high 143Nd/144Nd, 206Pb/204Pb and 176Hf/177Hf ratios, and highly variable 207Pb/204Pb and 208Pb/204Pb ratios. Group B pyroxenites (Al2O3 < 14 wt. %) have isotopic signatures characterized by relatively high initial 87Sr/86Sr and low 143Nd/144Nd, 206Pb/204Pb and 176Hf/177Hf ratios. Group C pyroxenites (Al2O3 ˜ 15 wt. %) display relatively low initial 87Sr/86Sr and 206Pb/204Pb ratios, high 143Nd/144Nd and 176Hf/177Hf ratios, and 207Pb/204Pb and 208Pb/204Pb ratios similar to Group B pyroxenites. The major and trace element, and isotopic compositions of the studied Ronda and Beni Bousera UHP garnet pyroxenites lend support to the "Marble Cake Mantle" model [7] for the genesis of these pyroxenites. This model envisions the mantle source of oceanic basalts as a mélange of subducted, ancient oceanic crust —-represented by garnet pyroxenites in orogenic peridotites—- intimately mixed with peridotites by mantle convection. The present study reveals, however, that besides this exotic component of ancient recycled oceanic crust, the genesis of these pyroxenites requires a previously unnoticed component of recycled lower continental crust akin to the lower crustal section of the lithosphere where these UHP garnet pyroxenites now reside in. The results of this study provide a new recipe for the marble cake hypothesis for the genesis of UHP garnet pyroxenites in orogenic peridotites. Furthermore, it establishes a connection between the genesis of UHP pyroxenites, the composition of the continental crust and the generation of Earth's mantle heterogeneities. References: [1] Pearson, D. G., Davies, G. R. & Nixon, P. H. (1993). Geochemical constraints on the petrogenesis of diamond facies pyroxenites from the Beni Bousera peridotite massif, North Morocco. Journal of Petrology 34, 125-172. [2] Blichert-Toft, J., Albarède, F. & Kornprobst, J. (1999). Lu-Hf Isotope systematics of garnet pyroxenites from Beni Bousera, Morocco: implications for basalt origin. Science 283, 1303-1306. [3] Garrido, C. J. & Bodinier, J. L. (1999). Diversity of mafic rocks in the Ronda peridotite: Evidence for pervasive melt-rock reaction during heating of subcontinental lithosphere by upwelling asthenosphere. Journal of Petrology 40, 729-754. [4] Marchesi, C., Garrido, C.J., Bosch, D., Bodinier, J.-L., Gervilla, F., Hidas, K., 2013. Mantle refertilization by melts of crustal-derived garnet pyroxenite: Evidence from the Ronda peridotite massif, southern Spain. Earth and Planetary Science Letters 362, 66-75. doi: 10.1016/j.epsl.2012.11.047. [5] Marchesi, C., Dale, C.W., Garrido, C.J., Pearson, D.G., Bosch, D., Bodinier, J.-L., Gervilla, F., Hidas, K., 2014. Fractionation of highly siderophile elements in refertilized mantle: Implications for the Os isotope composition of basalts. Earth and Planetary Science Letters 400, 33-44. doi: 10.1016/j.epsl.2014.05.025 [6] Montanini, A. & Tribuzio, R. (2015). Evolution of recycled crust within the mantle: Constraints from the garnet pyroxenites of the External Ligurian ophiolites (northern Apennines, Italy). Geology 43, 911-914. [7] Allègre, C. J. & Turcotte, D. L. (1986). Implications of a two-component marble-cake mantle. Nature 323, 123-127.

Chapter 16Tracing Nitrogen Sources and Cycling in Catchments

USGS Publications Warehouse

Kendall, Carol

1998-01-01

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

Latest developments for low-power infrared laser-based trace gas sensors for sensor networks

NASA Astrophysics Data System (ADS)

So, Stephen; Thomazy, David; Wang, Wen; Marchat, Oscar; Wysocki, Gerard

2011-09-01

Academic and industrial researchers require ultra-low power, compact laser based trace-gas sensor systems for the most demanding environmental and space-borne applications. Here the latest results from research projects addressing these applications will be discussed: 1) an ultra-compact CO2 sensor based on a continuous wave quantum cascade laser, 2) an ultra-sensitive Faraday rotation spectrometer for O2 detection, 3) a fully ruggedized compact and low-power laser spectrometer, and 4) a novel non-paraxial nonthin multipass cell. Preliminary tests and projection for performance of future sensors based on this technology is presented.

Introduction to IdentiFINDERs

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

Rees, Brian G.

These are slides from a presentation. The identiFINDER provides information on radiation levels. It can automatically identify isotopes in its library. It can save spectra for transfer to a computer, and has a 4-8 hour battery life. The following is covered: an overview, operating modes, getting started, finder mode, search, identification mode, dose & rate, warning & alarm, options (ultra LGH), options (identifinder2), and general procedure.

Trace element profiles in modern horse molar enamel as tracers of seasonality: Evidence from micro-XRF, LA-ICP-MS and stable isotope analysis

NASA Astrophysics Data System (ADS)

de Winter, Niels; Goderis, Steven; van Malderen, Stijn; Vanhaecke, Frank; Claeys, Philippe

2016-04-01

A combination of laboratory micro-X-ray Fluorescence (μXRF) and stable carbon and oxygen isotope analysis shows that trace element profiles from modern horse molars reveal a seasonal pattern that co-varies with seasonality in the oxygen isotope records of enamel carbonate from the same teeth. A combination of six cheek teeth (premolars and molars) from the same individual yields a seasonal isotope and trace element record of approximately three years recorded during the growth of the molars. This record shows that reproducible measurements of various trace element ratios (e.g., Sr/Ca, Zn/Ca, Fe/Ca, K/Ca and S/Ca) lag the seasonal pattern in oxygen isotope records by 2-3 months. Laser Ablation-ICP-Mass Spectrometry (LA-ICP-MS) analysis on a cross-section of the first molar of the same individual is compared to the bench-top tube-excitation μXRF results to test the robustness of the measurements and to compare both methods. Furthermore, trace element (e.g. Sr, Zn, Mg & Ba) profiles perpendicular to the growth direction of the same tooth, as well as profiles parallel to the growth direction are measured with LA-ICP-MS and μXRF to study the internal distribution of trace element ratios in two dimensions. Results of this extensive complementary line-scanning procedure shows the robustness of state of the art laboratory micro-XRF scanning for the measurement of trace elements in bioapatite. The comparison highlights the advantages and disadvantages of both methods for trace element analysis and illustrates their complementarity. Results of internal variation within the teeth shed light on the origins of trace elements in mammal teeth and their potential use for paleo-environmental reconstruction.

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

NASA Astrophysics Data System (ADS)

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

2012-01-01

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

Assimilation of benzene carbon through multiple trophic levels traced by different stable isotope probing methodologies.

PubMed

Bastida, Felipe; Jechalke, Sven; Bombach, Petra; Franchini, Alessandro G; Seifert, Jana; von Bergen, Martin; Vogt, Carsten; Richnow, Hans H

2011-08-01

The flow of benzene carbon along a food chain consisting of bacteria and eukaryotes, including larvae (Diptera: Chironomidae), was evaluated by total lipid fatty acids (TLFAs)-, amino acid- and protein-stable isotope probing (SIP). A coconut-fibre textile, colonized by a benzene-degrading biofilm, was sampled in a system established for the remediation of benzene, toluene, ethylbenzene and xylenes (BTEX)-polluted groundwater and incubated with (12)C- and [(13)C(6)]-benzene (>99 at.%) in a batch-scale experiment for 2-8 days. After 8 days, Chironomus sp. larvae were added to study carbon flow to higher trophic levels. Gas chromatography-combustion-isotope ratio monitoring mass spectrometry of TLFA showed increased isotope ratios in the (13)C-benzene-incubated biofilm. A higher (13)C-enrichment was observed in TLFAs, indicative of Gram-negative bacteria than for Gram-positive. Fatty acid indicators of eukaryotes showed significant (13)C-incorporation, but to a lower extent than bacterial indicators. Fatty acids extracted from larvae feeding on (13)C-biofilm reached an isotopic ratio of 1.55 at.%, illustrating that the larvae feed, to some extent, on labelled biomass. No (13)C-incorporation was detectable in larval proteins after their separation by sodium-dodecyl sulphate-polyacrylamide gel electrophoresis and analysis by nano-liquid-chromatography-mass spectrometry. The flow of benzene-derived carbon could be traced in a food web consisting of bacteria and eukaryotes. © 2011 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Considerations on ultra-trace analysis of phthalates in drinking water.

PubMed

Serôdio, P; Nogueira, J M F

2006-07-01

Stir bar sorptive extraction with liquid desorption followed by large volume injection and capillary gas chromatography coupled to mass spectrometry (SBSE-LD/LVI-GC-MS), had been applied for the determination of ultra-traces of seven-phthalates (dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, butyl benzyl phthalate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate and bis(1-octyl) phthalate) in drinking water samples, which are included in the priority lists set by several international regulatory organizations. Instrumental calibration under the selected-ion monitoring mode acquisition (LVI-GC-MS(SIM)), experimental parameters that could affect the SBSE-LD efficiency, as well as, the control of the contamination profile are fully discussed. Throughout systematic assays on 30 mL water samples spiked at the 0.40 microg/L level, it had been established that stir bars coated with 47 microL of polydimethylsiloxane, an equilibrium time of 60 min (1,000 rpm) and methanol as back extraction solvent, allowed the best analytical performance to monitor phthalates in water matrices. From the data obtained, good accuracy and a remarkable reproducibility (< 14.8%) were attained, providing experimental recovery data in agreement with the theoretical equilibrium described by the octanol-water partition coefficients (K(PDMS/W) approximately K(O/W)), with the exception of bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate and bis(1-octyl) phthalate, for which lower yields were measured. Additionally, a remarkable linear dynamic range between 25 and 2,000 ng/L (r(2)>0.99) and low detection limits (3-40 ng/L) were also achieved for the seven-phthalates studied. The application of the present method to monitor phthalates in tap and bottled mineral water samples, allowed convenient selectivity and high sensitivity up to 1.0 microg/L level, using the standard addition methodology. The proposed method showed to be feasible and sensitive with a low sample volume requirement to monitor phthalates in drinking water matrices at the ultra-trace level, in compliance with international regulatory directives on water quality.

The Chemistry of Ultra-Radiopure Materials

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

Miley, Harry S.; Aalseth, Craig E.; Day, Anthony R.

Ultra-pure materials are needed for the construction of the next generation of ultra-low level radiation detectors. These detectors are used for environmental research as well as rare nuclear decay experiments, e.g. probing the effective mass and character of the neutrino. Unfortunately, radioactive isotopes are found in most construction materials, either primordial isotopes, activation/spallation products from cosmic-ray exposure, or surface deposition of dust or radon progeny. Copper is an ideal candidate material for these applications. High-purity copper is commercially available and, when even greater radiopurity is needed, additional electrochemical purification can be combined with the final construction step, resulting in “electroformed”more » copper of extreme purity. Copper also offers desirable thermal, mechanical, and electrical properties. To bridge the gap between commercially-available high purity copper and the most stringent requirements of next-generation low-background experiments, a method of additional chemical purification is being developed based on well-known copper electrochemistry. This method is complemented with the co-development of surface cleaning techniques and more sensitive assay for both surface and bulk contamination. Developments in the electroplating of copper, surface cleaning, assay of U and Th in the bulk copper, and residual surface contamination will be discussed relative to goals of less than 1 microBq/kg Th.« less

Trace elements and common ions in southeastern Idaho snow: Regional air pollutant tracers for source area emissions

USGS Publications Warehouse

Abbott, M.; Einerson, J.; Schuster, P.; Susong, D.; Taylor, Howard E.; ,

2004-01-01

Snow sampling and analysis methods which produce accurate and ultra-low measurements of trace elements and common ion concentration in southeastern Idaho snow, were developed. Snow samples were collected over two winters to assess trace elements and common ion concentrations in air pollutant fallout across the southeastern Idaho. The area apportionment of apportionment of fallout concentrations measured at downwind location were investigated using pattern recognition and multivariate statistical technical techniques. Results show a high level of contribution from phosphates processing facilities located outside Pocatello in the southern portion of the Eastern Snake River Plain, and no obvious source area profiles other than at Pocatello.

A simple {sup 197}Hg RNAA procedure for the determination of mercury in urine, blood, and tissue

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

Blotcky, A.J.; Rack, E.P.; Meade, A.G.

1995-12-31

Mercury has been implicated as a causal agent in such central nervous system diseases as Alzheimer`s and Parkinson`s. Consequently, there has been increased interest in the determination of ultra-trace-level mercury in biological matrices, especially in tissue. While such nonnuclear techniques as cold vapor atomic absorption spectrometry and cold vapor atomic fluorescence spectrometry have been employed routinely for mercury determinations in urine and blood, there is a paucity of nonnuclear techniques for the determination of mercury in the low parts-per-billion range in biological tissue. As pointed out by Fardy and Warner, instrumental and radiochemical neutron activation analysis (INAA and RNAA) requiremore » no blank determinations in contrast to nonnuclear analytical techniques employing digestion and/or chemical operations. Therefore, INAA and RNAA become the obvious choices for determination of ultra-trace levels of mercury in tissue. Most separation methods reported in the literature require different and separate methodologies for mercury determinations in urine, blood, or tissue. The purposes of this study are to develop a single methodology for the determination of low levels of mercury in all biological matrices by RNAA and to optimize parameters necessary for an efficacious trace-level determination. Previously, few studies have taken into account the effects of the Szilard-Chalmers reactions of the radioactivatable analyte within a biological matrix. It also would appear that little attention has been given to the optimum postirradiation carrier concentration of the analyte species necessary. This study discusses these various considerations.« less

Re-187-Os-187, Pt-190-Os-186 Isotopic and Highly Siderophile Element Systematics of Group IVA Irons

NASA Technical Reports Server (NTRS)

Walker, R. J.; McCoy, T. J.; Schulte, R. F.; McDonough, W. F.; Ash, R. D.

2005-01-01

We have recently completed Re-187-Os-187 and Pt-190-Os-186 isotopic and elemental studies of the two largest magmatic iron meteorite groups, IIAB and IIIAB [1]. These studies revealed closed-system behavior of both isotopic systems, but complex trace element behavior for Re, Pt and Os in group IIIAB. Here we examine isotopic and trace elemental systematics of group IVA irons. The IVA irons are not as extensively fractionated as IIAB and IIIAB and their apparently less complex crystallization history may make for more robust interpretation of the relative partitioning behavior of Re, Pt and Os, as well as the other highly siderophile elements (HSE) measured here; Pd, Ru and Ir [e.g. 2]. An additional goal of our continuing research plan for iron meteorites is to assess the possibility of relating certain ungrouped irons with major groups via trace element modeling. Here, the isotopic and trace element systematics of the ungrouped irons Nedagolla and EET 83230 are compared with the IVA irons.

Simultaneous determination of chlorantraniliprole and cyantraniliprole in fruits, vegetables and cereals using ultra-high-performance liquid chromatography-tandem mass spectrometry with the isotope-labelled internal standard method.

PubMed

Pan, Xinglu; Dong, Fengshou; Xu, Jun; Liu, Xingang; Chen, Zenglong; Liu, Na; Chen, Xixi; Tao, Yan; Zhang, Hongjun; Zheng, Yongquan

2015-05-01

A reliable and sensitive isotope-labelled internal standard method for simultaneous determination of chlorantraniliprole and cyantraniliprole in fruits (apple and grape), vegetables (cucumber and tomato) and cereals (rice and wheat) using ultra-high-performance liquid chromatography-tandem mass spectrometry was developed. Isotope-labelled internal standards were effective in compensating for the loss in the pretreatment and overcoming the matrix effect. The analytes were extracted with acetonitrile and cleaned up with different kinds of sorbents. The determination of the target compounds was achieved in less than 4 min using a T3 column combined with an electrospray ionization source in positive mode. The overall average relative recoveries in all matrices at three spiking levels (10, 20 and 50 μg kg(-1)) ranged from 95.5 to 106.2 %, with all relative standard deviations being less than 14.4 % for all analytes. The limits of detection did not exceed 0.085 μg kg(-1) and the limits of quantification were below 0.28 μg kg(-1) in all matrices. The method was demonstrated to be convenient and accurate for the routine monitoring of chlorantraniliprole and cyantraniliprole in fruits, vegetables and cereals.

Long-term feeding ecology and habitat use in harbour porpoises Phocoena phocoena from Scandinavian waters inferred from trace elements and stable isotopes.

PubMed

Fontaine, Michaël C; Tolley, Krystal A; Siebert, Ursula; Gobert, Sylvie; Lepoint, Gilles; Bouquegneau, Jean-Marie; Das, Krishna

2007-01-17

We investigated the feeding ecology and habitat use of 32 harbour porpoises by-caught in 4 localities along the Scandinavian coast from the North Sea to the Barents Sea using time-integrative markers: stable isotopes (delta13C, delta15N) and trace elements (Zn, Cu, Fe, Se, total Hg and Cd), in relation to habitat characteristics (bathymetry) and geographic position (latitude). Among the trace elements analysed, only Cd, with an oceanic specific food origin, was found to be useful as an ecological tracer. All other trace elements studied were not useful, most likely because of physiological regulation and/or few specific sources in the food web. The delta13C, delta15N signatures and Cd levels were highly correlated with each other, as well as with local bathymetry and geographic position (latitude). Variation in the isotopic ratios indicated a shift in harbour porpoise's feeding habits from pelagic prey species in deep northern waters to more coastal and/or demersal prey in the relatively shallow North Sea and Skagerrak waters. This result is consistent with stomach content analyses found in the literature. This shift was associated with a northward Cd-enrichment which provides further support to the Cd 'anomaly' previously reported in polar waters and suggests that porpoises in deep northern waters include Cd-contaminated prey in their diet, such as oceanic cephalopods. As stable isotopes and Cd provide information in the medium and the long term respectively, the spatial variation found, shows that harbour porpoises experience different ecological regimes during the year along the Scandinavian coasts, adapting their feeding habits to local oceanographic conditions, without performing extensive migration.

An Ultra-Sensitive Method for the Analysis of Perfluorinated Alkyl Acids in Drinking Water using a Column Switching High-Performance Liquid Chromatography Tandem Mass Spectrometry

EPA Science Inventory

In epidemiological research, it has become increasingly important to assess subjects' exposure to different classes of chemicals in multiple environmental media. It is a common practice to aliquot limited volumes of samples into smaller quantities for specific trace level chemi...

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

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.

Ca-,Al-rich inclusions in the unique chondrite ALH85085 - Petrology, chemistry, and isotopic compositions

NASA Technical Reports Server (NTRS)

Kimura, Makoto; El-Goresy, Ahmed; Palme, Herbert; Zinner, Ernst

1993-01-01

A comprehensive study is performed for the Ca-,Al-rich inclusions (CAIs) in the unique chondrite ALH85085. The ALH85085 inclusions are smaller (5-80 microns) and more refractory than their counterparts in carbonaceous chondrites. The study includes 42 inclusions for petrography and mineralogy, 15 for bulk major and minor element chemical composition, six for Mg-Al isotopic systematics, 10 for Ca isotopes, nine for Ti isotopes, and six for trace element abundances. In addition, oxygen-isotopic compositions were determined in minerals from a single inclusion. No correlation is found between mineralogy, major element chemistry, and trace element abundances. It is further shown that the high-temperature geochemical behavior of ultrarefractory trace elements is decoupled from that of the major elements Ca and Ti (Ti is correlated with the relatively volatile elements Nb and Yb) implying that perovskite is of only minor importance as carrier of ultrarefractories.

Design study of an ultra-compact superconducting cyclotron for isotope production

NASA Astrophysics Data System (ADS)

Smirnov, V.; Vorozhtsov, S.; Vincent, J.

2014-11-01

A 12.5 MeV, 25 μA, proton compact superconducting cyclotron for medical isotope production has been designed and is currently in fabrication. The machine is initially aimed at producing 13N ammonia for Positron Emission Tomography (PET) cardiology applications. With an ultra-compact size and cost-effective price point, this system will offer clinicians unprecedented access to the preferred radiopharmaceutical isotope for cardiac PET imaging. A systems approach that carefully balanced the subsystem requirements coupled to precise beam dynamics calculations was followed. The system is designed to irradiate a liquid target internal to the cyclotron and to minimize the need for radiation shielding. The main parameters of the cyclotron, its design, and principal steps of the development work are presented here.

Al-26, Pu-244, Ti-50, REE, and trace element abundances in hibonite grains from CM and CV meteorites

NASA Technical Reports Server (NTRS)

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

1987-01-01

Hibonites from the CM meteorites Murchison, Murray, and Cold Bokkeveld, and hibonites and Ti-rich pyroxene from the CV chondrite Allende are studied. Electron microprobe measurements of major element concentrations and track and ion probe measurements of Mg and Ti isotopic ratios, rare earth elements (REEs), and trace element abundances are analyzed. Correlations between isotopic anomalies in Ti, Al-26, Pu-244, and Mg-26(asterisk) are examined. Ti isotopic anomalies are compared with REE and trace element abundance patterns. Reasons for the lack of Al-26 in the hibonites are investigated and discussed. It is observed that there is no correlation between the Ti isotopic compositions, and the presence of Mg-26(asterisk), Pu-244, and REE and trace element patterns in individual hibonite samples. The data reveal that hibonites are not interstellar dust grains but formed on a short time scale and in localized regions of the early solar system.

The Great White Guppy: Top Predator

NASA Astrophysics Data System (ADS)

Michalski, G. M.

2011-12-01

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

URBAN STORMWATER TRACING WITH THE NATURALLY OCCURRING DEUTERIUM ISOTOPE

EPA Science Inventory

Measurements of the naturally-occurring deuterium isotope assist the tracing of water components during wet-weather flows in an urban watershed. A transect of installations in the vadose and saturated zones was completed in the vicinity of a small stream and storm sewer. High-r...

Early Earth differentiation [rapid communication

NASA Astrophysics Data System (ADS)

Walter, Michael J.; Trønnes, Reidar G.

2004-09-01

The birth and infancy of Earth was a time of profound differentiation involving massive internal reorganization into core, mantle and proto-crust, all within a few hundred million years of solar system formation ( t0). Physical and isotopic evidence indicate that the formation of iron-rich cores generally occurred very early in planetesimals, the building blocks of proto-Earth, within about 3 million years of t0. The final stages of terrestrial planetary accretion involved violent and tremendously energetic giant impacts among core-segregated Mercury- to Mars-sized objects and planetary embryos. As a consequence of impact heating, the early Earth was at times partially or wholly molten, increasing the likelihood for high-pressure and high-temperature equilibration among core- and mantle-forming materials. The Earth's silicate mantle harmoniously possesses abundance levels of the siderophile elements Ni and Co that can be reconciled by equilibration between iron alloy and silicate at conditions comparable to those expected for a deep magma ocean. Solidification of a deep magma ocean possibly involved crystal-melt segregation at high pressures, but subsequent convective stirring of the mantle could have largely erased nascent layering. However, primitive upper mantle rocks apparently have some nonchondritic major and trace element refractory lithophile element ratios that can be plausibly linked to early mantle differentiation of ultra-high-pressure mantle phases. The geochemical effects of crystal fractionation in a deep magma ocean are partly constrained by high-pressure experimentation. Comparison between compositional models for the primitive convecting mantle and bulk silicate Earth generally allows, and possibly favors, 10-15% total fractionation of a deep mantle assemblage comprised predominantly of Mg-perovskite and with minor but geochemically important amounts of Ca-perovskite and ferropericlase. Long-term isolation of such a crystal pile is generally consistent with isotopic constraints for time-integrated Sm/Nd and Lu/Hf ratios in the modern upper mantle and might account for the characteristics of some mantle isotope reservoirs. Although much remains to be learned about the earliest formative period in the Earth's development, a convergence of theoretical, physical, isotopic and geochemical arguments is beginning to yield a self-consistent portrait of the infant Earth.

Tracing the origins, migrations, and other movements of fishes using stable isotopes

EPA Science Inventory

Although stable isotope studies are increasingly used to trace fish origin, migration, and movement, the approach has not been as widely adopted as extrinsic marking and tagging. This is, at least in part, because many fishery scientists do not have a background in biogeochemistr...

Origins of diamond-forming fluids: An isotopic and trace element study of diamonds and silicates from diamondiferous xenoliths

NASA Astrophysics Data System (ADS)

Laiginhas, Fernando; Pearson, D. Graham; McNeill, John; Gurney, John; Nowell, Geoff; Ottley, Chris

2010-05-01

While there is increasing understanding of the age of formation and nature of "gem" diamonds, significant debate revolves around the nature of the fluids/melts from which they form. Stable C and N isotopes have been shown to be highly variable and yet the role of subduction-related fluids remains strongly debated. Recent studies on fibrous diamonds have yielded new trace and major element data (e.g., Weiss et al., 2009) that, together with new radiogenic isotope data (Klein BenDavid et al., 2010) indicate such diamonds grow from fluids that comprise mixtures of hydrous silicic, hydrous saline and carbonatitic fluids, derived from different source components of asthenospheric and lithospheric origin. However, until now such data has been lacking from gem diamonds. Using a new laser-based technique (McNeill et al., 2009), we have analysed a suite of diamonds plus co-existing host silicates from several diamondiferous xenoliths (6 harzburgites, 1 eclogite) from the Finsch and Newlands kimberlites in order to try to understand the fluid compositions that produce gem diamonds and better understand their effects of their mantle wall rocks. Diamonds from the xenoliths show a wide variety of trace element enrichment levels. While the eclogitic diamond shows similar trace element systematics to some of the harzburgitic diamonds there are significant differences within the harzburgitic diamonds from different xenoliths, with those from Finsch being significantly enriched in Ba, Sr and Pb relative to other elements. Nd isotope data on the host silicates is variable and dominantly unradiogenic, indicative of long-term enrichment typically associated with the source of some diamond-forming fluids. We will present Sr isotopic data on host silicates and diamond fluids to constrain whether the "gem" diamonds require the complex sources of fluids that characterise the growth of fibrous diamonds. 1) Y. Weiss, R. Kessel, W.L. Griffin, I. Kiflawi, O. Klein-BenDavid, D.R. Bell, J.W. Harris and O. Navon (2009). A new model for the evolution of diamond-forming fluids: Evidence from microinclusion-bearing diamonds from Kankan, Guinea. Lithos 112, Supp. 2: 660-674. 2) O. Klein-BenDavid, D.G. Pearson, G.M. Nowell, C. Ottley, J.C.R. McNeill, P. Cartigny (2010). Mixed fluid sources involved in diamond growth constrained by Sr-Nd-Pb-C-N isotopes and trace elements. EPSL 289, 1-2: 123-133. 3) J. McNeill, D.G. Pearson, O. Klein-BenDavid, G.M. Nowell, C.J. Ottley and I. Chinn (2009). Quantitative analysis of trace element concentrations in some gem-quality diamonds. J. Phys.: Condens. Matter 21: 364207 (13pp).

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

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

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

1989-12-01

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

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.

Uniform deposition of uranium hexafluoride (UF6): Standardized mass deposits and controlled isotopic ratios using a thermal fluorination method

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

McNamara, Bruce K.; O’Hara, Matthew J.; Casella, Andrew M.

2016-07-01

Abstract: We report a convenient method for the generation of volatile uranium hexafluoride (UF6) from solid uranium oxides and other uranium compounds, followed by uniform deposition of low levels of UF6 onto sampling coupons. Under laminar flow conditions, UF6 is shown to interact with surfaces within the chamber to a highly predictable degree. We demonstrate the preparation of uranium deposits that range between ~0.01 and 470±34 ng∙cm-2. The data suggest the method can be extended to creating depositions at the sub-picogram∙cm-2 level. Additionally, the isotopic composition of the deposits can be customized by selection of the uranium source materials. Wemore » demonstrate a layering technique whereby two uranium solids, each with a different isotopic composition, are employed to form successive layers of UF6 on a surface. The result is an ultra-thin deposit of UF6 that bears an isotopic signature that is a composite of the two uranium sources. The reported deposition method has direct application to the development of unique analytical standards for nuclear safeguards and forensics.« less

Assessment of marine-derived nutrients in the Copper River Delta, Alaska, using natural abundance of the stable isotopes of nitrogen, sulfur, and carbon

USGS Publications Warehouse

Kline, Thomas C.; Woody, Carol Ann; Bishop, Mary Anne; Powers, Sean P.; Knudsen, E. Eric

2007-01-01

We performed nitrogen, sulfur, and carbon stable isotope analysis (SIA) on maturing and juvenile anadromous sockeye and coho salmon, and periphyton in two Copper River delta watersheds of Alaska to trace salmonderived nutrients during 2003–2004. Maturing salmon were isotopically enriched relative to alternate freshwater N, S, and C sources as expected, with differences consistent with species trophic level differences, and minor system, sex, and year-to-year differences, enabling use of SIA to trace these salmon-derived nutrients. Periphyton naturally colonized, incubated, and collected using Wildco Periphtyon Samplers in and near spawning sites was 34S- and 15N-enriched, as expected, and at all freshwater sites was 13C-depleted. At nonspawning and coho-only sites, periphyton 34S and 15N was generally low. However, 34S was low enough at some sites to be suggestive of sulfate reduction, complicating the use of S isotopes. Juvenile salmon SIA ranged in values consistent with using production derived from re-mineralization as well as direct utilization, but only by a minority fraction of coho salmon. Dependency on salmon-derived nutrients ranged from relatively high to relatively low, suggesting a space-limited system. No one particular isotope was found to be superior for determining the relative importance of salmon-derived nutrients.

Compound-specific isotopes of fatty acids as indicators of trophic interactions in the East China Sea ecosystem

NASA Astrophysics Data System (ADS)

Wu, Ying; Wang, Na; Zhang, Jing; Wan, Ruijing; Dai, Fangqun; Jin, Xianshi

2016-09-01

The composition and compound-specific isotopes of fatty acids were studied within food webs in the East China Sea. Lipid-normalized stable carbon isotopes of total organic carbon had a good correlation with trophic level. Variations in fatty acid compositions among diff erent species were observed but were unclear. Diff erent dietary structures could be traced from molecular isotopes of selected fatty acids in the Shiba shrimp ( Matapenaeus joyneri), the coastal mud shrimp ( Solenocera crassicornis) and the northern Maoxia shrimp ( Acetes chinensis). Both M. joyneri and S. crassicornis are mainly benthos feeders, while A. chinensis is a pelagic species, although they have a similar fatty acid composition. There was a good correlation for isotopes of arachidonic acid (C20:4n6; ARA) and docosahexaenoic acid (C22:6n3; DHA) among pelagic species from higher trophic levels. The isotopic compositions of DHA in benthic species were more negative than those of pelagic species at the same trophic level. The fact that the diet of benthic species contains more degraded items, the carbon isotopes of which are derived from a large biochemical fraction, may be the reason for this variation. A comparative study of benthic and pelagic species demonstrated the diff erent carbon sources in potential food items and the presence of a more complex system at the water-sediment interface.

New Hafnium Isotope and Trace Element Constraints on the Role of a Plume in Genesis of the Eastern Snake River Plain Basalts, Idaho

NASA Astrophysics Data System (ADS)

Taylor, R. D.; Reid, M. R.; Blichert-Toft, J.

2009-12-01

Bimodal volcanism associated with the eastern Snake River Plain (ESRP)-Yellowstone Plateau province has persisted since approximately 16 Ma. A time-transgressive track of rhyolitic eruptions which young progressively to the east and parallel the motion of the North American plate are overlain by younger basalts with no age progression. Interpretations for the origin of these basalts range from a thermo-chemical mantle plume to incipient melting of the shallow upper mantle, and remain controversial. The enigmatic ESRP basalts are characterized by high 3He/4He, diagnostic of a plume source, but also by lithophile radiogenic isotope signatures that are more enriched than expected for plume-derived OIBs. These features could possibly be caused by isotopic decoupling associated with shallow melting of a hybridized upper mantle, or derivation from an atypical mantle plume, or both by way of mixing. New Hf isotope and trace element data further constrain potential sources for the ESRP basalts. Their Hf isotopic signatures (ɛHf = +0.1 to -5.8) are moderately enriched and consistently fall above or in the upper part of the field of OIBs, with similar Nd isotope signatures (ɛNd = -2.0 to -5.8), indicating a source with high time-integrated Lu/Hf compared with Sm/Nd. The isotopic compositions of the basalts lie between those of Archean SCML and a more depleted end-member source, suggestive of contributions from at least two sources. The grouping of isotopic characteristics is compact compared to other regional volcanism, implying that the hybridization process is highly reproducible within the ESRP. Minor localized differences in isotopic composition may signify local variations in the relative proportions of the end-members. Trace element patterns also support genesis of the ESRP basalts from an enriched source. Our data detect evidence of deeper contributions derived from the garnet-stability field, and a greater affinity of the trace element signatures to plume sources than to sources in the mantle lithosphere. The Hf isotope and trace element characteristics of the ESRP basalts thus support a model of derivation from a deep mantle plume with additional melt contributions and isotopic overprinting from SCML.

Major, Trace Element Concentration and Triple-Oxygen Isotope Compositions of G- and I-Type Spherules from the Sør Rondane Mountains, East Antarctica

NASA Astrophysics Data System (ADS)

Soens, B.; Goderis, S.; Greenwood, R. C.; McKibbin, S.; Van Ginneken, M.; Vanhaecke, F.; Debaille, V.; Franchi, I. A.; Claeys, Ph.

2017-07-01

We present new major, trace element concentration (LA-ICP-MS) and triple-oxygen isotope (LF-IRMS) data for G- and I-type cosmic spherules. This study suggests that both types of micrometeorites may originate from ordinary chondrite parent bodies.

Beat frequency quartz-enhanced photoacoustic spectroscopy for fast and calibration-free continuous trace-gas monitoring

PubMed Central

Wu, Hongpeng; Dong, Lei; Zheng, Huadan; Yu, Yajun; Ma, Weiguang; Zhang, Lei; Yin, Wangbao; Xiao, Liantuan; Jia, Suotang; Tittel, Frank K.

2017-01-01

Quartz-enhanced photoacoustic spectroscopy (QEPAS) is a sensitive gas detection technique which requires frequent calibration and has a long response time. Here we report beat frequency (BF) QEPAS that can be used for ultra-sensitive calibration-free trace-gas detection and fast spectral scan applications. The resonance frequency and Q-factor of the quartz tuning fork (QTF) as well as the trace-gas concentration can be obtained simultaneously by detecting the beat frequency signal generated when the transient response signal of the QTF is demodulated at its non-resonance frequency. Hence, BF-QEPAS avoids a calibration process and permits continuous monitoring of a targeted trace gas. Three semiconductor lasers were selected as the excitation source to verify the performance of the BF-QEPAS technique. The BF-QEPAS method is capable of measuring lower trace-gas concentration levels with shorter averaging times as compared to conventional PAS and QEPAS techniques and determines the electrical QTF parameters precisely. PMID:28561065

Ultra-trace analysis of hormones, pharmaceutical substances, alkylphenols and phthalates in two French natural mineral waters.

PubMed

Dévier, Marie-Hélène; Le Menach, Karyn; Viglino, Liza; Di Gioia, Lodovico; Lachassagne, Patrick; Budzinski, Hélène

2013-01-15

The aim of this work was to investigate the potential presence of a broad range of organic compounds, such as hormones, alkylphenols, bisphenol A and phthalates, as well as pharmaceutical substances in two brands of bottled natural mineral waters (Evian and Volvic, Danone). The phthalates were determined by solid-phase microextraction coupled to gas chromatography-mass spectrometry (SPME-GC-MS) and the other compounds by liquid chromatography-tandem mass spectrometry (LC-MS/MS) or gas chromatography-mass spectrometry (GC-MS) after solid-phase extraction. The potential migration of alkylphenols, bisphenol A and phthalates from polyethylene terephthalate (PET) bottles was also investigated under standardized test conditions. Evian and Volvic natural mineral waters contain none of the around 120 targeted organic compounds. Traces of 3 pharmaceuticals (ketoprofen, salicylic acid, and caffeine), 3 alkylphenols (4-nonylphenol, 4-t-octylphenol, and 4-nonylphenol diethoxylate), and some phthalates including di(2-ethylhexyl)phthalate (DEHP) were detected in the samples, but they were also present in the procedural blanks at similar levels. The additional test procedures demonstrated that the few detected compounds originated from the background laboratory contamination. Analytical procedures have been designed both in the bottling factory and in the laboratory in order to investigate the sources of DEHP and to minimize to the maximum this unavoidable laboratory contamination. It was evidenced that no migration of the targeted compounds from bottles occurred under the test conditions. The results obtained in this study underline the complexity of reaching a reliable measure to qualify the contamination of a sample at ultra-trace level, in the field of very pure matrices. The analytical procedures involving glassware, equipment, hoods, and rooms specifically dedicated to trace analysis allowed us to reach reliable procedural limits of quantification at the ng/L level, by lowering the background laboratory contamination. Copyright © 2012 Elsevier B.V. All rights reserved.

New Isotopic Tracers for Shale Gas and Hydraulic Fracturing Fluids

EPA Pesticide Factsheets

The combined application of geochemistry, stable isotopes (δ18O, δ2H), strontium isotopes (87Sr/86Sr), boron isotopes (δ11B), and radium isotopes (228Ra/226Ra) provides a unique methodology for tracing and monitoring shale gas and fracking fluids in the environment.

Stratigraphic implications of trace element and strontium-isotope analyses of Kimmeridgian shell calcite from the Lower Saxony Basin, Germany

NASA Astrophysics Data System (ADS)

Zuo, Fanfan; Heimhofer, Ulrich; Huck, Stefan; Erbacher, Jochen; Bodin, Stephane

2017-04-01

Stratigraphic uncertainties due to the lack of open marine marker fossils (e.g. ammonites) hamper the precise age assignment and stratigraphic correlation of Kimmeridgian strata found in the Lower Saxony Basin of Northern Germany. Correlation of these deposits with the Jurassic standard ammonite zonation is still difficult, since the existing ostracod biostratigraphy is facies-controlled and of only limited stratigraphic precision. In this study, a chemostratigraphic approach has been chosen and biogenic shell material produced by brachiopods, oysters and lithiotids is evaluated for its reliability to act as proxy of the original Jurassic seawater strontium isotope composition. Low-Mg calcite shells have been collected from three stratigraphic sections accessible in open-cast quarries located in the Lower Saxony Basin of Northern Germany. In order to identify diagenetically altered shell calcite, trace element and stable isotope analysis of 227 calcite samples (oysters=101; brachiopods=60; Trichites=52) has been carried out. The geochemical results reveal that (1) concentration of different trace elements varies between the different groups of shell-forming organisms, which may be related to vital effects and (2) high strontium contents, low Mn and Fe contents and the lack of correlation between these elements indicate near-pristine calcite shells, and therefore shells are supposed to record the ambient sea water composition during the Late Jurassic. Strontium-isotope (87Sr/86Sr) analysis of diagenetically screened samples indicates an Early Kimmeridgian age of the studied deposits, which is in accordance with ostracod biostratigraphic data. An increasing trend in 87Sr/86Sr with stratigraphic height fits well with the global strontium-isotope curve. Besides, similar 87Sr/86Sr ratios derived from different organisms from a single stratigraphic level highlight the suitability of the shells for strontium-isotope stratigraphy. Despite the shallow-marine character of the studied deposits, no evidence for significant riverine influence on the strontium-isotope signature is observed. The new chemostratigraphic data will provide a more precise age assignment for Kimmeridgian strata in the Lower Saxony Basin and thus enable the establishment of a solid integrated stratigraphic scheme that can be used for correlation on both regional and global scale.

Effects of cleaning methods upon preservation of stable isotopes and trace elements in shells of Cyprideis torosa (Crustacea, Ostracoda): Implications for palaeoenvironmental reconstruction

NASA Astrophysics Data System (ADS)

Roberts, L. R.; Holmes, J. A.; Leng, M. J.; Sloane, H. J.; Horne, D. J.

2018-06-01

The trace element (Sr/Ca and Mg/Ca) and stable isotope (δ18O and δ13C) geochemistry of fossil ostracod valves provide valuable information, particularly in lacustrine settings, on palaeo-water composition and palaeotemperature. The removal of sedimentary and organic contamination prior to geochemical analysis is essential to avoid bias of the results. Previous stable isotope and trace element work on ostracod shells has, however, employed different treatments for the removal of contamination beyond simple 'manual' cleaning using a paint brush and methanol under a low-power binocular microscope. For isotopic work pre-treatments include chemical oxidation, vacuum roasting and plasma ashing, and for trace element work sonication, chemical oxidation and reductive cleaning. The impact of different treatments on the geochemical composition of the valve calcite has not been evaluated in full, and a universal protocol has not been established. Here, a systematic investigation of the cleaning methods is undertaken using specimens of the ubiquitous euryhaline species, Cyprideis torosa. Cleaning methods are evaluated by undertaking paired analyses on a single carapace (comprising two valves); in modern ostracods, whose valves are assumed to be unaltered, the two valves should have identical geochemical and isotopic composition. Hence, when one valve is subjected to the chosen treatment and the other to simple manual cleaning any difference in composition can confidently be assigned to the treatment method. We show that certain cleaning methods have the potential to cause alteration to the geochemical signal, particularly Mg/Ca and δ18O, and hence have implications for palaeoenvironmental reconstructions. For trace-element determinations we recommend cleaning by sonication and for stable isotope analysis, oxidation by hydrogen peroxide. These methods remove contamination, yet do not significantly alter the geochemical signal.

Mass Spectrometric Determination of Uranium and Thorium in High Radiopurity Polymers Using Ultra Low Background Electroformed Copper Crucibles for Dry Ashing.

PubMed

Arnquist, Isaac J; Hoppe, Eric J; Bliss, Mary; Grate, Jay W

2017-03-07

A rapid new method for determining the U and Th mass concentrations in high radiopurity plastics is described, consisting of (1) dry ashing the plastic sample and tracers in low mass crucibles made of ultra low background electroformed copper (ULB EF-Cu) foil cut and folded into boats, (2) dissolving both the ash and the boat in acid, (3) performing a column separation to remove copper, and (4) determining the elements of interest by isotope dilution mass spectrometry. This method was demonstrated on both unfluorinated and fluorinated plastics, demonstrating high tracer recoveries and detection limits to pg/g (i.e., parts per trillion) levels or below, corresponding to μBq/kg of material. Samples of biomedical polyester (Max-Prene 955) and a fluoropolymer (polyvinylidene fluoride, PVDF) were analyzed in powder raw material forms as well as solids in the form of pellets or injection molded parts. The polyester powder contained 6 pg/g and 2 pg/g for 232 Th and 238 U, respectively. These levels correspond to 25 and 25 μBq/kg radioactivity, respectively. Determinations on samples of PVDF powder were typically below 1 pg/g for 232 Th and 2 pg/g for 238 U, corresponding to 4 and 25 μBq/kg radioactivity, respectively. The use of low mass ULB EF-Cu boats for dry ashing successfully overcame the problem of crucible-generated contaminants in the analysis; absolute detection limits, calculated as 3 × standard deviation of the process blanks, were typically 20-100 fg within a sample set. Complete dissolution of the ash and low mass boat provided high tracer recoveries and provides a convincing method to recover both the tracer and sample isotopes when full equilibration of tracer isotopes with sample isotopes is not possible prior to beginning chemical sample processing on solids.

Mass Spectrometric Determination of Uranium and Thorium in High Radiopurity Polymers Using Ultra Low Background Electroformed Copper Crucibles for Dry Ashing

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

Arnquist, Isaac J.; Hoppe, Eric J.; Bliss, Mary

A rapid new method for determining the U and Th mass concentrations in high radiopurity plastics is described, consisting of 1) dry ashing the plastic sample and tracers in low mass crucibles made of ultra low background electroformed copper (ULB EF-Cu) foil cut and folded into boats, 2) dissolving both the ash and the boat in acid, 3) performing a column separation to remove copper, and 4) determining the elements of interest by isotope dilution mass spectrometry. This method was demonstrated on both unfluorinated and fluorinated plastics, demonstrating high tracer recoveries and detection limits to pg/g (i.e., parts per trillion)more » levels or below, corresponding to μBq/kg of material. Samples of biomedical polyester (Max-Prene® 955) and a fluoropolymer (polyvinylidene fluoride, PVDF) were analyzed in powder raw material forms as well as solids in the form of pellets or injection molded parts. The polyester powder contained 6 pg/g and 2 pg/g for Th and U respectively. These levels correspond to 25 and 25 μBq/kg radioactivity, respectively. Determinations on samples of PVDF powder were typically below 1 pg/g for Th and 2 pg/g for U, corresponding to 4 and 25 μBq/kg radioactivity, respectively. The use of low mass ULB EF-Cu boats for dry ashing successfully overcame the problem of crucible-generated contaminants in the analysis; absolute detection limits, calculated as 3 × standard deviation of the process blanks, were typically 20-100 fg within a sample set. Complete dissolution of the ash and low mass boat provided high tracer recoveries, and provides a convincing method to recover both the tracer and sample isotopes when full equilibration of tracer isotopes with sample isotopes is not possible prior to beginning chemical sample processing on solids.« less

Tracing biogeochemical subsidies from glacier runoff into Alaska's coastal marine food webs

USGS Publications Warehouse

Arimitsu, Mayumi L.; Hobson, Keith A.; Webber, D'Arcy N.; Piatt, John F.; Hood, Eran W.; Fellman, Jason B.

2018-01-01

Nearly half of the freshwater discharge into the Gulf of Alaska originates from landscapes draining glacier runoff, but the influence of the influx of riverine organic matter on the trophodynamics of coastal marine food webs is not well understood. We quantified the ecological impact of riverine organic matter subsidies to glacier-marine habitats by developing a multi-trophic level Bayesian three-isotope mixing model. We utilized large gradients in stable (δ13C, δ15N, δ2H) and radiogenic (Δ14C) isotopes that trace riverine and marine organic matter sources as they are passed from lower to higher trophic levels in glacial-marine habitats. We also compared isotope ratios between glacial-marine and more oceanic habitats. Based on isotopic measurements of potential baseline sources, ambient water and tissues of marine consumers, estimates of the riverine organic matter source contribution to upper trophic-level species including fish and seabirds ranged from 12% to 44%. Variability in resource use among similar taxa corresponded to variation in species distribution and life histories. For example, riverine organic matter assimilation by the glacier-nesting seabirds Kittlitz's murrelet (Brachyramphus brevirostris) was greater than that of the forest-nesting marbled murrelet (B. marmoratus). The particulate and dissolved organic carbon in glacial runoff and near surface coastal waters was aged (12100–1500 years BP 14C-age) but dissolved inorganic carbon and biota in coastal waters were young (530 years BP 14C-age to modern). Thus terrestrial-derived subsidies in marine food webs were primarily composed of young organic matter sources released from glacier ecosystems and their surrounding watersheds. Stable isotope compositions also revealed a divergence in food web structure between glacial-marine and oceanic sites. This work demonstrates linkages between terrestrial and marine ecosystems, and facilitates a greater understanding of how climate-driven changes in freshwater runoff have the potential to alter food web dynamics within coastal marine ecosystems in Alaska.

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.

Identifying the origins of local atmospheric deposition in the steel industry basin of Luxembourg using the chemical and isotopic composition of the lichen Xanthoria parietina.

PubMed

Hissler, Christophe; Stille, Peter; Krein, Andreas; Geagea, Majdi Lahd; Perrone, Thierry; Probst, Jean-Luc; Hoffmann, Lucien

2008-11-01

Trace metal atmospheric contamination was assessed in one of the oldest European industrial sites of steel production situated in the southern part of the Grand-Duchy of Luxembourg. Using elemental ratios as well as Pb, Sr, and Nd isotopic compositions as tracers, we found preliminary results concerning the trace metal enrichment and the chemical/isotopic signatures of the most important emission sources using the lichen Xanthoria parietina sampled at 15 sites along a SW-NE transect. The concentrations of these elements decreased with increasing distance from the historical and actual steel-work areas. The combination of the different tracers (major elements, Rare Earth Element ratios, Pb, Sr and Nd isotopes) enabled us to distinguish between three principal sources: the historical steel production (old tailings corresponding to blast-furnace residues), the present steel production (industrial sites with arc electric furnace units) and the regional background (baseline) components. Other anthropogenic sources including a waste incinerator and major roads had only weak impacts on lichen chemistry and isotopic ratios. The correlation between the Sr and Nd isotope ratios indicated that the Sr-Nd isotope systems represented useful tools to trace atmospheric emissions of factories using scrap metal for steel production.

Sensitive Quantification of Cannabinoids in Milk by Alkaline Saponification-Solid Phase Extraction Combined with Isotope Dilution UPLC-MS/MS.

PubMed

Wei, Binnian; McGuffey, James E; Blount, Benjamin C; Wang, Lanqing

2016-01-01

Maternal exposure to marijuana during the lactation period-either active or passive-has prompted concerns about transmission of cannabinoids to breastfed infants and possible subsequent adverse health consequences. Assessing these health risks requires a sensitive analytical approach that is able to quantitatively measure trace-level cannabinoids in breast milk. Here, we describe a saponification-solid phase extraction approach combined with ultra-high-pressure liquid chromatography-tandem mass spectrometry for simultaneously quantifying Δ9-tetrahydrocannabinol (THC), cannabidiol (CBD), and cannabinol (CBN) in breast milk. We demonstrate for the first time that constraints on sensitivity can be overcome by utilizing alkaline saponification of the milk samples. After extensively optimizing the saponification procedure, the validated method exhibited limits of detections of 13, 4, and 66 pg/mL for THC, CBN, and CBD, respectively. Notably, the sensitivity achieved was significantly improved, for instance, the limits of detection for THC is at least 100-fold more sensitive compared to that previously reported in the literature. This is essential for monitoring cannabinoids in breast milk resulting from passive or nonrecent active maternal exposure. Furthermore, we simultaneously acquired multiple reaction monitoring transitions for 12 C- and 13 C-analyte isotopes. This combined analysis largely facilitated data acquisition by reducing the repetitive analysis rate for samples exceeding the linear limits of 12 C-analytes. In addition to high sensitivity and broad quantitation range, this method delivers excellent accuracy (relative error within ±10%), precision (relative standard deviation <10%), and efficient analysis. In future studies, we expect this method to play a critical role in assessing infant exposure to cannabinoids through breastfeeding.

Blood-collection device for trace and ultra-trace metal specimens evaluated.

PubMed

Moyer, T P; Mussmann, G V; Nixon, D E

1991-05-01

We evaluated the evacuated phlebotomy tube designed specifically for trace metal analysis by Sherwood Medical Co. Pools of human serum containing known concentrations of aluminum, arsenic, calcium, cadmium, copper, chromium, iron, lead, magnesium, manganese, mercury, selenium, and zinc were exposed to the tube and rubber stopper for defined periods ranging from 5 min to 24 h. Analysis for each element was performed in a randomized fashion under rigidly controlled conditions by use of standard electrothermal atomization atomic absorption spectroscopy, inductively coupled plasma atomic emission spectroscopy, and cold vapor atomic absorption spectrometry. In addition, for comparative purposes, we collected blood samples from normal volunteers by use of ultra-clean polystyrene phlebotomy syringes as well as standard evacuated phlebotomy tubes. We conclude that, except for lead, there was no significant contribution of any trace element studied from the evaluated tube and stopper to the serum. Because whole blood is the usual specimen for lead testing, the observation of a trace amount of lead in this tube designed for serum collection is trivial.

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

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

NASA Astrophysics Data System (ADS)

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

2009-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Ultra-reducing conditions in average mantle peridotites and in podiform chromitites: a thermodynamic model for moissanite (SiC) formation

NASA Astrophysics Data System (ADS)

Golubkova, Anastasia; Schmidt, Max W.; Connolly, James A. D.

2016-05-01

Natural moissanite (SiC) is reported from mantle-derived samples ranging from lithospheric mantle keel diamonds to serpentinites to podiform chromitites in ophiolites related to suprasubduction zone settings (Luobusa, Dongqiao, Semail, and Ray-Iz). To simulate ultra-reducing conditions and the formation of moissanite, we compiled thermodynamic data for alloys (Fe-Si-C and Fe-Cr), carbides (Fe3C, Fe7C3, SiC), and Fe-silicides; these data were augmented by commonly used thermodynamic data for silicates and oxides. Computed phase diagram sections then constrain the P- T- fO2 conditions of SiC stability in the upper mantle. Our results demonstrate that: Moissanite only occurs at oxygen fugacities 6.5-7.5 log units below the iron-wustite buffer; moissanite and chromite cannot stably coexist; increasing pressure does not lead to the stability of this mineral pair; and silicates that coexist with moissanite have X Mg > 0.99. At upper mantle conditions, chromite reduces to Fe-Cr alloy at fO2 values 3.7-5.3 log units above the moissanite-olivine-(ortho)pyroxene-carbon (graphite or diamond) buffer (MOOC). The occurrence of SiC in chromitites and the absence of domains with almost Fe-free silicates suggest that ultra-reducing conditions allowing for SiC are confined to grain scale microenvironments. In contrast to previous ultra-high-pressure and/or temperature hypotheses for SiC origin, we postulate a low to moderate temperature mechanism, which operates via ultra-reducing fluids. In this model, graphite-/diamond-saturated moderately reducing fluids evolve in chemical isolation from the bulk rock to ultra-reducing methane-dominated fluids by sequestering H2O into hydrous phases (serpentine, brucite, phase A). Carbon isotope compositions of moissanite are consistent with an origin of such fluids from sediments originally rich in organic compounds. Findings of SiC within rocks mostly comprised by hydrous phases (serpentine + brucite) support this model. Both the hydrous phases and the limited diffusive equilibration of SiC with most minerals in the rocks indicate temperatures below 700-800 °C. Moissanite from mantle environments is hence a mineral that does not inform on pressure but on a low to moderate temperature environment involving ultra-reduced fluids. Any mineral in equilibrium with SiC could only contain traces of Fe2+ or Cr3+.

Detection of titanium in human tissues after craniofacial surgery.

PubMed

Jorgenson, D S; Mayer, M H; Ellenbogen, R G; Centeno, J A; Johnson, F B; Mullick, F G; Manson, P N

1997-04-01

Generally, titanium fixation plates are not removed after osteosynthesis, because they have high biocompatability and high corrosion resistance characteristics. Experiments with laboratory animals, and limited studies of analyses of human tissues, have reported evidence of titanium release into local and distant tissues. This study summarizes our results of the analysis of soft tissues for titanium in four patients with titanium microfixation plates. Energy dispersive x-ray analysis, scanning electron microscopy, and electrothermal atomic absorption spectrophotometry were used to detect trace amounts of titanium in surrounding soft tissues. A single metal inclusion was detected by scanning electron microscopy and energy dispersive x-ray analysis in one patient, whereas, electrothermal atomic absorption spectrophotometry analyses revealed titanium present in three of four specimens in levels ranging from 7.92 to 31.8 micrograms/gm of dry tissue. Results from this study revealed trace amounts of titanium in tissues surrounding craniofacial plates. At the atomic level, electrothermal atomic absorption spectrophotometry appears to be a sensitive tool to quantitatively detect ultra-trace amounts of metal in human tissue.

Analysis of 85Kr: a comparison at the 10-14 level using micro-liter samples

PubMed Central

Yang, G. -M.; Cheng, C. -F.; Jiang, W.; Lu, Z. -T.; Purtschert, R.; Sun, Y. -R.; Tu, L. -Y.; Hu, S. -M.

2013-01-01

The isotopic abundance of 85Kr in the atmosphere, currently at the level of 10−11, has increased by orders of magnitude since the dawn of nuclear age. With a half-life of 10.76 years, 85Kr is of great interest as tracers for environmental samples such as air, groundwater and ice. Atom Trap Trace Analysis (ATTA) is an emerging method for the analysis of rare krypton isotopes at isotopic abundance levels as low as 10−14 using krypton gas samples of a few micro-liters. Both the reliability and reproducibility of the method are examined in the present study by an inter-comparison among different instruments. The 85Kr/Kr ratios of 12 samples, in the range of 10−13 to 10−10, are measured independently in three laboratories: a low-level counting laboratory in Bern, Switzerland, and two ATTA laboratories, one in Hefei, China, and another in Argonne, USA. The results are in agreement at the precision level of 5%. PMID:23549244

Ultra-trace determination of Persistent Organic Pollutants in Arctic ice using stir bar sorptive extraction and gas chromatography coupled to mass spectrometry.

PubMed

Lacorte, S; Quintana, J; Tauler, R; Ventura, F; Tovar-Sánchez, A; Duarte, C M

2009-12-04

This study presents the optimization and application of an analytical method based on the use of stir bar sorptive extraction (SBSE) gas chromatography coupled to mass spectrometry (GC-MS) for the ultra-trace analysis of POPs (Persistent Organic Pollutants) in Arctic ice. In a first step, the mass-spectrometry conditions were optimized to quantify 48 compounds (polycyclic aromatic hydrocarbons, brominated diphenyl ethers, chlorinated biphenyls, and organochlorinated pesticides) at the low pg/L level. In a second step, the performance of this analytical method was evaluated to determine POPs in Arctic cores collected during an oceanographic campaign. Using a calibration range from 1 to 1800 pg/L and by adjusting acquisition parameters, limits of detection at the 0.1-99 and 102-891 pg/L for organohalogenated compounds and polycyclic aromatic hydrocarbons, respectively, were obtained by extracting 200 mL of unfiltered ice water. alpha-hexachlorocyclohexane, DDTs, chlorinated biphenyl congeners 28, 101 and 118 and brominated diphenyl ethers congeners 47 and 99 were detected in ice cores at levels between 0.5 to 258 pg/L. We emphasise the advantages and disadvantages of in situ SBSE in comparison with traditional extraction techniques used to analyze POPs in ice.

Development of Optical Crystals for High Power and Tunable Visible and Infrared Light Generation

DTIC Science & Technology

2015-02-11

ultra high chemical purity (5N), 95% isotopically enriched 6Li was purified in a multi-stage vacuum distillation process previously reported by...enriched 6Li was purified in a multi-stage vacuum distillation process previously reported by Stowe et al.[4]. 6LiIn alloy was synthesized in a... quantum mechanics, it has been determined that atoms, molecules, ions have discrete energy levels. Therefore there exists allowed atomic transitions

Trace element and isotope geochemistry of Cretaceous-Tertiary boundary sediments: identification of extra-terrestrial and volcanic components

NASA Technical Reports Server (NTRS)

Margolis, S. V.; Doehne, E. F.

1988-01-01

Trace element and stable isotope analyses were performed on a series of sediment samples crossing the Cretaceous-Tertiary (K-T) boundary from critical sections at Aumaya and Sopelano, Spain. The aim is to possibly distinguish extraterrestrial vs. volcanic or authigenic concentration of platinum group and other elements in K-T boundary transitional sediments. These sediments also have been shown to contain evidence for step-wise extinction of several groups of marine invertebrates, associated with negative oxygen and carbon isotope excursions occurring during the last million years of the Cretaceous. These isotope excursions have been interpreted to indicate major changes in ocean thermal regime, circulation, and ecosystems that may be related to multiple events during latest Cretaceous time. Results to date on the petrographic and geochemical analyses of the Late Cretaceous and Early Paleocene sediments indicate that diagenesis has obviously affected the trace element geochemistry and stable isotope compositions at Zumaya. Mineralogical and geochemical analysis of K-T boundary sediments at Zumaya suggest that a substantial fraction of anomalous trace elements in the boundary marl are present in specific mineral phases. Platinum and nickel grains perhaps represent the first direct evidence of siderophile-rich minerals at the boundary. The presence of spinels and Ni-rich particles as inclusions in aluminosilicate spherules from Zumaya suggests an original, non-diagenetic origin for the spherules. Similar spherules from southern Spain (Caravaca), show a strong marine authigenic overprint. This research represents a new approach in trying to directly identify the sedimentary mineral components that are responsible for the trace element concentrations associated with the K-T boundary.

The novel approach to the biomonitor survey using one- and two-dimensional Kohonen networks.

PubMed

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

2015-10-01

To compare the applicability of the leaves of horse chestnut (Aesculus hippocastanum) and linden (Tilia spp.) as biomonitors of trace element concentrations, a coupled approach of one- and two-dimensional Kohonen networks was applied for the first time. The self-organizing networks (SONs) and the self-organizing maps (SOMs) were applied on the database obtained for the element accumulation (Cr, Fe, Ni, Cu, Zn, Pb, V, As, Cd) and the SOM for the Pb isotopes in the leaves for a multiyear period (2002-2006). A. hippocastanum seems to be a more appropriate biomonitor since it showed more consistent results in the analysis of trace elements and Pb isotopes. The SOM proved to be a suitable and sensitive tool for assessing differences in trace element concentrations and for the Pb isotopic composition in leaves of different species. In addition, the SON provided more clear data on seasonal and temporal accumulation of trace elements in the leaves and could be recommended complementary to the SOM analysis of trace elements in biomonitoring studies.

Neodymium in the oceans: a global database, a regional comparison and implications for palaeoceanographic research

PubMed Central

Griffiths, Alexander M.; Lambelet, Myriam; Little, Susan H.; Stichel, Torben; Wilson, David J.

2016-01-01

The neodymium (Nd) isotopic composition of seawater has been used extensively to reconstruct ocean circulation on a variety of time scales. However, dissolved neodymium concentrations and isotopes do not always behave conservatively, and quantitative deconvolution of this non-conservative component can be used to detect trace metal inputs and isotopic exchange at ocean–sediment interfaces. In order to facilitate such comparisons for historical datasets, we here provide an extended global database for Nd isotopes and concentrations in the context of hydrography and nutrients. Since 2010, combined datasets for a large range of trace elements and isotopes are collected on international GEOTRACES section cruises, alongside classical nutrient and hydrography measurements. Here, we take a first step towards exploiting these datasets by comparing high-resolution Nd sections for the western and eastern North Atlantic in the context of hydrography, nutrients and aluminium (Al) concentrations. Evaluating those data in tracer–tracer space reveals that North Atlantic seawater Nd isotopes and concentrations generally follow the patterns of advection, as do Al concentrations. Deviations from water mass mixing are observed locally, associated with the addition or removal of trace metals in benthic nepheloid layers, exchange with ocean margins (i.e. boundary exchange) and/or exchange with particulate phases (i.e. reversible scavenging). We emphasize that the complexity of some of the new datasets cautions against a quantitative interpretation of individual palaeo Nd isotope records, and indicates the importance of spatial reconstructions for a more balanced approach to deciphering past ocean changes. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035258

Distribution of Cr, Pb, Cd, Zn, Fe and Mn in Lake Victoria sediments, East Africa

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

Onyari, J.M.; Wandiga, S.O.

1989-06-01

The presence of many metals at trace or ultra-trace levels in the human environment has received increased global attention. Sediments as a sink for pollutants are widely recognized pollution sources and diagenesis and biochemical transformations within the sediment may mobilize pollutants posing a threat to a wider biological community. The natural (background) concentrations of heavy metals in lake sediments can be estimated either by analysis of surface sediments in non-polluted regions or by analysis of core samples antedating modern pollution. The distribution pattern of heavy metals in tropical freshwater systems has been little studied. The authors found increased concentrations ofmore » lead and other trace metals in Lake Victoria. Thus this study was initiated in order to further investigate the distribution patterns of lead and other metals in Lake Victoria.« less

The development of a new technical platform to measure soil organic nitrogen cycling processes by microbes

NASA Astrophysics Data System (ADS)

Hu, Yuntao; Richter, Andreas; Wanek, Wolfgang

2016-04-01

Soil organic matter (SOM) decomposition is one of the most important processes of the global nitrogen cycle, having strong implications on soil N availability, terrestrial carbon cycling and soil carbon sequestration. During SOM decomposition low-molecular weight organic nitrogen (LMWON) is released which can be taken up by microbes (and plants). The breakdown of high-molecular weight organic nitrogen (HMWON, e.g. proteins, peptidoglycan, chitin, nucleic acids) represents the bottleneck of soil HMWON decomposition and is performed by extracellular enzymes released mainly by soil microorganisms. Despite that, the current understanding of the controls of these processes is incomplete. The only way to measure gross decomposition rates of these polymers is to use isotope pool dilution (IPD) techniques. In IPD approaches the product pool is isotopically enriched (by e.g. 15N) and the isotope dilution of this pool is measured over time. We have pioneered an IPD for protein and cellulose depolymerization, but IPD approaches for other polymers, specifically for important microbial necromass components such as chitin (fungi) and peptidoglycan (bacteria), or nucleic acids have not yet been developed. Here we present a workflow based on a universally applicable technical platform that allows to estimate the gross depolymerization rate of SOM (HMWON) at the molecular level, using ultra high performance liquid chromatography/high resolution Orbitrap mass spectrometry (UPLC/HRMS) combined with IPD techniques. The necessary isotopically labeled organic polymers (chitin, peptidoglycan and others) are extracted from laboratory bacterial and fungal cultures grown in fully isotopically labeled nutrient media (15N, 13C or both). A purification scheme for the different polymers is currently established. Labeled potential decomposition products (e.g. amino sugars and muropeptides from peptidoglycan, amino sugars and chitooligosaccharides from chitin, nucleotides and nucleosides from nucleic acids) are prepared by enzymatic and/or acid digestion of the polymers. Different UPLC separation columns (Hypercarb, HiliC and C18) make it possible to separate more than 100 related monomers and oligomers produced during polymer decomposition, a prerequisite for analyzing the concentrations and isotope kinetics of decomposition products in complex soil samples. The benchtop Orbitrap mass analyzer has a nominal mass resolving power of 100,000 (FWHM at m/z 200), which enables us to separate compounds that are 13C- and 15N-labelled (mass difference: 0.00632) in the same compound, allowing tracing carbon and nitrogen isotopes in the same compound in IPD experiments. With the accurate masses, retention times and the isotopic pattern we can quantify and qualify the target decomposition products and their isotope kinetics during soil incubation experiments. This will enable us to estimate in situ decomposition rates of the major organic nitrogen polymers in soils, allowing new insights into the major controls of the most important step in soil organic nitrogen recycling.

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

DOE PAGES

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

2018-02-19

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

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

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

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

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

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Organic Compounds, Trace Elements, Suspended Sediment, and Field Characteristics at the Heads-of-Tide of the Raritan, Passaic, Hackensack, Rahway, and Elizabeth Rivers, New Jersey, 2000-03

USGS Publications Warehouse

Bonin, Jennifer L.; Wilson, Timothy P.

2006-01-01

Concentrations of suspended sediment, particulate and dissolved organic carbon, trace elements, and organic compounds were measured in samples from the heads-of-tide of the five tributaries to the Newark and Raritan Bays during June 2000 to June 2003. The samples were collected as part of the New Jersey Department of Environmental Protection Toxics Reduction Workplan/Contaminant Assessment Reduction Program. Samples of streamwater were collected at water-quality sampling stations constructed near U.S. Geological Survey gaging stations on the Raritan, Passaic, Hackensack, Rahway, and Elizabeth Rivers. Sampling was conducted during base-flow conditions and storms. Constituent concentrations were measured to determine the water quality and to calculate the load of sediment and contaminants contributed to the bays from upstream sources. Water samples were analyzed for suspended sediment, dissolved organic carbon, particulate organic carbon, and specific conductance. Samples of suspended sediment and water were analyzed for 98 distinct polychlorinated biphenyl congeners, 7 dioxins, 10 furans, 27 pesticides, 26 polycyclic aromatic hydrocarbons, and the trace elements cadmium, lead, mercury, and methyl-mercury. Measurements of ultra-low concentrations of organic compounds in sediment and water were obtained by collecting 1 to 3 grams of suspended sediment on glass fiber filters and by passing at least 20 liters of filtered water through XAD-2 resin. The extracted sediment and XAD-2 resin were analyzed for organic compounds by high- and low-resolution gas chromatography mass-spectrometry that uses isotope dilution procedures. Trace elements in filtered and unfiltered samples were analyzed for cadmium, lead, mercury, and methyl-mercury by inductively coupled charged plasma and mass-spectrometry. All constituent concentrations are raw data. Interpretation of the data will be completed in the second phase of the study.

Uniform deposition of uranium hexafluoride (UF6): Standardized mass deposits and controlled isotopic ratios using a thermal fluorination method.

PubMed

McNamara, Bruce K; O'Hara, Matthew J; Casella, Andrew M; Carter, Jennifer C; Addleman, R Shane; MacFarlan, Paul J

2016-07-01

We report a convenient method for the generation of volatile uranium hexafluoride (UF6) from solid uranium oxides and other U compounds, followed by uniform deposition of low levels of UF6 onto sampling coupons. Under laminar flow conditions, UF6 is shown to interact with surfaces within a fixed reactor geometry to a highly predictable degree. We demonstrate the preparation of U deposits that range between approximately 0.01 and 500ngcm(-2). The data suggest the method can be extended to creating depositions at the sub-picogramcm(-2) level. The isotopic composition of the deposits can be customized by selection of the U source materials and we demonstrate a layering technique whereby two U solids, each with a different isotopic composition, are employed to form successive layers of UF6 on a surface. The result is an ultra-thin deposit that bears an isotopic signature that is a composite of the two U sources. The reported deposition method has direct application to the development of unique analytical standards for nuclear safeguards and forensics. Further, the method allows access to very low atomic or molecular coverages of surfaces. Copyright © 2016 Elsevier B.V. All rights reserved.

Co-detection: ultra-reliable nanoparticle-based electrical detection of biomolecules in the presence of large background interference.

PubMed

Liu, Yang; Gu, Ming; Alocilja, Evangelyn C; Chakrabartty, Shantanu

2010-11-15

An ultra-reliable technique for detecting trace quantities of biomolecules is reported. The technique called "co-detection" exploits the non-linear redundancy amongst synthetically patterned biomolecular logic circuits for deciphering the presence or absence of target biomolecules in a sample. In this paper, we verify the "co-detection" principle on gold-nanoparticle-based conductimetric soft-logic circuits which use a silver-enhancement technique for signal amplification. Using co-detection, we have been able to demonstrate a great improvement in the reliability of detecting mouse IgG at concentration levels that are 10(5) lower than the concentration of rabbit IgG which serves as background interference. Copyright © 2010 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Electron-hole pairs generation rate estimation irradiated by isotope Nickel-63 in silicone using GEANT4

NASA Astrophysics Data System (ADS)

Kovalev, I. V.; Sidorov, V. G.; Zelenkov, P. V.; Khoroshko, A. Y.; Lelekov, A. T.

2015-10-01

To optimize parameters of beta-electrical converter of isotope Nickel-63 radiation, model of the distribution of EHP generation rate in semiconductor must be derived. By using Monte-Carlo methods in GEANT4 system with ultra-low energy electron physics models this distribution in silicon calculated and approximated with Gauss function. Maximal efficient isotope layer thickness and maximal energy efficiency of EHP generation were estimated.

Tracing subducted crustal materials in the mantle by using magnesium isotopes

NASA Astrophysics Data System (ADS)

Teng, F. Z.

2016-12-01

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

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.

Lu-Hf, in-situ Sr and Pb isotope and trace element systematics for mantle eclogites from the Diavik diamond mine: Evidence for Paleoproterozoic subduction beneath the Slave craton, Canada

NASA Astrophysics Data System (ADS)

Schmidberger, Stefanie S.; Simonetti, Antonio; Heaman, Larry M.; Creaser, Robert A.; Whiteford, Sean

2007-02-01

Lu-Hf, Sm-Nd and in-situ clinopyroxene Sr and Pb isotope systematics, and mineral major and in-situ trace element compositions were obtained for a suite of non-diamond and diamond-bearing eclogites from the Diavik kimberlites (A154; 55 Ma old), Slave craton (Canada). Temperature estimates of last equilibration in the lithosphere for the non-diamond-bearing Diavik eclogites define two groups; low-temperature (800-1050 °C) and high-temperature eclogites (1100-1300 °C). Most diamond-eclogites indicate temperatures similar to those of the high-temperature eclogites. Isotopic and major and trace element systematics for the non-diamond- and diamond-bearing eclogites indicate overlapping chemical compositions suggesting similar rock formational histories. Calculated whole rock major and trace element abundances using chemical and modal abundances for constituent minerals exhibit broad similarities with mafic cumulates from ophiolite sequences. Most importantly the calculated whole rock eclogite compositions display positive Sr and Eu anomalies, typically interpreted as the result of plagioclase accumulation in cumulate rocks of oceanic crust sequences. Initial whole rock Hf isotopic values and in-situ Sr isotope data from clinopyroxene grains provide evidence that the eclogites were derived from precursor rocks with depleted mantle isotope characteristics. These combined results support the interpretation that the eclogites from Diavik represent remnants of subducted oceanic crust. Lu-Hf isotope systematics indicate that the oceanic protolith for the eclogites formed in the Paleoproterozoic at ˜ 2.1 Ga, which is in agreement with the in-situ Pb isotope data from clinopyroxene. This result also corroborates the ˜ 2.1 Ga Lu-Hf model ages recorded by mantle zircons from eclogite found within the Jericho kimberlite in the northern Slave Province (˜ 200 km northwest of Diavik). The results from both studies indicate a link between eclogite formation and Paleoproterozoic subduction of oceanic lithosphere along the present-day western margin of the Archean Slave craton.

Applications of Ultra-Intense, Short Laser Pulses

NASA Astrophysics Data System (ADS)

Ledingham, Ken W. D.

The high intensity laser production of electron, proton, ion and photon beams is reviewed particularly with respect to the laser-plasma interaction which drives the acceleration process. A number of applications for these intense short pulse beams is discussed e.g. ion therapy, PET isotope production and laser driven transmutation studies. The future for laser driven nuclear physics at the huge new, multi-petawatt proposed laser installation ELI in Bucharest is described. Many people believe this will take European nuclear research to the next level.

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

NASA Technical Reports Server (NTRS)

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

2013-01-01

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

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.

Application of major and trace elements as well as boron isotopes for tracing hydrochemical processes: the case of Trifilia coastal karst aquifer, Greece

NASA Astrophysics Data System (ADS)

Panagopoulos, G.

2009-09-01

The Trifilia karst aquifer presents a complex hydrochemical character due to the intricate geochemical processes that take place in the area. Their discernment was achieved by using the chemical analyses of major, trace elements and boron isotopes. Major ion composition indicates mixing between seawater and freshwater is occurring. Five hydrochemical zones corresponding to five respective groundwater types were distinguished, in which the chemical composition of groundwater is influenced mainly due to the different salinization grade of the aquifer. The relatively increased temperature of the aquifer indicates the presence of hydrothermal waters. Boron isotopes and trace elements indicate that the intruding seawater has been hydrothermally altered, as it is shown by the δ11B depleted signature and the increased concentrations of Li and Sr. Trace elements analyses showed that the groundwater is enriched in various metallic elements, which derive from the solid hydrocarbons (bitumens), contained in the carbonate sediments of the Tripolis zone. The concentration of these trace elements depends on the redox environment. Thus, in reductive conditions As, Mn, Co and NH4 concentrations are high, in oxidized conditions the V, Se, Mo, Tl and U concentration increases while Ni is not redox sensitive and present high concentration in both environments.

The role of pre-event canopy storage in throughfall and stemflow by using isotopic tracers

Treesearch

S.T. Allen; J.R. Brooks; R.F. Keim; B.J. Bond; J.J. McDonnell

2014-01-01

Stable isotopes can be a valuable tool for tracing the redistribution, storage, and evaporation of water associated with canopy interception of rainfall. Isotopic differences between throughfall and rainfall have been attributed to three mechanisms: evaporative fractionation, isotopic exchange with ambient vapor, and temporal redistribution. We demonstrate the...

Evaluating cleansing effects on trace elements and stable isotope values in feathers of oiled birds.

PubMed

Valladares, Sonia; Moreno, Roćio; Jover, Lluis; Sanpera, Carola

2010-01-01

Feathers of seabirds are widely used as a nondestructive tissue for pollution monitoring of trace elements, as well as convenient samples for trophic ecology studies by means of stable isotope analysis (SIA). Nevertheless, feathers can be occasionally impregnated with oil from deliberate ship discharges and from massive oil spill accidents. The feather structure makes them effective traps for particles and are subject to external contamination. It is unknown to what extent the oil adhered to feathers can change trace element concentrations or stable isotope signatures. This study has two primary objectives: (1) to assess if there are differences between trace element concentrations and stable isotope signatures of oiled and clean feathers, and (2) to determine if the cleansing of oiled feathers using commonly applied techniques such as sodium hydroxide (NaOH) washes in combination with an organic solvent (hexane) is more effective than using NaOH alone. In order to do this, we analysed trace elements (Se, Hg, Pb, Cu and Zn) and stable isotopes (delta(13)C and delta(15)N) of individual feathers of yellow-legged gulls (Larus michahellis) which were affected by the 2002 Prestige oil spill in Galicia (NW Spain). Two sets of feathers were analysed, one group were oil-free (Control group) and the other had oil adhered to its surface (Oiled group). We expected to find differences between control and oiled feathers when cleaning exclusively with NaOH and no differences when using hexane. Our results did not show significant differences between Control and Oiled groups as a consequence of the cleansing method used. Unexpectedly, the additional cleansing with hexane resulted in decreasing selenium concentrations and increasing zinc and delta(15)N values in all groups of feathers.

Re-187 Os-187 Isotopic and Highly Siderophile Element Systematics of Group IVB Irons

NASA Technical Reports Server (NTRS)

Honesto, J.; McDonough, W. F.; Walker, R. J.; McCoy, T. J.; Ash, R. D.

2005-01-01

Study of the magmatic iron meteorite groups permits constraints to be placed on the chemical and isotopic composition of parent bodies, and the timing of, and crystal-liquid fractionation processes involved in the crystallization of asteroidal cores. Here we examine Re-Os isotopic and trace elemental systematics of group IVB irons. Compared to most irons, the irons comprising this group are enriched in some of the most refractory siderophile elements, yet highly-depleted in most volatile siderophile elements. These characteristics have been attributed to processes such as high temperature condensation of precursor materials and oxidation in the parent body. Most recently it has been suggested that both processes may be involved in the chemical complexity of the group. Here, high precision isotopic and highly siderophile element (HSE) concentrations are used to further examine these possible origins, and the crystallization history of the group. In addition, we have begun to assess the possibility of relating certain ungrouped irons with major groups via multi-element, trace element modeling. In a companion abstract, the isotopic and trace element systematics of the ungrouped iron Tishomingo are compared with the IVB irons.

The peculiar geochemical signatures of São Miguel (Azores) lavas: Metasomatised or recycled mantle sources?

NASA Astrophysics Data System (ADS)

Beier, Christoph; Stracke, Andreas; Haase, Karsten M.

2007-07-01

The island of São Miguel, Azores consists of four large volcanic systems that exhibit a large systematic intra-island Sr-Nd-Pb-Hf isotope and trace element variability. The westernmost Sete Cidades volcano has moderately enriched Sr-Nd-Pb-Hf isotope ratios. In contrast, lavas from the easternmost Nordeste volcano have unusually high Sr and Pb and low Nd and Hf isotope ratios suggesting a long-term evolution with high Rb/Sr, U/Pb, Th/Pb, Th/U and low Sm/Nd and Lu/Hf parent-daughter ratios. They have trace element concentrations similar to those of the HIMU islands, with the exception of notably higher alkali element (Cs, Rb, K, Ba) and Th concentrations. The time-integrated parent-daughter element evolution of both the Sete Cidades and Nordeste source matches the incompatibility sequence commonly observed during mantle melting and consequently suggests that the mantle source enrichment is caused by a basaltic melt, either as a metasomatic agent or as recycled oceanic crust. Our calculations show that a metasomatic model involving a small degree basaltic melt is able to explain the isotopic enrichment but, invariably, produces far too enriched trace element signatures. We therefore favour a simple recycling model. The trace element and isotopic signatures of the Sete Cidades lavas are consistent with the presence of ancient recycled oceanic crust that has experienced some Pb loss during sub-arc alteration. The coherent correlation of the parent-daughter ratios (e.g. Rb/Sr, Th/U, U/Pb) and incompatible element ratios (e.g. Nb/Zr, Ba/Rb, La/Nb) with the isotope ratios in lavas from the entire island suggest that the Sete Cidades and Nordeste source share a similar genetic origin. The more enriched trace element and isotopic variations of Nordeste can be reproduced by recycled oceanic crust in the Nordeste source that contains small amounts of evolved lavas (˜ 1-2%), possibly from a subducted seamount. The rare occurrence of enriched source signatures comparable to Nordeste may be taken as circumstantial evidence that stirring processes in the Earth's mantle are not able to homogenise material within the size of seamounts over timescales of mantle recycling.

Following isotopes in pulse-chase enriched aspen seedlings

NASA Astrophysics Data System (ADS)

Norris, C. E.; Wasylishen, R. E.; Landhäusser, S.; Quideau, S. A.

2011-12-01

One method to quantitatively trace biogeochemical fluxes through ecosystems, such as organic matter decomposition, is to use plant material enriched with stable isotopes. However, as plant macromolecules are known to vary in their rate of formation and decomposition, both the enrichment levels and the location of enrichment within the plant material should be characterized prior to decomposition and tracing studies. Aspen (Populus tremuloides Michx.) is a common tree species with a diverse organic matter chemical structure found in the western Canadian boreal forest. This study used a multi pulse and multi chase enrichment of stable isotopes (15N and 13C) on aspen seedlings to determine the seedling enrichment, isotope movement among plant tissues and translocation of isotopes within plant macromolecules e.g., carbohydrates and lignin. As expected, all tissues experienced increased enrichment with multiple pulses. An initial enrichment with 13C was observed in the leaves followed by translocation to the stems and roots while the 15N moved upward from the roots to leaves. The macromolecular chemistry of the organic carbon was further characterized using 13C solid state nuclear magnetic resonance spectroscopy. After the initial two hour chase period enrichment of the O-alkyl type (carbohydrate) carbon within the leaves was identified, followed by redistribution to more complex carbon compounds after the one week chase period. Root and stem tissues did not show the same pattern. Rather, changes in 13C enrichment were observed in shifting ethyl and methyl alkyl (lipid) carbon peak intensities for the stem samples while roots did not preferentially allocate 13C to a specific macromolecule. These results confirm that stable isotope enrichment of plants was non-uniform across macromolecules and tissue types. Enrichment of aspen seedlings was therefore dependant on the pulse-chase sequence used.

Novel electrochemical biosensor based on PVP capped CoFe2O4@CdSe core-shell nanoparticles modified electrode for ultra-trace level determination of rifampicin by square wave adsorptive stripping voltammetry.

PubMed

Asadpour-Zeynali, Karim; Mollarasouli, Fariba

2017-06-15

This work introduces a new electrochemical sensor based on polyvinyl pyrrolidone capped CoFe 2 O 4 @CdSe core-shell modified electrode for a rapid detection and highly sensitive determination of rifampicin (RIF) by square wave adsorptive stripping voltammetry. The new PVP capped CoFe 2 O 4 @CdSe with core-shell nanostructure was synthesized by a facile synthesis method for the first time. PVP can act as a capping and etching agent for protection of the outer surface nanoparticles and formation of a mesoporous shell, respectively. Another important feature of this work is the choice of the ligand (1,10-phenanthroline) for precursor cadmium complex that works as a chelating agent in order to increase optical and electrical properties and stability of prepared nanomaterial. The nanoparticles have been characterized by field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), UV-vis, photoluminescence (PL) spectroscopy, FT-IR, and cyclic voltammetry techniques. The PL spectroscopy study of CoFe 2 O 4 @CdSe has shown significant PL quenching by the formation of CoFe 2 O 4 core inside CdSe, this shows that CoFe 2 O 4 NPs are efficient electron acceptors with the CdSe. It is clearly observed that the biosensor can significantly enhance electrocatalytic activity towards the oxidation of RIF, under the optimal conditions. The novelty of this work arises from the new synthesis method for the core-shell of CoFe 2 O 4 @CdSe. Then, the novel electrochemical biosensor was fabricated for ultra-trace level determination of rifampicin with very low detection limit (4.55×10 -17 M) and a wide linear range from 1.0×10 -16 to 1.0×10 -7 M. The fabricated biosensor showed high sensitivity and selectivity, good reproducibility and stability. Therefore, it was successfully applied for the determination of ultra-trace RIF amounts in biological and pharmaceutical samples with satisfactory recovery data. Copyright © 2016 Elsevier B.V. All rights reserved.

THE ROLE OF PRE-EVENT CANOPY STORAGE IN THROUGHFALL AND STEMFLOW USING ISOTOPIC TRACERS

EPA Science Inventory

Stable isotopes can be a valuable tool for tracing the redistribution, storage, and evaporation of water associated with canopy interception of rainfall. Isotopic differences between throughfall and rainfall have been attributed to three mechanisms: evaporative fractionation, iso...

Multi-stage metasomatism revealed by trace element and Li isotope distributions in minerals of peridotite xenoliths from Allègre volcano (French Massif Central)

NASA Astrophysics Data System (ADS)

Gu, Xiaoyan; Deloule, Etienne; France, Lydéric; Ingrin, Jannick

2016-11-01

The modal, chemical, and isotopic compositions of mantle peridotite are largely modified by metasomatic processes, which may affect them repeatedly. Xenoliths are commonly used to characterize those metasomatic processes along with the structure, and chemical and isotopic compositions of mantle domains. Nevertheless, the original mantle signatures born by mantle xenoliths are potentially obscured by the interactions occurring between the host magma and the xenolith itself. Here we attempt to identify to which degree the original Li content and isotopic composition, as well as other trace element contents of mantle xenoliths, can be modified by interaction with the host magma. Peridotite xenoliths that have suffered extensive exchange with the entraining magma were sampled in the solidified lava lake of Allègre, Southern French Massif Central, in order to decipher the signature related to peridotite-melt interaction, and to further unravel the evolution of the sub-continental lithospheric mantle. In-situ trace element analyses of clinopyroxene (Cpx) were performed via LA-ICP-MS, and the Li content and isotopic composition of pyroxene and olivine (Ol) via SIMS. Negative HFSE anomalies (Ti/Eu ratios as low as 437) and markedly high LREE/HREE ratios ((La/Yb)N as high as 79) are characteristic of mantle metasomatism at depth. Lithium isotope systematics indicates that at least two different metasomatic events affected the peridotite. Exceptionally high Li contents in Cpx (up to 50 ppm) and slight Li enrichment of Ol rims are ascribed to diffusive Li influx with a positive δ7Li value (+ 3.2‰) from the host magma after entrainment. Conversely, Ol cores preserve extremely light Li isotopic compositions (δ7Li as low as - 25‰) with high Li contents (up to 4.4 ppm) compared to normal mantle, indicating a metasomatic event that occurred before xenolith entrainment. The negative δ7Li signature of this early metasomatism may be related to subduction-related fluids released during the Variscan orogeny. Trace element distributions in minerals reveal that the HFSE and REE composition of Cpx and the negative δ7Li signature in Ol cores were not acquired simultaneously. Therefore at least three successive metasomatic events affected the Allegre peridotites, as revealed through the use of detailed in-situ Li isotopic analyses to trace melt-rock interactions.

Isotopic and trace element constraints on the petrogenesis of lavas from the Mount Adams volcanic field, Washington

USGS Publications Warehouse

Jicha, B.R.; Hart, G.L.; Johnson, C.M.; Hildreth, Wes; Beard, B.L.; Shirey, S.B.; Valley, J.W.

2009-01-01

Strontium, Nd, Pb, Hf, Os, and O isotope compositions for 30 Quaternary lava flows from the Mount Adams stratovolcano and its basaltic periphery in the Cascade arc, southern Washington, USA indicate a major component from intraplate mantle sources, a relatively small subduction component, and interaction with young mafic crust at depth. Major- and trace-element patterns for Mount Adams lavas are distinct from the rear-arc Simcoe volcanic field and other nearby volcanic centers in the Cascade arc such as Mount St. Helens. Radiogenic isotope (Sr, Nd, Pb, and Hf) compositions do not correlate with geochemical indicators of slab-fluids such as (Sr/P)n and Ba/Nb. Mass-balance modeling calculations, coupled with trace-element and isotopic data, indicate that although the mantle source for the calc-alkaline Adams basalts has been modified with a fluid derived from subducted sediment, the extent of modification is significantly less than what is documented in the southern Cascades. The isotopic and trace-element compositions of most Mount Adams lavas require the presence of enriched and depleted mantle sources, and based on volume-weighted chemical and isotopic compositions for Mount Adams lavas through time, an intraplate mantle source contributed the major magmatic mass of the system. Generation of basaltic andesites to dacites at Mount Adams occurred by assimilation and fractional crystallization in the lower crust, but wholesale crustal melting did not occur. Most lavas have Tb/Yb ratios that are significantly higher than those of MORB, which is consistent with partial melting of the mantle in the presence of residual garnet. ??18O values for olivine phenocrysts in Mount Adams lavas are within the range of typical upper mantle peridotites, precluding involvement of upper crustal sedimentary material or accreted terrane during magma ascent. The restricted Nd and Hf isotope compositions of Mount Adams lavas indicate that these isotope systems are insensitive to crustal interaction in this juvenile arc, in stark contrast to Os isotopes, which are highly sensitive to interaction with young, mafic material in the lower crust. ?? Springer-Verlag 2008.

High Precision Isotopic Analysis of Actinide Bearing Materials: Performance of a New Generation of Purpose Built Actinide Multi-Collector ICPMS Instruments

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

Eiden, Gregory C.; Duffin, Andrew M.; Liezers, Martin

2014-11-14

Recently, a new class of multi-collector inductively coupled plasma mass spectrometers (MC-ICPMS) has been introduced commercially that includes detector arrays purpose built for actinide measurements. These detector arrays significantly enhance the data quality possible for applications encountered in nuclear forensics. Two such instruments are described in this paper, the NeptunePlusTM, developed by Thermo-Fisher (Bremen, Germany), and the NuPlasma2, developed by Nu Instruments (Wrexham, UK). Research results are presented that have been obtained by the authors using the first commercial NeptunePlusTM. This paper also presents performance characteristics and results for traditional liquid introduction, including a means for ultra-trace detection via electrochemicalmore » separation prior to solution nebulization, as well as solid sample introduction with femtosecond-laser ablation. We also discuss the advantages and limitations of the current systems for detection of the transient signals associated with these two methods for introducing sample into the plasma.« less

Removal and recovery of mercury(II) from hazardous wastes using 1-(2-thiazolylazo)-2-naphthol functionalized activated carbon as solid phase extractant.

PubMed

Starvin, A M; Rao, T Prasada

2004-09-10

As a part of removal of toxic heavy metals from hazardous wastes, solid phase extraction (SPE) of mercury(II) at trace and ultra trace levels was studied using 1-(2-thiazolylazo)-2-naphthol (TAN) functionalized activated carbon (AC). The SPE material removes traces of mercury(II) quantitatively in the pH range 6.0 +/- 0.2. Other parameters that influence quantitative recovery of mercury(II), viz. percent concentration of TAN in AC, amount of TAN-AC, preconcentration time and volume of aqueous phase were varied and optimized. The possible means of removal of Hg(II) from other metal ions that are likely to be present in the wastes of the chloroalkali industry is discussed. The potential of TAN-functionalized AC SPE material for decontaminating mercury from the brine sludge and cell house effluent of a chloralkali plant has been evaluated.

CISOCUR - Residence time modelling in the Curonian Lagoon and validation through stable isotope measurements

NASA Astrophysics Data System (ADS)

Umgiesser, Georg; Razinkovas-Baziukas, Arturas; Zemlys, Petras; Ertürk, Ali; Mėžinė, Jovita

2015-04-01

The spatial pattern of the hydrodynamic circulation of the Curonian lagoon, the largest European coastal lagoon, is still little understood. In absence of automatic current registration data all the existing models relied mostly on such data as water levels leaving high level of uncertainty. Here we present CISOCUR, a new project financed by European Social Fund under the Global Grant measure. The project applies a new methodology that uses the carbon stable isotope (SI) ratio of C12 and C13 that characterize different water sources entering the lagoon and may be altered by internal kinetic processes. Through the tracing of these isotope ratios different water masses can be identified. This gives the possibility to validate several hypotheses of water circulation and validate hydrodynamic models. In particular it will be possible to 1) trace water masses entering the lagoon through the Nemunas and the Klaipeda strait; 2) test the hypothesis of sediment transport mechanisms inside the lagoon; 3) evaluate the importance of physical forcing on the lagoon circulation. The use of a hydrodynamic finite element model, coupled with the SI method, will allow for a realistic description of the transport processes inside the Curonian lagoon. So the main research goal is to apply the stable isotope tracers and a finite element model to determine the circulation patterns in the Curonian lagoon. Here we show how the SI analysis was used to validate the hydrodynamic model on the basis of residence time. The average residence time of the Nemunas waters is estimated through SI data and is then compared with the model data computed through standard algorithms. Seasonal changes of carbon content are taken care of through a preliminary application of a carbon kinetic model. The results are compared to literature data.

Seasonality Records From Stable Isotopes and Trace Elements in Mussel and Limpet Shells From Archaeological Sites on Gibraltar

NASA Astrophysics Data System (ADS)

Fa, D.; Ferguson, J. E.; Atkinson, T. C.; Barton, R. N.; Ditchfield, P.; Finlayson, G.; Finlayson, J. C.; Henderson, G. M.

2007-12-01

Seasonal resolution climate records from mid and high latitudes would allow investigation of the role of seasonality in controlling mean climate on diverse timescales, and of the evolution of climate systems such as the North Atlantic Oscillation (NAO). But achieving such seasonal resolution is difficult for regions outside the growth range of surface corals. Marine mollusc shells provide a possible archive and contain growth increments varying in scale from tidal to annual. However, finding and dating sequences of marine mollusc shells spanning long periods of time is difficult due to sea-level change and the destructional nature of most coastal environments. In this study, we have made use of the habit of hominins on Gibraltar to collect molluscs for food over at least the last 120 kyr. In archaeological excavations of two caves (Gorham's and Vanguard Caves), mollusc shells were found, in habitation levels and in sediment blown into the caves. Existing 14C, OSL, and U-series chronologies provide a chronological framework for this suite of samples. The species found are predominantly Mytilus (mussels) or Patella (limpets). Gibraltar is an interesting location for paleoclimate reconstruction due to its proximity to the boundary of modern day climate belts but also due to its anthropological and archaeological importance. To gain a quantitative understanding of the local controls on stable isotopes and trace elements within Gibraltarian shells, we have initiated a water-sampling programme; emplaced a temperature and salinity logger near the sampling site; and marked live Patella and Mytilus with fluorescent dye to firmly establish growth rates and controls on chemical composition. We have also conducted stable-isotope and trace-element analysis of modern and fossil Patella and Mytilus shells by micromilling. Recent Patella and Mytilus shells show that the oxygen isotope composition of modern shells allow the accurate reconstruction of the full seasonal range in sea-surface temperature. Analysis of three fossil Mytilus samples contained within a Neanderthal occupation level from approximately 115 kyr show clear annual cycles in δ 18O but with different absolute values. Patella samples have also been analysed from the last glacial and from 800-300B.C. Results allow an assessment of past changes in seasonality and of the utility of this archeological shell material as an archive for past change.

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.

The chemical and isotopic differentiation of an epizonal magma body: Organ Needle pluton, New Mexico

USGS Publications Warehouse

Verplanck, P.L.; Farmer, G.L.; McCurry, M.; Mertzman, S.A.

1999-01-01

Major and trace element, and Nd and Sr isotopic compositions of whole rocks and mineral separates from the Oligocene, alkaline Organ Needle pluton (ONP), southern New Mexico, constrain models for the differentiation of the magma body parental to this compositionally zoned and layered epizonal intrusive body. The data reveal that the pluton is rimmed by lower ??(Nd) (~-5) and higher 87Sr/86Sr (~0.7085) syenitic rocks than those in its interior (??(Nd) ~ 2, 87Sr/86Sr ~0.7060) and that the bulk compositions of the marginal rocks become more felsic with decreasing structural depth. At the deepest exposed levels of the pluton, the ??(Nd)~-5 lithology is a compositionally heterogeneous inequigranular syenite. Modal, compositional and isotopic data from separates of rare earth element (REE)-bearing major and accesory mineral phases (hornblende, titanite, apatite, zircon) demonstrate that this decoupling of trace and major elements in the inequigranular syenite results from accumulation of light REE (LREE)-bearing minerals that were evidently separated from silicic magmas as the latter rose along the sides of the magma chamber. Chemical and isotopic data for microgranular mafic enclaves, as well as for restite xenoliths of Precambrian granite wall rock, indicate that the isotopic distinction between the marginal and interior facies of the ONP probably reflects assimilation of the wall rock by ??(Nd) ~-2 mafic magmas near the base of the magma system. Fractional crystallization and crystal liquid separation of the crystally contaminated magma at the base and along the margins of the chamber generated the highly silicic magmas that ultimately pooled at the chamber top.

Isotopic insights into biological regulation of zinc in contaminated systems

USGS Publications Warehouse

Wanty, Richard B.; Balistrieri, Laurie S.; Wesner, Jeff S.; Walters, David; Schmidt, Travis S.; Podda, Francesca; De Giudici, G.; Stricker, Craig A.; Kraus, Johanna M.; Lattanzi, Pierfranco; Wolf, Ruth E.; Cidu, R.

2015-01-01

Aquatic organisms use a variety of biogeochemical reactions to regulate essential and non-essential trace metals. Many of these mechanisms can lead to isotopic fractionation, thus measurement of metal isotopes may yield insights into the processes by which organisms respond to metal exposure. We illustrate these concepts with two case studies, one involving an intra- and the other an extra-cellular mechanism of Zn sequestration. In the first study, the mayfly Neocloeon triangulifer was grown in the laboratory, and fed a diet of Zn-doped diatoms at Zn levels exceeding the requirements for normal mayfly life functions. The N. triangulifer larvae consumed the diatoms and retained their Zn isotopic signature. Upon metamorphosis, the subimago life stage lost Zn mass either in the exuvia or by excretion, and the Zn retained was isotopically enriched. Thus, Zn uptake is nonfractionating, but Zn regulation favors the lighter isotope. Thus the Zn remaining in the subimago was isotopically heavier. In the second study, Zn was adsorbed on the cell walls and exopolysaccharide secretions of cyanobacteria, which favored the heavier Zn isotope. Continued adsorption eventually resulted in nucleation and biomineralization of hydrozincite {Zn5(CO3)2(OH)6}. These case studies demonstrate the utility of Zn isotopes to provide insights into how aquatic insects respond to metal exposure.

Carbon Stable Isotopes as Indicators of Coastal Eutrophication

EPA Science Inventory

Coastal ecologists and managers have frequently used nitrogen stable isotopes (δ15N) to trace and monitor anthropogenic nitrogen (N) in coastal ecosystems. However, the interpretation of δ15N data can often be challenging, if not confounding, as the isotope values fractionate su...

Combining stable isotope isotope geochemistry and carbonic anhydrase activity to trace vital effect in carbonate precipitation experiments

NASA Astrophysics Data System (ADS)

Thaler, C.; Ader, M.; Menez, B.; Guyot, F. J.

2013-12-01

Carbonates precipitated by skeleton-forming eukaryotic organisms are often characterized by non-equilibrium isotopic signatures. This specificity is referred to as the "vital effect" and can be used as an isotopic evidence to trace life. Combining stable isotope geochemistry and enzymology (using the enzyme carbonic anhydrase) we aim to demonstrate that prokaryotes are also able to precipitate carbonate with a non-equilibrium d18OCaCO3. Indeed, if in an biomineralization experiment carbonates are precipitated with a vital effect, the addition of carbonic anhydrase should drive the system to isotope equilibrium, And provide a comparison point to estimate the vital effect range. This protocol allowed us to identify a -20‰ vital effect for the d18O of carbonates precipitated by Sporosarcina pasteurii, a bacterial model of carbonatogen metabolisms. This approach is thus a powerfull tool for the understanding of microbe carbonatogen activity and will probably bring new insights into the understanding of bacterial activity in subsurface and during diagenesis.

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.

Multielemental analysis of 18 essential and toxic elements in amniotic fluid samples by ICP-MS: Full procedure validation and estimation of measurement uncertainty.

PubMed

Markiewicz, B; Sajnóg, A; Lorenc, W; Hanć, A; Komorowicz, I; Suliburska, J; Kocyłowski, R; Barałkiewicz, D

2017-11-01

Amniotic fluid is the substantial factor in the development of an embryo and fetus due to the fact that water and solutes contained in it penetrate the fetal membranes in an hydrostatic and osmotic way as well as being swallowed by the fetus. Elemental composition of amniotic fluid influences the growth and health of the fetus, therefore, an analysis of amniotic fluid is important because the results would indicate abnormal levels of minerals or toxic elements. Inductively coupled plasma mass spectroscopy (ICP-MS) is often used for determination of trace and ultra-trace level elements in a wide range of matrices including biological samples because of its unique analytical capabilities. In the case of trace and ultra-trace level analysis detailed characteristics of analytical procedure as well as properties of the analytical result are particularly important. The purpose of this study was to develop a new analytical procedure for multielemental analysis of 18 elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Mg, Mn, Ni, Pb, Sb, Se, Sr, U, V and Zn) in amniotic fluid samples using ICP-MS. Dynamic reaction cell (DRC) with two reaction gases, ammonia and oxygen, was involved in the experiment to eliminate spectral interferences. Detailed validation was conducted using 3 certified reference mterials (CRMs) and real amniotic fluid samples collected from patients. Repeatability for all analyzed analytes was found to range from 0.70% to 8.0% and for intermediate precision results varied from 1.3% to 15%. Trueness expressed as recovery ranged from 80% to 125%. Traceability was assured through the analyses of CRMs. Uncertainty of the results was also evaluated using single-laboratory validation approach. The obtained expanded uncertainty (U) results for CRMs, expressed as a percentage of the concentration of an analyte, were found to be between 8.3% for V and 45% for Cd. Standard uncertainty of the precision was found to have a greater influence on the combined standard uncertainty than on trueness factor. Copyright © 2017 Elsevier B.V. All rights reserved.

Tracing biogeochemical subsidies from glacier runoff into Alaska's coastal marine food webs.

PubMed

Arimitsu, Mayumi L; Hobson, Keith A; Webber, D'Arcy N; Piatt, John F; Hood, Eran W; Fellman, Jason B

2018-01-01

Nearly half of the freshwater discharge into the Gulf of Alaska originates from landscapes draining glacier runoff, but the influence of the influx of riverine organic matter on the trophodynamics of coastal marine food webs is not well understood. We quantified the ecological impact of riverine organic matter subsidies to glacier-marine habitats by developing a multi-trophic level Bayesian three-isotope mixing model. We utilized large gradients in stable (δ 13 C, δ 15 N, δ 2 H) and radiogenic (Δ 14 C) isotopes that trace riverine and marine organic matter sources as they are passed from lower to higher trophic levels in glacial-marine habitats. We also compared isotope ratios between glacial-marine and more oceanic habitats. Based on isotopic measurements of potential baseline sources, ambient water and tissues of marine consumers, estimates of the riverine organic matter source contribution to upper trophic-level species including fish and seabirds ranged from 12% to 44%. Variability in resource use among similar taxa corresponded to variation in species distribution and life histories. For example, riverine organic matter assimilation by the glacier-nesting seabirds Kittlitz's murrelet (Brachyramphus brevirostris) was greater than that of the forest-nesting marbled murrelet (B. marmoratus). The particulate and dissolved organic carbon in glacial runoff and near surface coastal waters was aged (12100-1500 years BP 14 C-age) but dissolved inorganic carbon and biota in coastal waters were young (530 years BP 14 C-age to modern). Thus terrestrial-derived subsidies in marine food webs were primarily composed of young organic matter sources released from glacier ecosystems and their surrounding watersheds. Stable isotope compositions also revealed a divergence in food web structure between glacial-marine and oceanic sites. This work demonstrates linkages between terrestrial and marine ecosystems, and facilitates a greater understanding of how climate-driven changes in freshwater runoff have the potential to alter food web dynamics within coastal marine ecosystems in Alaska. Published 2017. This article is a U.S. Government work and is in the public domain in the USA.

Determination of ultra-trace aluminum in human albumin by cloud point extraction and graphite furnace atomic absorption spectrometry.

PubMed

Sun, Mei; Wu, Qianghua

2010-04-15

A cloud point extraction (CPE) method for the preconcentration of ultra-trace aluminum in human albumin prior to its determination by graphite furnace atomic absorption spectrometry (GFAAS) had been developed in this paper. The CPE method was based on the complex of Al(III) with 1-(2-pyridylazo)-2-naphthol (PAN) and Triton X-114 was used as non-ionic surfactant. The main factors affecting cloud point extraction efficiency, such as pH of solution, concentration and kind of complexing agent, concentration of non-ionic surfactant, equilibration temperature and time, were investigated in detail. An enrichment factor of 34.8 was obtained for the preconcentration of Al(III) with 10 mL solution. Under the optimal conditions, the detection limit of Al(III) was 0.06 ng mL(-1). The relative standard deviation (n=7) of sample was 3.6%, values of recovery of aluminum were changed from 92.3% to 94.7% for three samples. This method is simple, accurate, sensitive and can be applied to the determination of ultra-trace aluminum in human albumin. 2009 Elsevier B.V. All rights reserved.

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.

Diamond brecciation and annealing accompanying major metasomatism in eclogite xenoliths from the Sask Craton, Canada

NASA Astrophysics Data System (ADS)

Czas, Janina; Stachel, Thomas; Pearson, D. Graham; Stern, Richard A.; Read, George H.

2018-05-01

We studied eclogite xenoliths (diamond-free n = 28; diamondiferous n = 22) from the Cretaceous Fort à la Corne Kimberlite Field in Western Canada for their major element, trace element and oxygen isotope compositions to assess their origin and metasomatic history, and possible relationships between metasomatism and diamond formation. All eclogites have major element and oxygen isotope compositions consistent with a derivation from different levels of subducted, seawater altered oceanic crust. While barren xenoliths are more likely to be of gabbroic origin, diamond-bearing samples commonly have signatures consistent with shallow basaltic protoliths. The mineral chemistry in bimineralic diamond-free eclogites spans a wide compositional range, yet it is typically homogenous within individual xenoliths. Temperatures calculated from Mg-Fe exchange between garnet and clinopyroxene range widely for these eclogites, from 740 to 1300 °C, indicating the presence of eclogite through most of the lithospheric mantle. Diamondiferous samples are restricted to high temperatures (1180-1390 °C), consistent with derivation from the zone of diamond stability. Compositionally, diamond-bearing eclogites span a broad range similar to their barren counterparts, but there is also heterogeneity in mineral chemistry on the intra-sample level and in particular garnets are characterised by strong internal chemical gradients. This intra-sample heterogeneity is interpreted as the result of intense melt metasomatism, which occurred in temporal proximity to host kimberlite magmatism, strongly affected major, trace and even oxygen isotope values and resulted in diamond brecciation and annealing.

Integration of stable isotope and trace contaminant concentration for enhanced forensic acetone discrimination.

PubMed

Moran, James J; Ehrhardt, Christopher J; Wahl, Jon H; Kreuzer, Helen W; Wahl, Karen L

2013-11-15

We analyzed 21 neat acetone samples from 15 different suppliers to demonstrate the utility of a coupled stable isotope and trace contaminant strategy for distinguishing forensically-relevant samples. By combining these two pieces of orthogonal data we could discriminate all of the acetones that were produced by the 15 different suppliers. Using stable isotope ratios alone, we were able to distinguish 8 acetone samples, while the remaining 13 fell into four clusters with highly similar signatures. Adding trace chemical contaminant information enhanced discrimination to 13 individual acetones with three residual clusters. The acetones within each cluster shared a common manufacturer and might, therefore, not be expected to be resolved. The data presented here demonstrates the power of combining orthogonal data sets to enhance sample fingerprinting and highlights the role disparate data could play in future forensic investigations. © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Shielding concepts for low-background proportional counter arrays in surface laboratories

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

Aalseth, Craig E.; Humble, Paul H.; Mace, Emily K.

2016-02-01

Development of ultra low background gas proportional counters has made the contribution from naturally occurring radioactive isotopes – primarily and activity in the uranium and thorium decay chains – inconsequential to instrumental sensitivity levels when measurements are performed in above ground surface laboratories. Simple lead shielding is enough to mitigate against gamma rays as gas proportional counters are already relatively insensitive to naturally occurring gamma radiation. The dominant background in these surface laboratory measurements using ultra low background gas proportional counters is due to cosmic ray generated muons, neutrons, and protons. Studies of measurements with ultra low background gas proportionalmore » counters in surface and underground laboratories as well as radiation transport Monte Carlo simulations suggest a preferred conceptual design to achieve the highest possible sensitivity from an array of low background gas proportional counters when operated in a surface laboratory. The basis for a low background gas proportional counter array and the preferred shielding configuration is reported, especially in relation to measurements of radioactive gases having low energy decays such as 37Ar.« less

An isotope dilution ultra high performance liquid chromatography-tandem mass spectrometry method for the simultaneous determination of sugars and humectants in tobacco products.

PubMed

Wang, Liqun; Cardenas, Roberto Bravo; Watson, Clifford

2017-09-08

CDC's Division of Laboratory Sciences developed and validated a new method for the simultaneous detection and measurement of 11 sugars, alditols and humectants in tobacco products. The method uses isotope dilution ultra high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) and has demonstrated high sensitivity, selectivity, throughput and accuracy, with recoveries ranging from 90% to 113%, limits of detection ranging from 0.0002 to 0.0045μg/mL and coefficients of variation (CV%) ranging from 1.4 to 14%. Calibration curves for all analytes were linear with linearity R 2 values greater than 0.995. Quantification of tobacco components is necessary to characterize tobacco product components and their potential effects on consumer appeal, smoke chemistry and toxicology, and to potentially help distinguish tobacco product categories. The researchers analyzed a variety of tobacco products (e.g., cigarettes, little cigars, cigarillos) using the new method and documented differences in the abundance of selected analytes among product categories. Specifically, differences were detected in levels of selected sugars found in little cigars and cigarettes, which could help address appeal potential and have utility when product category is unknown, unclear, or miscategorized. Copyright © 2017. Published by Elsevier B.V.

ION COMPOSITION ELUCIDATION (ICE): AN INVESTIGATIVE ...

EPA Pesticide Factsheets

Ion Composition Elucidation (ICE) often leads to identification of compounds and provides high quality evidence for tracking compounds to their sources. Mass spectra for most organic compounds are not found in mass spectral libraries used to tentatively identify analytes. In addition, multiple matches are common. Ion Composition Elucidation provides the numbers of atoms of each element in the ions in the mass spectrum, greatly limiting the number of possible compounds that could produce the mass spectrum. Review of chemical and commercial literature then limits the number of possible compounds to one or a few that can be purchased to confirm tentative compound identifications by comparison of mass spectra and chromatographic retention times. Ion Composition Elucidation is conceptually simple relative to other analytical techniques and more easily explained to a judge or jury. It is based on sums of the exact masses of atoms and their isotopic abundances. Several applications of ICE are demonstrated for ultra-trace-level compounds in an extract of the effluent from a tertiary sewage treatment plant including: (i) measurement of five values to determine an ion's composition and to generate evidence for the compound's identity, (ii) rejection of incorrect library matches, (iii) rapid screening for a target compound in an extract, and (iv) a strategy for tracking unidentified compounds to their sources. The research focused on in the subtasks is the development and

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Subseafloor Microbial Life in Venting Fluids from the Mid Cayman Rise Hydrothermal System

NASA Astrophysics Data System (ADS)

Huber, J. A.; Reveillaud, J.; Reddington, E.; McDermott, J. M.; Sylva, S. P.; Breier, J. A.; German, C. R.; Seewald, J.

2012-12-01

In hard rock seafloor environments, fluids emanating from hydrothermal vents are one of the best windows into the subseafloor and its resident microbial community. The functional consequences of an extensive population of microbes living in the subseafloor remains unknown, as does our understanding of how these organisms interact with one another and influence the biogeochemistry of the oceans. Here we report the abundance, activity, and diversity of microbes in venting fluids collected from two newly discovered deep-sea hydrothermal vents along the ultra-slow spreading Mid-Cayman Rise (MCR). Fluids for geochemical and microbial analysis were collected from the Von Damm and Piccard vent fields, which are located within 20 km of one another, yet have extremely different thermal, geological, and depth regimes. Geochemical data indicates that both fields are highly enriched in volatiles, in particular hydrogen and methane, important energy sources for and by-products of microbial metabolism. At both sites, total microbial cell counts in the fluids ranged in concentration from 5 x 10 4 to 3 x 10 5 cells ml-1 , with background seawater concentrations of 1-2 x 10 4 cells ml-1 . In addition, distinct cell morphologies and clusters of cells not visible in background seawater were seen, including large filaments and mineral particles colonized by microbial cells. These results indicate local enrichments of microbial communities in the venting fluids, distinct from background populations, and are consistent with previous enumerations of microbial cells in venting fluids. Stable isotope tracing experiments were used to detect utilization of acetate, formate, and dissolve inorganic carbon and generation of methane at 70 °C under anaerobic conditions. At Von Damm, a putatively ultra-mafic hosted site located at ~2200 m with a maximum temperature of 226 °C, stable isotope tracing experiments indicate methanogenesis is occurring in most fluid samples. No activity was detected in Piccard vent fluids, a basalt-hosted black smoker site located at ~4950 m with a maximum temperature of 403 °C. However, hyperthermophilic and thermophilic heterotrophs of the genus Thermococcus were isolated from Piccard vent fluids, but not Von Damm. These obligate anaerobes, growing optimally at 55-90 °C, are ubiquitous at hydrothermal systems and serve as a readily cultivable indicator organism of subseafloor populations. Finally, molecular analysis of vent fluids is on-going and will define the microbial population structure in this novel ecosystem and allow for direct comparisons with other deep-sea and subsurface habitats as part of our continuing efforts to explore the deep microbial biosphere on Earth.

A carbon isotope challenge to the snowball Earth.

PubMed

Sansjofre, P; Ader, M; Trindade, R I F; Elie, M; Lyons, J; Cartigny, P; Nogueira, A C R

2011-10-05

The snowball Earth hypothesis postulates that the planet was entirely covered by ice for millions of years in the Neoproterozoic era, in a self-enhanced glaciation caused by the high albedo of the ice-covered planet. In a hard-snowball picture, the subsequent rapid unfreezing resulted from an ultra-greenhouse event attributed to the buildup of volcanic carbon dioxide (CO(2)) during glaciation. High partial pressures of atmospheric CO(2) (pCO2; from 20,000 to 90,000 p.p.m.v.) in the aftermath of the Marinoan glaciation (∼635 Myr ago) have been inferred from both boron and triple oxygen isotopes. These pCO2 values are 50 to 225 times higher than present-day levels. Here, we re-evaluate these estimates using paired carbon isotopic data for carbonate layers that cap Neoproterozoic glacial deposits and are considered to record post-glacial sea level rise. The new data reported here for Brazilian cap carbonates, together with previous ones for time-equivalent units, provide estimates lower than 3,200 p.p.m.v.--and possibly as low as the current value of ∼400 p.p.m.v. Our new constraint, and our re-interpretation of the boron and triple oxygen isotope data, provide a completely different picture of the late Neoproterozoic environment, with low atmospheric concentrations of carbon dioxide and oxygen that are inconsistent with a hard-snowball Earth.

Application of environmental isotopes and hydrochemistry in the identification of source of seepage and likely connection with lake water in Lesser Himalaya, Uttarakhand, India

NASA Astrophysics Data System (ADS)

Rai, Shive Prakash; Singh, Dharmaveer; Rai, Ashwani Kumar; Kumar, Bhishm

2017-12-01

Oxygen (δ^{18}O) and hydrogen (δ2H and 3H) isotopes of water, along with their hydrochemistry, were used to identify the source of a newly emerged seepage water in the downstream of Lake Nainital, located in the Lesser Himalayan region of Uttarakhand, India. A total of 57 samples of water from 19 different sites, in and around the seepage site, were collected. Samples were analysed for chemical tracers like Ca^{++}, Mg^{++}, Na+, K+, {SO4}^{-} and Cl- using an Ion Chromatograph (Dionex IC-5000). A Dual Inlet Isotope Ratio Mass Spectrometer (DIIRMS) and an Ultra-Low Level Liquid Scintillation Counter (ULLSC), were used in measurements of stable isotopes (δ2H and δ^{18}O) and a radioisotope (3H), respectively. Results obtained in this study repudiate the possibility of any likely connection between seepage water and the lake water, and indicate that the source of seepage water is mainly due to locally recharged groundwater. The study suggests that environmental isotopes (δ2H, δ^{18}O and 3H) can effectively be used as `tracers' in the detection of the source of seepage water in conjunction with other hydrochemical tracers, and can help in water resource management and planning.

Utility of multiple chemical techniques in archaeological residential mobility studies: case studies from Tiwanaku- and Chiribaya-affiliated sites in the Andes.

PubMed

Knudson, Kelly J; Price, T Douglas

2007-01-01

In the south central Andes, archaeologists have long debated the extent of Tiwanaku colonization during the Middle Horizon (AD 500-1000). We tested the hypotheses regarding the nature of Tiwanaku influence using strontium isotope, trace element concentration, and oxygen isotope data from archaeological human tooth enamel and bone from Tiwanaku- and Chiribaya-affiliated sites in the south central Andes. Strontium isotope analysis of 25 individuals buried at the Tiwanaku-affiliated Moquegua Valley site of Chen Chen demonstrates that it was likely a Tiwanaku colony. In contrast, no immigrants from the Lake Titicaca Basin were present in 27 individuals analyzed from the San Pedro de Atacama cemeteries of Coyo Oriental, Coyo-3, and Solcor-3; it is likely that these sites represent economic and religious alliances, but not colonies. However, strontium isotope analysis alone cannot distinguish movement between the Tiwanaku- and Chiribaya-affiliated sites in the Moquegua and Ilo Valleys of southern Peru. Analyzing oxygen isotope and trace element concentration data and comparing it with strontium isotope data from the same individuals provides a more detailed picture of residential mobility in the Tiwanaku and Chiribaya polities. In addition to monitoring diagenetic contamination, trace element concentration data identified movement during adulthood for certain individuals. However, these data could not distinguish movement between the Moquegua and Ilo Valleys. While oxygen isotope data could clearly distinguish the high-altitude sites from others, more data is needed to characterize the local oxygen isotope ratios of these regions. These data demonstrate the potential for archaeological reconstruction of residential mobility through multiple lines of evidence. (c) 2006 Wiley-Liss, Inc

Chemical Sensing for Buried Landmines - Fundamental Processes Influencing Trace Chemical Detection

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

PHELAN, JAMES M.

2002-05-01

Mine detection dogs have a demonstrated capability to locate hidden objects by trace chemical detection. Because of this capability, demining activities frequently employ mine detection dogs to locate individual buried landmines or for area reduction. The conditions appropriate for use of mine detection dogs are only beginning to emerge through diligent research that combines dog selection/training, the environmental conditions that impact landmine signature chemical vapors, and vapor sensing performance capability and reliability. This report seeks to address the fundamental soil-chemical interactions, driven by local weather history, that influence the availability of chemical for trace chemical detection. The processes evaluated include:more » landmine chemical emissions to the soil, chemical distribution in soils, chemical degradation in soils, and weather and chemical transport in soils. Simulation modeling is presented as a method to evaluate the complex interdependencies among these various processes and to establish conditions appropriate for trace chemical detection. Results from chemical analyses on soil samples obtained adjacent to landmines are presented and demonstrate the ultra-trace nature of these residues. Lastly, initial measurements of the vapor sensing performance of mine detection dogs demonstrates the extreme sensitivity of dogs in sensing landmine signature chemicals; however, reliability at these ultra-trace vapor concentrations still needs to be determined. Through this compilation, additional work is suggested that will fill in data gaps to improve the utility of trace chemical detection.« less

Trace and minor element variations and sulfur isotopes in crystalline and colloform ZnS: Incorporation mechanisms and implications for their genesis

USGS Publications Warehouse

Pfaff, Katharina; Koenig, Alan; Wenzel, Thomas; Ridley, Ian; Hildebrandt, Ludwig H.; Leach, David L.; Markl, Gregor

2011-01-01

Various models have been proposed to explain the formation mechanism of colloform sphalerite, but the origin is still under debate. In order to decipher influences on trace element incorporation and sulfur isotope composition, crystalline and colloform sphalerite from the carbonate-hosted Mississippi-Valley Type (MVT) deposit near Wiesloch, SW Germany, were investigated and compared to sphalerite samples from 52 hydrothermal vein-type deposits in the Schwarzwald ore district, SW Germany to study the influence of different host rocks, formation mechanisms and fluid origin on trace element incorporation. Trace and minor element incorporation in sphalerite shows some correlation to their host rock and/or origin of fluid, gangue, paragenetic minerals and precipitation mechanisms (e.g., diagenetic processes, fluid cooling or fluid mixing). Furthermore, crystalline sphalerite is generally enriched in elements like Cd, Cu, Sb and Ag compared to colloform sphalerite that mainly incorporates elements like As, Pb and Tl. In addition, sulfur isotopes are characterized by positive values for crystalline and strongly negative values for colloform sphalerite. The combination of trace element contents, typical minerals associated with colloform sphalerite from Wiesloch, sulfur isotopes and thermodynamic considerations helped to evaluate the involvement of sulfate-reducing bacteria in water-filled karst cavities. Sulfate-reducing bacteria cause a sulfide-rich environment that leads in case of a metal-rich fluid supply to a sudden oversaturation of the fluid with respect to galena, sphalerite and pyrite. This, however, exactly coincides with the observed crystallization sequence of samples involving colloform sphalerite from the Wiesloch MVT deposit.

Multivariate statistical analysis of the polyphenolic constituents in kiwifruit juices to trace fruit varieties and geographical origins.

PubMed

Guo, Jing; Yuan, Yahong; Dou, Pei; Yue, Tianli

2017-10-01

Fifty-one kiwifruit juice samples of seven kiwifruit varieties from five regions in China were analyzed to determine their polyphenols contents and to trace fruit varieties and geographical origins by multivariate statistical analysis. Twenty-one polyphenols belonging to four compound classes were determined by ultra-high-performance liquid chromatography coupled with ultra-high-resolution TOF mass spectrometry. (-)-Epicatechin, (+)-catechin, procyanidin B1 and caffeic acid derivatives were the predominant phenolic compounds in the juices. Principal component analysis (PCA) allowed a clear separation of the juices according to kiwifruit varieties. Stepwise linear discriminant analysis (SLDA) yielded satisfactory categorization of samples, provided 100% success rate according to kiwifruit varieties and 92.2% success rate according to geographical origins. The result showed that polyphenolic profiles of kiwifruit juices contain enough information to trace fruit varieties and geographical origins. Copyright © 2017 Elsevier Ltd. All rights reserved.

Magnetic ionic liquid-based dispersive liquid-liquid microextraction technique for preconcentration and ultra-trace determination of Cd in honey.

PubMed

Fiorentini, Emiliano F; Escudero, Leticia B; Wuilloud, Rodolfo G

2018-04-19

A simple, highly efficient, batch, and centrifuge-less dispersive liquid-liquid microextraction method based on a magnetic ionic liquid (MIL-DLLME) and electrothermal atomic absorption spectrometry (ETAAS) detection was developed for ultra-trace Cd determination in honey. Initially, Cd(II) was chelated with ammonium diethyldithiophosphate (DDTP) at pH 0.5 followed by its extraction with the MIL trihexyl(tetradecyl)phosphonium tetrachloroferrate(III) ([P 6,6,6,14 ]FeCl 4 ) and acetonitrile as dispersant. The MIL phase containing the analyte was separated from the aqueous phase using only a magnet. A back-extraction procedure was applied to recover Cd from the MIL phase using diluted HNO 3 and this solution was directly injected into the graphite furnace of ETAAS instrument. An extraction efficiency of 93% and a sensitivity enhancement factor of 112 were obtained under optimal experimental conditions. The detection limit (LOD) was 0.4 ng L -1 Cd, while the relative standard deviation (RSD) was 3.8% (at 2 μg L -1 Cd and n = 10), calculated from the peak height of absorbance signals. This work reports the first application of the MIL [P 6,6,6,14 ]FeCl 4 along with the DLLME technique for the successful determination of Cd at trace levels in different honey samples. Graphical abstract Preconcentration of ultratraces of Cd in honey using a magnetic ionic liquid and dispersive liquid-liquid microextraction technique.

Changes in magma storage conditions following caldera collapse at Okataina Volcanic Center, New Zealand

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

Rubin, Allison; Cooper, Kari M.; Leever, Marissa

Large silicic volcanic centers produce both small rhyolitic eruptions and catastrophic caldera-forming eruptions. Although changes in trace element and isotopic compositions within eruptions following caldera collapse have been observed at rhyolitic volcanic centers such as Yellowstone and Long Valley, much still remains unknown about the ways in which magma reservoirs are affected by caldera collapse. We present 238U– 230Th age, trace element, and Hf isotopic data from individual zircon crystals from four eruptions from the Okataina Volcanic Center, Taupo Volcanic Zone, New Zealand, in order to assess changes in trace element and isotopic composition of the reservoir following the 45-kamore » caldera-forming Rotoiti eruption. Our data indicate that (1) mixing of magmas derived from crustal melts and mantle melts takes place within the shallow reservoir; (2) while the basic processes of melt generation likely did not change significantly between pre- and post-caldera rhyolites, post-caldera zircons show increased trace element and isotopic heterogeneity that suggests a decrease in the degree of interconnectedness of the liquid within the reservoir following collapse; and (3) post-caldera eruptions from different vents indicate different storage times of the amalgamated melt prior to eruption. Furthermore, these data further suggest that the timescales needed to generate large volumes of eruptible melt may depend on the timescales needed to increase interconnectedness and achieve widespread homogenization throughout the reservoir.« less

Changes in magma storage conditions following caldera collapse at Okataina Volcanic Center, New Zealand

DOE PAGES

Rubin, Allison; Cooper, Kari M.; Leever, Marissa; ...

2015-12-15

Large silicic volcanic centers produce both small rhyolitic eruptions and catastrophic caldera-forming eruptions. Although changes in trace element and isotopic compositions within eruptions following caldera collapse have been observed at rhyolitic volcanic centers such as Yellowstone and Long Valley, much still remains unknown about the ways in which magma reservoirs are affected by caldera collapse. We present 238U– 230Th age, trace element, and Hf isotopic data from individual zircon crystals from four eruptions from the Okataina Volcanic Center, Taupo Volcanic Zone, New Zealand, in order to assess changes in trace element and isotopic composition of the reservoir following the 45-kamore » caldera-forming Rotoiti eruption. Our data indicate that (1) mixing of magmas derived from crustal melts and mantle melts takes place within the shallow reservoir; (2) while the basic processes of melt generation likely did not change significantly between pre- and post-caldera rhyolites, post-caldera zircons show increased trace element and isotopic heterogeneity that suggests a decrease in the degree of interconnectedness of the liquid within the reservoir following collapse; and (3) post-caldera eruptions from different vents indicate different storage times of the amalgamated melt prior to eruption. Furthermore, these data further suggest that the timescales needed to generate large volumes of eruptible melt may depend on the timescales needed to increase interconnectedness and achieve widespread homogenization throughout the reservoir.« less

Seabird satellite tracking validates the use of latitudinal isoscapes to depict predators' foraging areas in the Southern Ocean.

PubMed

Jaeger, Audrey; Lecomte, Vincent J; Weimerskirch, Henri; Richard, Pierre; Cherel, Yves

2010-12-15

Stable isotopes are increasingly being used to trace wildlife movements. A fundamental prerequisite of animal isotopic tracking is a good knowledge of spatial isotopic variations in the environment. Few accessible reference maps of the isotopic landscape ("isoscapes") are available for marine predators. Here, we validate for the first time an isotopic gradient for higher trophic levels by using a unique combination of a large number of satellite-tracks and subsequent blood plasma isotopic signatures from a wide-ranging oceanic predator. The plasma δ(13)C and δ(15)N values of wandering albatrosses (n = 45) were highly and positively correlated to the Southern Ocean latitudes at which the satellite-tracked individuals foraged. The well-defined latitudinal baseline carbon isoscapes in the Southern Ocean is thus reflected in the tissue of consumers, but with a positive shift due to the cumulative effect of a slight (13)C-enrichment at each trophic level. The data allowed us to estimate the carbon isotopic position of the main oceanic fronts in the area, and thus to delineate robust isoscapes of the main foraging zones for top predators. The plasma δ(13)C and δ(15)N values were positively and linearly correlated, thus suggesting that latitudinal isoscapes also occur for δ(15)N at the base of the food web in oceanic waters of the Southern Ocean. The combination of device deployments with sampling of relevant tissues for isotopic analysis appears to be a powerful tool for investigating consumers' isoscapes at various spatio-temporal scales. Copyright © 2010 John Wiley & Sons, Ltd.

Tracing thallium contamination in soils using isotopes

NASA Astrophysics Data System (ADS)

Vaněk, Aleš; Grösslová, Zuzana; Mihaljevič, Martin; Ettler, Vojtěch; Trubač, Jakub; Teper, Leslaw; Cabala, Jerzy; Rohovec, Jan; Penížek, Vít; Zádorová, Tereza; Pavlů, Lenka; Holubík, Ondřej; Drábek, Ondřej; Němeček, Karel; Houška, Jakub; Ash, Christopher

2017-04-01

We report the thallium (Tl) isotope record in moderately contaminated soils, which have been historically affected by emissions from coal-fired power plants. Our findings clearly demonstrate that Tl of anthropogenic (high-temperature) origin with light isotope composition was deposited onto the studied soils, where heavier Tl (ɛ205Tl -1) naturally occurs. The results show a positive linear relationship (R2 = 0.71) between 1/Tl and the isotope record, as determined for all the soils and bedrocks, also indicative of binary Tl mixing between two dominant reservoirs. We also identified significant Tl isotope variations within the products from coal combustion and thermo-desorption experiments with local Tl-rich coal pyrite. Bottom ash exhibited the heaviest Tl isotope composition (ɛ205Tl 0), followed by fly ash (ɛ205Tl between -2.5 and -2.8) and volatile Tl fractions (ɛ205Tl between -6.2 and -10.3), suggesting partial Tl isotope fractionations. Despite the evident role of soil processes in the isotope redistribution, we demonstrate that Tl contamination can be traced in soils, and propose that the isotope data represent a possible tool to aid our understanding of post-depositional Tl dynamics in surface environments for the future. This research was supported by the Czech Science Foundation (grant no. 14-01866S and 17-03211S).

Tracing carbon flow in an arctic marine food web using fatty acid-stable isotope analysis.

PubMed

Budge, S M; Wooller, M J; Springer, A M; Iverson, S J; McRoy, C P; Divoky, G J

2008-08-01

Global warming and the loss of sea ice threaten to alter patterns of productivity in arctic marine ecosystems because of a likely decline in primary productivity by sea ice algae. Estimates of the contribution of ice algae to total primary production range widely, from just 3 to >50%, and the importance of ice algae to higher trophic levels remains unknown. To help answer this question, we investigated a novel approach to food web studies by combining the two established methods of stable isotope analysis and fatty acid (FA) analysis--we determined the C isotopic composition of individual diatom FA and traced these biomarkers in consumers. Samples were collected near Barrow, Alaska and included ice algae, pelagic phytoplankton, zooplankton, fish, seabirds, pinnipeds and cetaceans. Ice algae and pelagic phytoplankton had distinctive overall FA signatures and clear differences in delta(13)C for two specific diatom FA biomarkers: 16:4n-1 (-24.0+/-2.4 and -30.7+/-0.8 per thousand, respectively) and 20:5n-3 (-18.3+/-2.0 and -26.9+/-0.7 per thousand, respectively). Nearly all delta(13)C values of these two FA in consumers fell between the two stable isotopic end members. A mass balance equation indicated that FA material derived from ice algae, compared to pelagic diatoms, averaged 71% (44-107%) in consumers based on delta(13)C values of 16:4n-1, but only 24% (0-61%) based on 20:5n-3. Our estimates derived from 16:4n-1, which is produced only by diatoms, probably best represented the contribution of ice algae relative to pelagic diatoms. However, many types of algae produce 20:5n-3, so the lower value derived from it likely represented a more realistic estimate of the proportion of ice algae material relative to all other types of phytoplankton. These preliminary results demonstrate the potential value of compound-specific isotope analysis of marine lipids to trace C flow through marine food webs and provide a foundation for future work.

Isotopic tracking of Hanford 300 area derived uranium in the Columbia River.

PubMed

Christensen, John N; Dresel, P Evan; Conrad, Mark E; Patton, Gregory W; DePaolo, Donald J

2010-12-01

Our objectives in this study are to quantify the discharge rate of uranium (U) to the Columbia River from the Hanford Site's 300 Area and to follow that U downriver to constrain its fate. Uranium from the Hanford Site has variable isotopic composition due to nuclear industrial processes carried out at the site. This characteristic makes it possible to use high-precision isotopic measurements of U in environmental samples to identify even trace levels of contaminant U, determine its sources, and estimate discharge rates. Our data on river water samples indicate that as much as 3.2 kg/day can enter the Columbia River from the 300 Area, which is only a small fraction of the total load of dissolved natural background U carried by the Columbia River. This very low level of Hanford-derived U can be discerned, despite dilution to <1% of natural background U, 400 km downstream from the Hanford Site. These results indicate that isotopic methods can allow the amounts of U from the 300 Area of the Hanford Site entering the Columbia River to be measured accurately to ascertain whether they are an environmental concern or insignificant relative to natural uranium background in the Columbia River.

The Cadmium Isotope Record of the Great Oxidation Event from the Turee Creek Group, Hamersley Basin, Australia

NASA Astrophysics Data System (ADS)

Abouchami, W.; Busigny, V.; Philippot, P.; Galer, S. J. G.; Cheng, C.; Pecoits, E.

2016-12-01

The evolution of the ocean, atmosphere and biosphere throughout Earth's history has impacted on the biogeochemistry of some key trace metals that are of particular importance in regulating the exchange between Earth's reservoirs. Several geochemical proxies exhibit isotopic shifts that have been linked to major changes in the oxygenation levels of the ancient oceans during the Great Oxygenation Event (GOE) between 2.45 and 2.2 Ga and the Neoproterozoic Oxygenation Event at ca. 0.6 Ga. Studies of the modern marine biogeochemical cycle of the transition metal Cadmium have shown that stable Cd isotope fractionation is mainly driven by biological uptake of light Cd into marine phytoplankton in surface waters leaving behind the seawater enriched in the heavy Cd isotopes. Here we use of the potential of this novel proxy to trace ancient biological productivity which remains an enigma, particularly during the early stages of Earth history. The Turee Creek Group in the Hamersley Basin, Australia, provides a continuous stratigraphic sedimentary section covering the GOE and at least two glacial events, offering a unique opportunity to examine the changes that took place during these periods and possibly constrain the evolution, timing and onset of oxygenic photosynthesis. Stable Cd isotope data were obtained on samples from the Boolgeeda Iron Fm. (BIFs), the siliciclastic and carbonate successions of Kungara (including the Meteorite Bore Member) and the Kazputt Fm., using a double spike technique by TIMS (ThermoFisher Triton) and Cd concentrations were determined by isotope dilution. The Boolgeeda BIFs have generally low Cd concentrations varying between 8 and 50ppb, with two major excursions marked by an increase in Cd content, reaching similar levels to those in the overlying Kungarra Fm. (≥150 ppb). These variations are associated with a large range in ɛ112/110Cd values (-2 to +2), with the most negative values typically found in the organic and Cd-rich shales and siltstones of the Kungara and Kazput formations. This suggests that a significant portion of the Cd present is organically bound, as also supported by the relationship with δ13Corg and TOC. These data will serve to assess the size of the ancient biomass during the GOE in view of our understanding of the modern Cd isotope biogeochemical cycling in the oceans.

CISOCUR - Hydrodynamic circulation in the Curonian Lagoon inferred through stable isotope measurements and numerical modelling

NASA Astrophysics Data System (ADS)

Umgiesser, Georg; Razinkovas-Baziukas, Arturas; Barisevičiūtė, Ruta; Baziukė, Dalia; Ertürk, Ali; Gasiūnaitė, Jovita; Gulbinskas, Saulius; Lubienė, Irma; Maračkinaite, Jurgita; Petkuvienė, Jolita; Pilkaitytė, Renata; Ruginis, Tomas; Zemlys, Petras; Žilius, Mindaugas

2013-04-01

The spatial pattern of the hydrodynamic circulation of the Curonian lagoon, the largest European coastal lagoon, is still little understood. In absence of automatic current registration data all the existing models relied mostly on such data as water levels leaving high level of uncertainty. Here we present CISOCUR, a new project financed by the European Social Fund under the Global Grant measure. The project applies a new methodology that uses the carbon stable isotope (SI) ratio of C12 and C13 that characterize different water sources entering the lagoon and may be altered by internal kinetic processes. Through the tracing of these isotope ratios different water masses can be identified. This gives the possibility to validate several hypotheses of water circulation and validate hydrodynamic models. In particular it will be possible to 1) trace water masses entering the lagoon through the Nemunas and the Klaipeda strait; 2) test the hypothesis of sediment transport mechanisms inside the lagoon; 3) evaluate the importance of physical forcing on the lagoon circulation. The use of a hydrodynamic finite element model, coupled with the SI method, will allow for a realistic description of the transport processes inside the Curonian lagoon. So the main research goal is to apply the stable isotope tracers and a finite element model to determine the circulation patterns in the Curonian lagoon. Overall, the project will develop according to 4 main phases: 1) A pilot study to measure the isotope composition of different carbon compounds (dissolved and suspended) in different water bodies that feed water into the central lagoon. Through this pilot study the optimal study sites for the seasonal campaign will be identified as well. 2) Seasonal field campaigns in the monitoring stations identified in phase 1 to measure the carbon isotope ratio. 3) Development of a model that describes the kinetics of carbon isotopes and its transformation. 4) Application of a hydrodynamic model that includes the kinetic model and uses the data in order to describe the overall circulation patterns in the Curonian lagoon. Project activities will be carried out as common co-ordinated effort of field an SI group and the modeling group that will have to calibrate the hydrodynamic model. In this way the expertise of different groups (physicists and oceanographers) will result in added value, providing the best available expertise along the eastern coast of the Baltic.

Design and operation of a continuous 13C and 15N labeling chamber for uniform or differential, metabolic and structural, plant tissue isotope labeling

USDA-ARS?s Scientific Manuscript database

Tracing heavy stable isotopes from plant material through the ecosystem provides the most sensitive information about ecosystem processes; from CO2 fluxes and soil organic matter formation to small-scale stable-isotope biomarker probing. Coupling multiple stable isotopes such as 13C with 15N, 18O o...

The MESSIER surveyor: unveiling the ultra-low surface brightness universe

NASA Astrophysics Data System (ADS)

Valls-Gabaud, David; MESSIER Collaboration

2017-03-01

The MESSIER surveyor is a small mission designed at exploring the very low surface brightness universe. The satellite will drift-scan the entire sky in 6 filters covering the 200-1000 nm range, reaching unprecedented surface brightness levels of 34 and 37 mag arcsec-2 in the optical and UV, respectively. These levels are required to achieve the two main science goals of the mission: to critically test the ΛCDM paradigm of structure formation through (1) the detection and characterisation of ultra-faint dwarf galaxies, which are predicted to be extremely abundant around normal galaxies, but which remain elusive; and (2) tracing the cosmic web, which feeds dark matter and baryons into galactic haloes, and which may contain the reservoir of missing baryons at low redshifts. A large number of science cases, ranging from stellar mass loss episodes to intracluster light through fluctuations in the cosmological UV-optical background radiation are free by-products of the full-sky maps produced.

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.

Nuclear astrophysics at FRANZ

NASA Astrophysics Data System (ADS)

Reifarth, R.; Dababneh, S.; Fiebiger, S.; Glorius, J.; Göbel, K.; Heil, M.; Hillmann, P.; Heftrich, T.; Langer, C.; Meusel, O.; Plag, R.; Schmidt, S.; Slavkovská, Z.; Veltum, D.; Weigand, M.; Wiesner, C.; Wolf, C.; Zadeh, A.

2018-01-01

The neutron capture cross section of radioactive isotopes for neutron energies in the keV region will be measured by a time-of-flight (TOF) experiment. NAUTILUS will provide a unique facility realizing the TOF technique with an ultra-short flight path at the FRANZ setup at Goethe-University Frankfurt am Main, Germany. A highly optimized spherical photon calorimeter will be built and installed at an ultra-short flight path. This new method allows the measurement of neutron capture cross sections on extremely small sample as needed in the case of 85Kr, which will be produced as an isotopically pure radioactive sample. The successful measurement will provide insights into the dynamics of the late stages of stars, an important independent check of the evolution of the Universe and the proof of principle.

Comparative analysis of monoclonal antibody N-glycosylation using stable isotope labelling and UPLC-fluorescence-MS.

PubMed

Millán Martín, Silvia; Delporte, Cédric; Farrell, Amy; Navas Iglesias, Natalia; McLoughlin, Niaobh; Bones, Jonathan

2015-03-07

A twoplex method using (12)C6 and (13)C6 stable isotope analogues (Δmass = 6 Da) of 2-aminobenzoic acid (2-AA) is described for quantitative analysis of N-glycans present on monoclonal antibodies and other glycoproteins using ultra performance liquid chromatography with sequential fluorescence and accurate mass tandem quadrupole time of flight (QToF) mass spectrometric detection.

Temperature Programmed Desorption of Quench-condensed Krypton and Acetone in Air; Selective Concentration of Ultra-trace Gas Components.

PubMed

Suzuki, Taku T; Sakaguchi, Isao

2016-01-01

Selective concentration of ultra-trace components in air-like gases has an important application in analyzing volatile organic compounds in the gas. In the present study, we examined quench-condensation of the sample gas on a ZnO substrate below 50 K followed by temperature programmed desorption (TPD) (low temperature TPD) as a selective gas concentration technique. We studied two specific gases in the normal air; krypton as an inert gas and acetone as a reactive gas. We evaluated the relationship between the operating condition of low temperature TPD and the lowest detection limit. In the case of krypton, we observed the selective concentration by exposing at 6 K followed by thermal desorption at about 60 K. On the other hand, no selectivity appeared for acetone although trace acetone was successfully concentrated. This is likely due to the solvent effect by a major component in the air, which is suggested to be water. We suggest that pre-condensation to remove the water component may improve the selectivity in the trace acetone analysis by low temperature TPD.

Gold nanochestnut arrays as ultra-sensitive SERS substrate for detecting trace pesticide residue.

PubMed

Geng, Fei; Zhao, Huaping; Fu, Qun; Mi, Yan; Miao, Likun; Li, Wei; Dong, Yulian; Wu, Minghong; Lei, Yong

2018-07-20

In comparison to conventional spectroscopic techniques based on chromatography, surface-enhanced Raman spectroscopy (SERS) enables the rapid identification and detection of trace pesticide residues present in trace amounts in the environment and foods. Herein, a facile approach to fabricate unique gold nanochestnuts (GNCs) as an ultra-sensitive SERS substrate for detecting trace pesticide residues has been developed based on anodic aluminum oxide (AAO) templates. The GNCs are synthesized through the galvanic replacement of Ag on the top of Ni nanorod arrays. The as-prepared GNCs have well-controlled structural parameters, and importantly have unique anisotropic morphologies that benefit the enhancement in SERS performance. As a result, rhodamine 6 G (R6G) can be efficiently detected with GNCs as the SERS substrate even with a concentration of only 10 -12 M, and the Raman enhancement factor reaches up to 5.4 × 10 9 at this concentration. Further SERS measurement of thiram indicates a remarkable SERS-active sensitivity of the as-prepared GNCs with a detection limit of thiram up to 10 -14 M. The GNCs also exhibit a high signal-to-noise ratio.

Germanium Isotopes - the Global Budget and Paleoceanographic Potential

NASA Astrophysics Data System (ADS)

Baronas, J. J.; Hammond, D. E.; Rouxel, O. J.

2017-12-01

The distribution of element isotope ratios in rocks, sediments, rivers, and seawater can provide key insights about the operation and coupling of various biogeochemical cycles that are directly or indirectly responsible for the climate and habitability of the Earth surface environment. Germanium (Ge) is a trace element that shares many chemical similarities with silicon (Si), in addition to some siderophilic, chalcophilic, and organophilic properties. As a result, Ge stable isotope ratios (δ74Ge) and Ge/Si ratios can be used to trace various biogeochemical processes. These include silicate rock weathering, which modulates atmospheric pCO2 and supplies nutrients to ecosystems, biogenic silica formation, which is coupled to ocean productivity, and marine sediment diagenesis, which ultimately controls the removal of material from the Earth's surface. I will present an overview of my dissertation research concerning the global Ge isotope cycle, with insights into Ge isotope fractionation during secondary mineral precipitation during weathering on continents and during authigenesis in marine sediments. I will also discuss the potential for the δ74Ge sedimentary record to be used as a paleoceanographic proxy, given the constraints on the global Ge isotope budget.

Investigating isotopic signatures of atmospheric nitrous acid (HONO)

NASA Astrophysics Data System (ADS)

Chai, J.; Miller, D. J.; Hastings, M. G.

2016-12-01

Nitrous acid (HONO) is an important reactive nitrogen species that can be easily photolyzed to nitrogen oxide and hydroxyl radical in the troposphere. HONO greatly influences atmospheric oxidation capacity, affecting the formation of tropospheric ozone (O3) and secondary aerosol. Recent studies have indicated that in addition to heterogeneous NOx reactions, biomass burning, soil emission and photolysis of nitric acid (HNO3) on surfaces (e.g. aerosol particles and soot) are also important sources of HONO. However, these sources have not yet been well constrained. The stable isotope ratios in nitrate have been successfully used to trace NOx sources and oxidation chemistry in the atmosphere. Can the isotopic signatures of HONO be used to trace NOx oxidation and renoxification pathways? For this purpose, we have built an annular denuder HONO collection system for the stable isotope study of HONO. Preliminary tests show successful collection and recovery of HONO synthesized in our lab. Nitrogen and oxygen isotopic analysis of the recovered HONO also shows consistent isotopic signatures. Results from field applications of this method in near road and on road environments, agricultural settings, and laboratory based biomass burns will be presented.

Isotopes and Trace Elements as Natal Origin Markers of Helicoverpa armigera – An Experimental Model for Biosecurity Pests

PubMed Central

Holder, Peter W.; Armstrong, Karen; Van Hale, Robert; Millet, Marc-Alban; Frew, Russell; Clough, Timothy J.; Baker, Joel A.

2014-01-01

Protecting a nation's primary production sector and natural estate is heavily dependent on the ability to determine the risk presented by incursions of exotic insect species. Identifying the geographic origin of such biosecurity breaches can be crucial in determining this risk and directing the appropriate operational responses and eradication campaigns, as well as ascertaining incursion pathways. Reading natural abundance biogeochemical markers using mass spectrometry is a powerful tool for tracing ecological pathways as well as provenance determination of commercial products and items of forensic interest. However, application of these methods to trace insects has been underutilised to date and our understanding in this field is still in a phase of basic development. In addition, biogeochemical markers have never been considered in the atypical situation of a biosecurity incursion, where sample sizes are often small, and of unknown geographic origin and plant host. These constraints effectively confound the interpretation of the one or two isotope geo-location markers systems that are currently used, which are therefore unlikely to achieve the level of provenance resolution required in biosecurity interceptions. Here, a novel approach is taken to evaluate the potential for provenance resolution of insect samples through multiple biogeochemical markers. The international pest, Helicoverpa armigera, has been used as a model species to assess the validity of using naturally occurring δ2H, 87Sr/86Sr, 207Pb/206Pb and 208Pb/206Pb isotope ratios and trace element concentration signatures from single moth specimens for regional assignment to natal origin. None of the biogeochemical markers selected were individually able to separate moths from the different experimental regions (150–3000 km apart). Conversely, using multivariate analysis, the region of origin was correctly identified for approximately 75% of individual H. armigera samples. The geographic resolution demonstrated with this approach has considerable potential for biosecurity as well as other disciplines including forensics, ecology and pest management. PMID:24664236

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

NASA Astrophysics Data System (ADS)

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

1988-01-01

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

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

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

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

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

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

DOE PAGES

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

2015-09-05

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

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.

All fats are not equal: Considerations when using fatty acid biomarkers in compound-specific stable isotope soil and sediment tracing

NASA Astrophysics Data System (ADS)

Reiffarth, Dominic; Petticrew, Ellen; Owens, Philip; Lobb, David

2013-04-01

The development of cost-effective, convenient and reliable methods for tracing sediment movement will help establish water security. The use of compound-specific stable isotopes (CSSIs) has seen limited, small-scale applications, often in watersheds exhibiting exotic and highly diverse vegetation types. The CSSI tracing technique relies on the detection and transport of naturally occurring organics of plant origin (biomarkers); the biomarkers of interest are produced by flora, deposited on the soil and potentially mobilized along with soil particles. In part, the uniqueness of a biomarker is dependent on its biological pathway. As a plant fixes CO2-its primary source of carbon for building larger organic molecules-discrimination against the heavier 13C isotope leads to an enrichment of 12C. The more complex the biological pathway the biomarker has been subjected to, the more discrimination and unique isotopic signature the biomarker exhibits. Successfully implementing CSSI tracing requires recognizing: (i) factors contributing to the natural variability of the isotopic signature (ii) the suitability of a biomarker and (iii) factors affecting sensitivity during analysis. Considering the relatively low input of suitable organic biomarkers into the soil and degree of signal dispersion, care must be taken to isolate and correctly identify biomarkers, particularly where vegetation types show low variability and where long-range transport occurs. Research is currently being conducted in the Horsefly River (British Columbia, Canada) and South Tobacco Creek (Manitoba, Canada) watersheds; the research seeks to address some of these concerns, particularly in a temperate climate where exotic vegetation types are not common and variability is expected to be low.

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.

Using lead isotopes and trace element records from two contrasting Lake Tanganyika sediment cores to assess watershed – Lake exchange

USGS Publications Warehouse

Odigie, Kingsley; Cohen, A.D.; Swarzenski, Peter W.; Flegal, R

2014-01-01

Lead isotopic and trace element records of two contrasting sediment cores were examined to reconstruct historic, industrial contaminant inputs to Lake Tanganyika, Africa. Observed fluxes of Co, Cu, Mn, Ni, Pb, and Zn in age-dated sediments collected from the lake varied both spatially and temporally over the past two to four centuries. The fluxes of trace elements were lower (up to 10-fold) at a mid-lake site (MC1) than at a nearshore site (LT-98-58), which is directly downstream from the Kahama and Nyasanga River watersheds and adjacent to the relatively pristine Gombe Stream National Park. Trace element fluxes at that nearshore site did not measurably change over the last two centuries (1815–1998), while the distal, mid-lake site exhibited substantial changes in the fluxes of trace elements – likely caused by changes in land use – over that period. For example, the flux of Pb increased by ∼300% from 1871 to 1991. That apparent accelerated weathering and detrital mobilization of lithogenic trace elements was further evidenced by (i) positive correlations (r = 0.77–0.99, p < 0.05) between the fluxes of Co, Cu, Mn, Ni, Pb, and Zn and those of iron (Fe) at both sites, (ii) positive correlations (r = 0.82–0.98, p < 0.01, n = 9) between the fluxes of elements (Al, Co, Cu, Fe, Mn, Ni, Pb, and Zn) and the mass accumulation rates at the offshore site, (iii) the low enrichment factors (EF < 5) of those trace elements, and (iv) the temporal consistencies of the isotopic composition of Pb in the sediment. These measurements indicate that accelerated weathering, rather than industrialization, accounts for most of the increases in trace element fluxes to Lake Tanganyika in spite of the development of mining and smelting operations within the lake’s watershed over the past century. The data also indicate that the mid-lake site is a much more sensitive and useful recorder of environmental changes than the nearshore site. Furthermore, the lead isotopic compositions of sediment at the sites differed spatially, indicating that the Pb (and other trace elements by association) originated from different natural sources at the two locations.

Simultaneous visualization of the subfemtomolar expression of microRNA and microRNA target gene using HILO microscopy† †Electronic supplementary information (ESI) available: The LED device for the sample photobleaching, a schematic presentation of HILO microscopy, fluorescence spectra and hybridization curves of the molecular beacons, the linear correlation between the miRNA fluorescence intensity and the miRNA copy number, a validation of the miRNA adsorption and miRNA target gene expression via RT-qPCR, a validation of RT-qPCR using capillary electrophoresis, the reproducibility of RT-qPCR and Poisson distribution of the miRNA pipetting as well as a complete list of the oligonucleotides used in this study. See DOI: 10.1039/c7sc02701j Click here for additional data file.

PubMed Central

Lin, Yi-Zhen; Ou, Da-Liang; Chang, Hsin-Yuan; Lin, Wei-Yu; Hsu, Chiun

2017-01-01

The family of microRNAs (miRNAs) not only plays an important role in gene regulation but is also useful for the diagnosis of diseases. A reliable method with high sensitivity may allow researchers to detect slight fluctuations in ultra-trace amounts of miRNA. In this study, we propose a sensitive imaging method for the direct probing of miR-10b (miR-10b-3p, also called miR-10b*) and its target (HOXD10 mRNA) in fixed cells based on the specific recognition of molecular beacons combined with highly inclined and laminated optical sheet (HILO) fluorescence microscopy. The designed dye-quencher-labelled molecular beacons offer excellent efficiencies of fluorescence resonance energy transfer that allow us to detect miRNA and the target mRNA simultaneously in hepatocellular carcinoma cells using HILO fluorescence microscopy. Not only can the basal trace amount of miRNA be observed in each individual cell, but the obtained images also indicate that this method is useful for monitoring the fluctuations in ultra-trace amounts of miRNA when the cells are transfected with a miRNA precursor or a miRNA inhibitor (anti-miR). Furthermore, a reasonable causal relation between the miR-10b and HOXD10 expression levels was observed in miR-10b* precursor-transfected cells and miR-10b* inhibitor-transfected cells. The trends of the miRNA alterations obtained using HILO microscopy completely matched the RT-qPCR data and showed remarkable reproducibility (the coefficient of variation [CV] = 0.86%) and sensitivity (<1.0 fM). This proposed imaging method appears to be useful for the simultaneous visualisation of ultra-trace amounts of miRNA and target mRNA and excludes the procedures for RNA extraction and amplification. Therefore, the visualisation of miRNA and the target mRNA should facilitate the exploration of the functions of ultra-trace amounts of miRNA in fixed cells in biological studies and may serve as a powerful tool for diagnoses based on circulating cancer cells. PMID:28989695

Mercury Stable Isotopes Discriminate Different Populations of European Seabass and Trace Potential Hg Sources around Europe.

PubMed

Cransveld, Alice; Amouroux, David; Tessier, Emmanuel; Koutrakis, Emmanuil; Ozturk, Ayaka A; Bettoso, Nicola; Mieiro, Cláudia L; Bérail, Sylvain; Barre, Julien P G; Sturaro, Nicolas; Schnitzler, Joseph; Das, Krishna

2017-11-07

Our study reports the first data on mercury (Hg) isotope composition in marine European fish, for seven distinct populations of the European seabass, Dicentrarchus labrax. The use of δ 202 Hg and Δ 199 Hg values in SIBER enabled us to estimate Hg isotopic niches, successfully discriminating several populations. Recursive-partitioning analyses demonstrated the relevance of Hg stable isotopes as discriminating tools. Hg isotopic values also provided insight on Hg contamination sources for biota in coastal environment. The overall narrow range of δ 202 Hg around Europe was suggested to be related to a global atmospheric contamination while δ 202 Hg at some sites was linked either to background contamination, or with local contamination sources. Δ 199 Hg was related to Hg levels of fish but we also suggest a relation with ecological conditions. Throughout this study, results from the Black Sea population stood out, displaying a Hg cycling similar to fresh water lakes. Our findings bring out the possibility to use Hg isotopes in order to discriminate distinct populations, to explore the Hg cycle on a large scale (Europe) and to distinguish sites contaminated by global versus local Hg source. The interest of using Hg sable isotopes to investigate the whole European Hg cycle is clearly highlighted.

Analysis of a Uranium Oxide Sample Interdicted in Slovakia (FSC 12-3-1)

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

Borg, Lars E.; Dai, Zurong; Eppich, Gary R.

2014-01-17

We provide a concise summary of analyses of a natural uranium sample seized in Slovakia in November 2007. Results are presented for compound identification, water content, U assay, trace element abundances, trace organic compounds, isotope compositions for U, Pb, Sr and O, and age determination using the 234U – 230Th and 235U – 231Pa chronometers. The sample is a mixture of two common uranium compounds - schoepite and uraninite. The uranium isotope composition is indistinguishable from natural; 236U was not detected. The O, Sr and Pb isotope compositions and trace element abundances are unremarkable. The 234U – 230Th chronometer givesmore » an age of 15.5 years relative to the date of analysis, indicating the sample was produced in January 1997. A comparison of the data for this sample with data in the Uranium Sourcing database failed to find a match, indicating the sample was not produced at a facility represented in the database.« less

Gas chromatographic/mass spectrometric determination of carbon isotope composition in unpurified samples: methamphetamine example.

PubMed

Low, I A; Liu, R H; Legendre, M G; Piotrowski, E G; Furner, R L

1986-10-01

A gas chromatograph/quadrupole mass spectrometer system, operated in electron impact/selected ion monitoring mode, is used to determine the intensity ratio of the m/z 59 and the m/z 58 ions of the [C3H8N]+ fragment derived from methamphetamine samples synthesized with varying amounts of 13C-labeled methylamine. Crude products are introduced into the gas chromatograph without prior cleanup. The ratios measured were in excellent agreement with those calculated. A change in 0.25% use of 13C-methylamine is sufficient for product differentiation. The feasibility of using isotope labeling and subsequent mass spectrometric isotope ratio measurement as the basis of a compound tracing mechanism is discussed. Specifically, if methamphetamine samples manufactured from legal sources are asked to incorporate distinct 13C compositions, their sources can be traced when samples are diverted into illegal channels. Samples derived from illicit preparations can also be traced if the manufacturers of a precursor (methylamine in this case) incorporate distinct 13C compositions in their products.

An investigation of mercury sources in the Puyango-Tumbes River: Using stable Hg isotopes to characterize transboundary Hg pollution.

PubMed

Schudel, Gary; Miserendino, Rebecca Adler; Veiga, Marcello M; Velasquez-López, P Colon; Lees, Peter S J; Winland-Gaetz, Sean; Davée Guimarães, Jean Remy; Bergquist, Bridget A

2018-07-01

Mercury (Hg) concentrations and stable isotopes along with other trace metals were examined in environmental samples from Ecuador and Peru's shared Puyango-Tumbes River in order to determine the extent to which artisanal- and small-scale gold mining (ASGM) in Portovelo-Zaruma, Ecuador contributes to Hg pollution in the downstream aquatic ecosystem. Prior studies investigated the relationship between ASGM activities and downstream Hg pollution relying primarily on Hg concentration data. In this study, Hg isotopes revealed an isotopically heavy Hg signature with negligible mass independent fractionation (MIF) in downstream sediments, which was consistent with the signature observed in the ASGM source endmember. This signature was traced as far as ∼120 km downstream of Portovelo-Zaruma, demonstrating that Hg stable isotopes can be used as a tool to fingerprint and trace sources of Hg over vast distances in freshwater environments. The success of Hg isotopes as a source tracer in fresh waters is largely due to the particle-reactive nature of Hg. Furthermore, the magnitude and extent of downstream Hg, lead, copper and zinc contamination coupled with the Hg isotopes suggest that it is unlikely that the smaller artisanal-scale activities, which do not use cyanidation, are responsible for the pollution. More likely it is the scale of ores processed and the cyanide leaching, which can release other metals and enhance Hg transport, used during small-scale gold mining that is responsible. Thus, although artisanal- and small-scale gold mining occur in tandem in Portovelo-Zaruma, a distinction should be made between these two activities. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2010-01-01

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

Controls on the Transition Metal Isotopic Composition of Seawater: Diatom Culture Experiments

NASA Astrophysics Data System (ADS)

Vance, D.; Archer, C.; Kennaway, G.; Cox, E.; Statham, P. J.

2004-12-01

Many transition metals are essential micronutrients for marine phytoplankton. As a result the expectation is that biological processes play an important, perhaps a dominant, role in their marine isotope geochemistry. These observations raise the prospect of using isotope records to trace transition metal micronutrient usage in the past oceans, an issue that is of importance to the efficiency of the biological pump and atmospheric carbon dioxide. As such, the characterisation of trace metal isotopic fractionations associated with marine primary productivity are an important scientific goal. Here we report fractionations associated with Fe, Cu and Zn sequestration by diatoms, one of the main primary producers in the oceans. Axenic unialgal cultures of Thalassiosira weissflogii and Thalassiosira pseudonana were established in artificial seawater + F/2 medium at 18° C on a 16:8 light:dark cycle. The cultures were filtered to separate diatom material from residual media and analysed for Zn, Cu and Fe concentrations and isotope composition using techniques described elsewhere1,2. Aliquots of the starting medium were also measured for each batch of cultures. The diatom organic material shows small, but consistent and resolvable, positive fractionations (0.1-0.3 per mil) for Fe, Cu and Zn relative to the starting medium. In the case of all three metals, but particularly for Zn (70-95% depending on experiment size), the diatoms had sequestered a large proportion of the available metal, suggesting that the fractionation factor for metal usage by the diatoms is much greater than 1.0001 to 1.0003. Time-series experiments are under way to determine the exact magnitude of the fractionation factor. The mass-balance is supported by the fact that the residual medium is around -0.4 per mil for Zn. The fact that diatoms incorporate trace metals that are isotopically heavier than the nutrient pool is a surprising result, the expectation having been that, as with carbon, the biological usage of trace metals would result in kinetic fractionations3. The positive fractionations necessitate an equilibrium process and, perhaps, active extra-cellular sequestration of trace metals. The second broader implication is that given the proposed role of diatoms in controlling the extreme depletion of Zn in open ocean surface waters, particularly in the Pacific where surface waters are have up to a factor of 250 less Zn than deep waters4, the depletion of the light isotope in surface waters and its enrichment in deep waters are predicted to be extreme. Zn, and other trace metal, isotopes may have an important role in recording this process in the past oceans. 1 C. Archer and D. Vance, 2004, J. Anal. Atom. Spectr. 19, 656-665. 2 J. Bermin, et al., 2004, this volume. 3 Pichat, S et al., 2003, Earth Planet. Sci. Lett. 210, 167-178. 4 Lohan, M.C. et al., 2002, Deep-Sea Res. II 49, 5793-5808.

High H2O/Ce of K-rich MORB from Lena Trough and Gakkel Ridge, Arctic Ocean

NASA Astrophysics Data System (ADS)

Snow, J. E.; Feig, S. T.

2014-12-01

Lena Trough in the Arctic ocean is the oblique spreading continuation of Gakkel Ridge through the Fram Strait (eg Snow et al. 2011). Extreme trace element and isotopic compositions seen in Lena Trough basalt appear to be the enriched end member dominating the geochemistry of the Western Volcanic Zone of the Western Gakkel Ridge as traced by Pb isotopes, K2O/TiO2, Ba/Nb and other isotopic, major and trace element indicators of mixing (Nauret et al., 2011). This is in contrast to neighboring Gakkel Ridge which has been spreading for 50-60 million years. Basalts from Lena Trough also show a pure MORB noble gas signature (Nauret et al., 2010) and peridotites show no evidence of ancient components in their Os isotopes (Lassiter, et al., in press). The major and trace element compositions of the basalts, however are very distinct from MORB, being far more potassic than all but a single locality on the SW Indian Ridge. We determined H2O and trace element composiitions of a suite of 17 basalt glasses from the Central Lena Trough (CLT) and the Gakkel Western Volcanic Zone, including many of those previously analyzed by Nauret et al. (2012). The Western Gakkel glasses have high H2O/Ce for MORB (>300) suggesting a water rich source consistent with the idea that the northernmost Atlantic mantle is enriched in water (Michael et al., 1995). They are within the range of Eastern Gakkel host glasses determined by Wanless et al, 2013. The Lena Trough (CLT) glasses are very rich in water for MORB (>1% H2O) and are among the highest H2O/Ce (>400) ever measured in MORB aside from melt inclusions in olivine. Mantle melting dynamics and melt evolution cannot account for the H2O/Ce variations in MORB, as these elements have similar behavior during melting and crustal evolution. Interestingly, the H2O/K2O ratios in the basalts are only around 1. This is because the K2O levels in the CLT glasses are very high as well relative to REE. The absolutely linear relationship between H2O and K2O/TiO2 in Lena and Gakkel basalts shows that water systematics in these rocks are completely governed by source composition, with little or no modification by mantle melting dynamics or crystal fractionation. The geochemical influence of the WVZ enriched mantle source declines with distance from Lena Trough along Gakkel Ridge.

Optical molecular fluorescence determination of ultra-trace beryllium in occupational and environmental samples using highly alkaline conditions.

PubMed

Adams, Lori; Agrawal, Anoop; Cronin, John P; Ashley, Kevin

2017-01-01

Exposures to beryllium (Be), even at extremely low levels, can cause severe health effects in a percentage of those exposed; consequently, occupational exposure limits (OELs) promulgated for this element are the lowest established for any element. This work describes the advantages of using highly alkaline dye solutions for determination of Be in occupational hygiene and environmental samples by means of an optical molecular fluorescence technique after sample extraction in 1-3% (w˖w -1 ) aqueous ammonium bifluoride (NH 4 HF 2 ). Improved attributes include the ability to further enhance the detection limits of Be in extraction solutions of high acidity with minimal dilution, which is particularly beneficial when NH 4 HF 2 solutions of higher concentration are used for extraction of Be from soil samples. Significant improvements in Be method detection limits (MDLs) are obtained at levels many-fold below those reported previously for this methodology. Notably, MDLs for Be of <0.01 ng l -1 / 0.1 ng per sample have been attained, which are superior to MDLs routinely reported for this element by means of the most widely used ultra-trace elemental measurement technique, inductively coupled plasma mass spectrometry (ICP-MS). Very low MDLs for Be are essential in consideration of reductions in OELs for this element in workplace air by health organizations and regulatory agencies in the USA and internationally. Applications of enhanced Be measurements to air filter samples, surface wipe samples, soils and newly-designed occupational air sampler inserts are illustrated.

Speciation analysis of mercury by solid-phase microextraction and multicapillary gas chromatography hyphenated to inductively coupled plasma-time-of-flight-mass spectrometry.

PubMed

Jitaru, Petru; Adams, Freddy C

2004-11-05

This paper reports the development of an analytical approach for speciation analysis of mercury at ultra-trace levels on the basis of solid-phase microextraction and multicapillary gas chromatography hyphenated to inductively coupled plasma-time-of-flight mass spectrometry. Headspace solid-phase microextraction with a carboxen/polydimethylsyloxane fiber is used for extraction/preconcentration of mercury species after derivatization with sodium tetraethylborate and subsequent volatilization. Isothermal separation of methylmercury (MeHg), inorganic mercury (Hg2+) and propylmercury (PrHg) used as internal standard is achieved within a chromatographic run below 45 s without the introduction of spectral skew. Method detection limits (3 x standard deviation criteria) calculated for 10 successive injections of the analytical reagent blank are 0.027 pg g(-1) (as metal) for MeHg and 0.27 pg g(-1) for Hg2+. The repeatability (R.S.D., %) is 3.3% for MeHg and 3.8% for Hg2+ for 10 successive injections of a standard mixture of 10pg. The method accuracy for MeHg and total mercury is validated through the analysis of marine and estuarine sediment reference materials. A comparison of the sediment data with those obtained by a purge-and-trap injection (PTI) method is also addressed. The analytical procedure is illustrated with some results for the ultra-trace level analysis of ice from Antarctica for which the accuracy is assessed by spike recovery experiments.

Evaluation of the UV/H2O2 system for treating natural water with a mixture of anthracene and benzo[a]pyrene at ultra-trace levels.

PubMed

Rubio-Clemente, Ainhoa; Chica, Edwin; Peñuela, Gustavo

2018-06-05

The presence of polycyclic aromatic hydrocarbons, such as anthracene (AN) and benzo[a]pyrene (BaP), in water has become a problem of great concern due to the detrimental health effects caused to humans and living beings. In this work, the efficiency of the UV/H 2 O 2 system for degrading the target compounds at ultra-trace levels in surface water has been evaluated. For this purpose, a previous optimization step using a face-centered central composite experimental design has been conducted, considering the effect of the UV-C irradiance and the initial concentration of H 2 O 2 . It was evidenced that under optimal operating conditions (11 mg L -1 H 2 O 2 and 0.63 mW cm -2 irradiance), AN and BaP removal percentages were higher than 99.8%. Additionally, 69.3% of the organic matter, in terms of total organic carbon, was mineralized without the production of transformation by-products more harmful than the parent compounds. These findings demonstrate the oxidation capacity of the examined system in a natural matrix for degrading micropollutants that cannot be converted through conventional treatment processes. Consequently, new horizons are opened for the effective use of the UV/H 2 O 2 system for drinking water production, providing the accomplishment of other regulated parameters related to water quality.

Trends in Trace Element Fractionation Between Foraminiferal Species and the Role of Biomineralization

NASA Astrophysics Data System (ADS)

Reichart, G. J.; Nooijer, L. D.; Geerken, E.; Mezger, E.; van Dijk, I. V.; Daemmer, L. K.

2017-12-01

Reconstructions of past climate and environments are largely based on stable isotopes and trace element concentrations measured on fossil foraminiferal calcite. Their element and isotope composition roughly reflects seawater composition and physical conditions, which in turn, are related to paleoceanographic parameters. More recently, attempts are being made to infer ranges in environmental parameters using the observed differences in the composition within individual tests. Remarkably, inter-species differences in trace element incorporation are well-correlated over a wide range of environmental conditions. This is particularly remarkable knowing that different environmental factors influence incorporation of these elements at various magnitudes. Most likely the complex biomineralization of foraminifera potentially offsets trace elements similarly at all these scales and also between different species. This suggests that at least parts of the mechanisms underlying foraminiferal biomineralization are similar for all species, which in turn provides important clues on the cellular mechanisms operating during calcification. Moreover, the systematics in trace element partitioning between species could potentially provide important clues for unravelling past changes in trace element composition of the ancient ocean.

Stable water isotopes suggest sub-canopy water recycling in a northern forested catchment

Treesearch

Mark B. Green; Bethany K. Laursen; John L. Campbell; Kevin J. McGuire; Eric P. Kelsey

2015-01-01

Stable water isotopes provide a means of tracing many hydrologic processes, including poorly understood dynamics like soil water interactions with the atmosphere. We present a four-year dataset of biweekly water isotope samples from eight fluxes and stores in a headwater catchment at the Hubbard Brook Experimental Forest, New Hampshire, USA. We use Dansgaard's...

Identification of process related trace level impurities in the actinide decorporation agent 3,4,3-LI(1,2-HOPO): Nozzle–skimmer fragmentation via ESI LC–QTOFMS

DOE PAGES

Panyala, Nagender R.; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J.

2014-08-12

We report that 3,4,3-LI(1,2-HOPO) is a chelating ligand and decorporation agent that can remove radioactive lanthanides and actinides from the body. Identification of trace impurities in drug samples is gaining much interest due to their significant influence on drug activity. In this study, trace impurities were detected in manufactured lots of 3,4,3-LI(1,2-HOPO) by a developed method of Liquid Chromatography coupled with photo-diode array UV detection and Electrospray Ionization-Quadrupole Time of Flight Mass spectrometry (LC-QTOFMS), via induced-in-source or collision-induced mass fragmentation (Nozzle-Skimmer Fragmentation). Molecular ions were fragmented within the nozzle-skimmer region of electrospray ionization (ESI) mass spectrometer equipped with a Timemore » of Flight detector. Eight major (detected at levels higher than a 0.1% threshold) and seven minor trace impurities were identified. The respective structures of these impurities were elucidated via analysis of the generated fragment ions using mass fragmentation and elemental composition software. Proposed structures of impurities were further confirmed via isotopic modeling.« less

Geochemical sources of metal contamination in a coal mining area in Chhattisgarh, India using lead isotopic ratios.

PubMed

Das, Avijit; Patel, Subhra Sarita; Kumar, Rajeev; Krishna, K V S S; Dutta, Saikat; Saha, Manik Chandra; Sengupta, Siladitya; Guha, Dipayan

2018-04-01

A geochemical study of the trace metals and lead isotopic ratios of soil and sediments in Korba, Chhattisgarh, India is presented here for the first time. Korba, the nation's 'power hub' is also the fifth among its eighty-eight most critically polluted industrial hotspots. A very high mean concentration (in mg kg-1) of V (308), Cr (567), Mn (3442), Co (92), Cu (218), Zn (426), Pb (311), Th (123) and U (32) characterized the sediments of the studied area with mean I geo values of the trace metals ranging from -2.29 to 3.27. In the two-ratio scatter Pb isotope plot of the different environmental matrices, except for human blood, coal, soil, sediments, non-washed leaves, flyash and diesel overlapped linearly in the mixing line between diesel as the highest anthropogenic end member and a core sediment fraction representing its geogenic counterpart. The mean 207 Pb/ 206 Pb Pb ratio decreased in the order of diesel (0.9012) > flyash (0.8757) > coal (0.8498) soils and sediments (0.8374) > lowest core sediment fraction (0.8017). Principal Component Analysis (PCA) of the trace metal data extracted V, Cr, Cu, Zn, Pb, U and Th in the first component PC1. The northeastern part of the study area revealed major hotspots of V, Cu, Co, Zn and Pb near the flyash dykes of the power stations. Human blood used as a biomarker for Pb pollution in this study had a mean blood lead level of 28 μg/dl with a distinctive high 207 Pb/ 206 Pb ratio of 0.8828. Published by Elsevier Ltd.

Chromium Isotopes in Marine Carbonates - an Indicator for Climatic Change?

NASA Astrophysics Data System (ADS)

Frei, R.; Gaucher, C.

2010-12-01

Chromium (Cr) stable isotopes experience an increased interest as a tracer of Cr (VI) reduction in groundwater and thus showed their potential as a monitor of remediation of anthropogenic and natural contamination in water (Berna et al., 2009; Izbicki et al., 2008). Chromium stable isotopes in Fe-rich chemical sediments (BIFs and Fe-cherts) have recently also been used as a tracer for Earth's atmospheric oxygenation through time (Frei et al., 2009). We have applied the Cr isotope system to organic-rich carbonates from a late Ediacaran succession in Uruguay (Polanco Formation), from which we have previously analyzed BIFs with extremely fractionated (δ53Cr up to 5.0 ‰) Cr isotope signatures that are part of an underlying deep water clastic sediment (shale-dominated) sequence (Yerbal Formation) deposited in a glacio-marine environment (Gaucher et al.,2004). δ53Cr values of organic rich carbonates correlate with positive and negative carbon isotope excursions (δ13C PDB between -3 and +3 ‰) and with systematic changes in strontium isotope compositions, commonly interpreted as to reflect fluctuations in organic (photosynthetic algae) production related to fluctuations in atmospheric oxygen and weathering intensities, respectively. Slightly positively fractioned δ53Cr values (up to +0.25‰), paralleling positive (δ13C PDB and 87Sr/86Sr ratio excursions would thereby trace elevated atmospheric oxygen levels/pulses possibly related to glacier retreat/melting stages that caused bioproductivity to increase. While the causal link between these multiple isotopic tracers and the mechanisms of Cr stripping into carbonates has to be further investigated in detail, the first indications from this study point to a potentially promising use of stable Cr isotopes in organic-rich carbonates to monitor fluctuations of atmospheric oxygen, particularly over the Neoproterozoic and Phanerozoic ice age periods. E.C. Berna et al. (2010) Cr stable isotopes as indicators of Cr(VI) reduction in groundwater: a detailed time-series study of a point-source plume. Environ. Sci. Technol., v. 44, p. 1043-1048. J.A. Izbicki et al. (2008) Chromium, chromium isotopes and selected trace elements, western Mojave Desert, USA. Applied Geochemistry, v.23, p. 1325-1352. R. Frei et al. (2009) Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes. Nature, v. 461, p. 250-253. C. Gaucher et al. (2004) Chemostratigraphy of the Lower Arroyo del Soldado Group (Vendian, Uruguay) and palaeoclimatic implications. Gondwana Research, v.7, p. 715-730

Chemical durability of alkali-borosilicate glasses studied by analytical SEM, IBA, isotopic-tracing and SIMS

NASA Astrophysics Data System (ADS)

Trocellier, P.; Djanarthany, S.; Chêne, J.; Haddi, A.; Brass, A. M.; Poissonnet, S.; Farges, F.

2005-10-01

Simple and complex alkali-borosilicate glasses were submitted to aqueous corrosion at room temperature, 60 and 90 °C in solutions with pH ranging between 0 and 12. Analytical scanning electron microscopy (SEM), ion beam analysis (IBA) techniques, isotopic tracing and secondary ion mass-depth profiling (SIMS) have been used to investigate the variations of the surface composition of glass. In acidic medium, the glass surface is generally covered by a thick hydrated silica layer, mobile elements like Li, Na and B and transition elements (Fe, Zr, Mo, etc.) are strongly depleted. Near pH 7, relative enrichments of aluminium, iron and rare earths are shown together with strong Li, Na and B depletions. In basic medium, the glass surface exhibits relative enrichments of the major part of transition metals (from Cr to U) whereas mobile elements seem to be kept close to their nominal concentration level at the glass surface and Si is severely impoverished. Hydrogen incorporated at the glass surface after leaching is much more immobile in neutral and basic media than in acid medium.

Cell Surface Display of Four Types of Solanum nigrum Metallothionein on Saccharomyces cerevisiae for Biosorption of Cadmium.

PubMed

Wei, Qinguo; Zhang, Honghai; Guo, Dongge; Ma, Shisheng

2016-05-28

We displayed four types of Solanum nigrum metallothionein (SMT) for the first time on the surface of Saccharomyces cerevisiae using an α-agglutinin-based display system. The SMT genes were amplified by RT-PCR. The plasmid pYES2 was used to construct the expression vector. Transformed yeast strains were confirmed by PCR amplification and custom sequencing. Surface-expressed metallothioneins were indirectly indicated by the enhanced cadmium sorption capacity. Flame atomic absorption spectrophotometry was used to examine the concentration of Cd(2+) in this study. The transformed yeast strains showed much higher resistance ability to Cd(2+) compared with the control. Strikingly, their Cd(2+) accumulation was almost twice as much as that of the wild-type yeast cells. Furthermore, surface-engineered yeast strains could effectively adsorb ultra-trace cadmium and accumulate Cd(2+) under a wide range of pH levels, from 3 to 7, without disturbing the Cu(2+) and Hg(2+). Four types of surfaceengineered Saccharomyces cerevisiae strains were constructed and they could be used to purify Cd(2+)-contaminated water and adsorb ultra-trace cadmium effectively. The surface-engineered Saccharomyces cerevisiae strains would be useful tools for the bioremediation and biosorption of environmental cadmium contaminants.

Application of l-cystine modified zeolite for preconcentration and determination of ultra-trace levels of cadmium by flame atomic absorption spectrometry.

PubMed

Rezvani, Seyyed Ahmad; Soleymanpour, Ahmad

2016-03-04

A very convenient, sensitive and precise solid phase extraction (SPE) system was developed for enrichment and determination of ultra-trace of cadmium ion in water and plant samples. This method was based on the retention of cadmium(II) ions by l-cystine adsorbed in Y-zeolite and carry out in a packed mini-column. The retained cadmium ions then were eluted and determined by flame atomic absorption spectrometry. The scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and Fourier Transform Infrared (FT-IR) spectroscopy techniques were applied for the characterization of cystine modified zeolite (CMZ). Some experimental conditions affecting the analytical performance such as pH, eluent type, concentration of sample, eluent flow rate and also the presence of interfering ions were investigated. The calibration graph was linear within the range of 0.1-7.5ngmL(-1) and limit of detection was obtained 0.04ngmL(-1) with the preconcentration factor of 400. The relative standard deviation (RSD) was obtained 1.4%, indicating the excellent reproducibility of this method. The proposed method was successfully applied for the extraction and determination of cadmium(II) ion in black tea, cigarette's tobacco and also various water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Cavity ring-down spectroscopy using an EC-QCL operating at 7.5 µm for direct monitoring of methane isotopes in air

NASA Astrophysics Data System (ADS)

Maity, Abhijit; Pal, Mithun; Dutta Banik, Gourab; Maithani, Sanchi; Pradhan, Manik

2017-11-01

A number of atmospheric pollutants and greenhouse gases have strong fundamental vibrational transitions within the spectral range of 7.5-8 µm, which marks the region as particularly important for trace gas sensing. Here, we report the development of a mid-infrared continuous-wave (cw) cavity ring-down spectroscopy (CRDS) technique coupled with an external-cavity (EC) mode-hop-free quantum cascade laser (QCL) operating at 7.5 µm. We validated the EC-QCL based high-resolution cw-CRDS system by measuring 12CH4 and 13CH4 isotopes of methane (CH4) which served as a benchmark molecule. The direct, quantitative and selective measurements of 12C and 13C isotopes of CH4 in ambient air as well as in human breath samples in the levels of parts per billion by volume were made by probing one of the strongest fundamental vibrational transitions of CH4 arising from the asymmetric bending (ν 4 band) vibrations of the bonds centred at ~1327.244 cm-1 and ~1332.946 cm-1, respectively. We achieved a noise-equivalent absorption coefficient of 1.86  ×  10-9 cm-1 Hz-1/2 with 100 Hz data acquisition rate for the current cw-CRDS spectrometer. The current high-resolution cw-CRDS system could be further exploited to harness the full advantage of the spectral region covering 7.5-8 µm to monitor several other trace molecular species along with their isotopic compositions.

Genesis of ultra-high pressure garnet pyroxenites in orogenic peridotites and its bearing on the compositional heterogeneity of the Earth's mantle

NASA Astrophysics Data System (ADS)

Varas-Reus, María Isabel; Garrido, Carlos J.; Marchesi, Claudio; Bosch, Delphine; Hidas, Károly

2018-07-01

We present an integrated geochemical study of ultra-high pressure (UHP) garnet pyroxenites from the Ronda and Beni Bousera peridotite massifs (Betic-Rif Belt, westernmost Mediterranean). Based on their Sr-Nd-Pb-Hf isotopic systematics, we classify UHP garnet pyroxenites into three groups: Group A pyroxenites (Al2O3: 15-17.5 wt.%) have low initial 87Sr/86Sr, relatively high εNd, εHf and 206Pb/204Pb ratios, and variable 207Pb/204Pb and 208Pb/204Pb. Group B pyroxenites (Al2O3 < 14 wt.%) are characterized by high initial 87Sr/86Sr and relatively low εNd, εHf and 206Pb/204Pb ratios. Group C pyroxenites (Al2O3 ∼ 15 wt.%) have depleted radiogenic signatures with relatively low initial 87Sr/86Sr and 206Pb/204Pb, high εNd and εHf, and their 207Pb/204Pb and 208Pb/204Pb ratios are similar to those of Group B pyroxenites. The major and trace element and isotopic compositions of UHP garnet pyroxenites support their derivation from ancient (1.5-3.5 Ga) oceanic crust recycled into the mantle and intimately stirred with peridotites by convection. However, the genesis of these pyroxenites requires also the involvement of recycled continental lower crust with an isotopic composition akin to the lower crustal section of the lithosphere where these UHP garnet pyroxenites now reside in. These oceanic and continental crustal components were stirred in different proportions in the convective mantle, originating pyroxenites with a more marked geochemical imprint of either oceanic (Group A) or continental lower crust (Group B), or hybrid compositions (Group C). The pyroxenite protoliths likely underwent several melting events, one of them related to the formation of the subcontinental lithospheric mantle and continental crust, generating restitic UHP garnet pyroxenites now preserved in the Ronda and Beni Bousera orogenic peridotites. The extent of melting was mostly controlled by the bulk Mg-number (Mg#) of the pyroxenite protoliths, where protoliths with low Mg# experienced higher degrees of partial melting than sources with higher Mg#. Positive Eu and Sr anomalies in bulk rocks, indicative of their origin from cumulitic crustal gabbros, are preserved mostly in high Mg# pyroxenites due to their higher melting temperatures and consequent lower partial melting degrees. The results of this study show that the genesis of UHP garnet pyroxenites in orogenic peridotites requires a new recipe for the marble cake mantle hypothesis, combining significant recycling and stirring of both oceanic and continental lower crust in the Earth's mantle. Furthermore, this study establishes a firm connection between the isotopic signatures of UHP pyroxenite heterogeneities in the mantle and the continental lower crust.

Trace elements study of high purity nanocrystalline silicon carbide (3C-SiC) using k0-INAA method

NASA Astrophysics Data System (ADS)

Huseynov, Elchin; Jazbec, Anze

2017-07-01

Silicon carbide (3C-SiC) nanoparticles have been irradiated by neutron flux (2×1013 n·cm-2·s-1) at TRIGA Mark II type research reactor. After neutron irradiation, the radioisotopes of trace elements in the nanocrystalline 3C-SiC were studied as time functions. The identification of isotopes which significantly increased the activity of the samples as a result of neutron radiation was carried out. Nanocrystalline 3C-SiC are synthesized by standard laser technique and the purity of samples was determined by the k0-based Instrumental Neutron Activation Analysis (k0-INAA) method. Trace elements concentration in the 3C-SiC nanoparticles were determined by the radionuclides of appropriate elements. The trace element isotopes concentration have been calculated in percentage according to k0-INAA method.

Isotopic tracing of perchlorate in the environment

USGS Publications Warehouse

Sturchio, Neil C.; Böhlke, John Karl; Gu, Baohua; Hatzinger, Paul B.; Jackson, W. Andrew; Baskaran, Mark

2012-01-01

Isotopic measurements can be used for tracing the sources and behavior of environmental contaminants. Perchlorate (ClO 4 − ) has been detected widely in groundwater, soils, fertilizers, plants, milk, and human urine since 1997, when improved analytical methods for analyzing ClO 4 −concentration became available for routine use. Perchlorate ingestion poses a risk to human health because of its interference with thyroidal hormone production. Consequently, methods for isotopic analysis of ClO 4 − have been developed and applied to assist evaluation of the origin and migration of this common contaminant. Isotopic data are now available for stable isotopes of oxygen and chlorine, as well as 36Cl isotopic abundances, in ClO 4 − samples from a variety of natural and synthetic sources. These isotopic data provide a basis for distinguishing sources of ClO 4 − found in the environment, and for understanding the origin of natural ClO 4 − . In addition, the isotope effects of microbial ClO 4 − reduction have been measured in laboratory and field experiments, providing a tool for assessing ClO 4 − attenuation in the environment. Isotopic data have been used successfully in some areas for identifying major sources of ClO 4 − contamination in drinking water supplies. Questions about the origin and global biogeochemical cycle of natural ClO 4 − remain to be addressed; such work would benefit from the development of methods for preparation and isotopic analysis of ClO 4 − in samples with low concentrations and complex matrices.

Simultaneous determination of nine neonicotinoids in human urine using isotope-dilution ultra-performance liquid chromatography-tandem mass spectrometry.

PubMed

Zhang, Quan; Wang, Ximing; Li, Zhe; Jin, Hangbiao; Lu, Zhengbiao; Yu, Chang; Huang, Yu-Fang; Zhao, Meirong

2018-05-14

Neonicotinoids (neonics), a class of systemic insecticides, have been frequently detected in pollen, vegetables, and fruits. Recently, an increasing concern has been aroused for human exposure to neonics. However, biological monitoring for quantifying body burden of neonics has rarely been reported. In this study, we developed an isotope-dilution ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) method to simultaneously quantify nine neonics, including acetamiprid (ACE), thiamethoxam (THIAM), imidacloprid (IMIP), clothianidin (CLO), flonicamid (FLO), thiacloprid (THIAC), dinotefuran (DIN), nitenpyram (NIT), and imidaclothiz (IMIT) in urine. The limits of quantification were 0.1 μg/L for ACE, FLO, DIN, NIT and IMIT, and 0.2 μg/L for THIAM, IMIP, CLO, and THIAC. The overall recoveries were 80.8-103%, 81.5-91.7% and 83.0-92.3% for QA/QC samples fortifying at 1, 25, and 100 μg/L levels, respectively. UPLC/MS/MS method was used to analyze urine samples obtained from 10 children in Hangzhou, China. The detection frequencies were 80% for ACE and IMIP, 70% for THIAM and CLO, 20% for DIN and IMIT and 10% for THIAC. FLO and NIT were not detected in those urine samples. The data provided here will be helpful for conducting biological monitoring of neonics exposure in the future. Copyright © 2018 Elsevier Ltd. All rights reserved.

Trace and Ultra-trace Elements in the Deepest Part of the Vostok Ice Core, Antarctica: Geochemical Characterization of the Sub-glacial Lake Environment

NASA Astrophysics Data System (ADS)

Turetta, C.; Planchon, F.; Gabrielli, P.; Cozzi, G.; Cairns, W.; Barbaro, E.; Petit, J. R.; Bulat, S.; Boutron, C.; Barbante, C.

2016-12-01

We present in this study comprehensive data on the occurrence of 25 trace and ultra-trace elements in the deepest part of the Vostok ice core. The determination of Li, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Ba, Pb, Bi and U has been performed in the different types of ice encountered from 3271 m to 3609 m of depth, corresponding to atmospheric ice, glacial flour and to accreted ice originating from the freezing of Lake Vostok waters. From atmospheric ice and glacial flour, the relative contributions of primary aerosols were evaluated for each element using a chemical mass balance approach in order to provide a first order evaluation of their partition between soluble (sea-salt) and insoluble (wind-blown dust) fractions in the ice. Sea-salt spray aerosols are the main source of impurities to the ice for certain elements (Na, Mg and K levels, and in a lesser extent to Ca, Sr, Rb, Li and U) while for other elements (Al, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, Sb, Ba and Pb as well as the non sea salt fractions of Mg, K, Ca, Sr, Rb, Li and U) dust inputs appear to primarily control their depositional variability. For the glacial flour, the comparable levels of elements with the overlying atmospheric ice suggest that incorporation of abrasion debris at the glacier is quite limited in the sections considered. For the accreted ice originating from the subglacial waters of Lake Vostok, we observed a major chemical shift in the composition of the ice showing two distinct trends that we assumed to be derived from the chemical speciation of elements. The study of the glacier ice and the glacial flour has allowed us to perform a detailed characterisation of elemental abundances related to the aerosol sources variability and also to illustrate the interaction between the ice-sheet and the bedrock.

Sulfur isotopic fractionation of carbonyl sulfide during degradation by soil bacteria and enzyme

NASA Astrophysics Data System (ADS)

Kamezaki, Kazuki; Hattori, Shohei; Ogawa, Takahiro; Toyoda, Sakae; Kato, Hiromi; Katayama, Yoko; Yoshida, Naohiro

2017-04-01

Carbonyl sulfide (COS) is an atmospheric trace gas that possess great potential for tracer of carbon cycle (Campbell et al., 2008). COS is taken up by vegetation during photosynthesis like absorption of carbon dioxide but COS can not emit by respiration of vegetation, suggesting possible tracer for gross primary production. However, some studies show the COS-derived GPP is larger than the estimates by using carbon dioxide flux because COS flux by photolysis and soil flux are not distinguished (e.g. Asaf et al., 2013). Isotope analysis is a useful tool to trace sources and transformations of trace gases. Recently our group developed a promising new analytical method for measuring the stable sulfur isotopic compositions of COS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ enabling us to easily analyze sulfur isotopes in COS (Hattori et al., 2015). Soil is thought to be important as both a source and a sink of COS in the troposphere. In particular, soil has been reported as a large environmental sink for atmospheric COS. Bacteria isolated from various soils actively degrade COS, with various enzymes such as carbonic anhydrase and COSase (Ogawa et al., 2013) involved in COS degradation. However, the mechanism and the magnitude of bacterial contribution in terms of a sink for atmospheric COS is still uncertain. Therefore, it is important to quantitatively evaluate this contribution using COS sulfur isotope analysis. We present isotopic fractionation constants for COS by laboratory incubation experiments during degradation by soil bacteria and COSase. Incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia, Cupriavidus, and Thiobacillus, isolated from natural soil or activated sludge and enzyme purified from a bacteria. As a result, the isotopic compositions of OCS were increased during degradation of OCS, indicating that reaction for OC32S was faster than that for OC33S and OC34S (Kamezaki et al., 2016). Although OCS degradation rates divided by cell numbers were different among strains of the same genus, the isotopic fractionation constants for same genus showed no significant differences. At the presentation, we discuss the mechanism of isotopic fractionation for OCS during degradation by comparing soil bacteria with enzyme. References Asaf, D., Rotenberg, E., Tatarinov, F., Dicken, U., Montzka, S. A., Yakir, D. Nat. Geosci., 6, 186-190, 2013 Campbell, J. E., Carmichael, G. R., Chai, T., Mena-Carrasco, M., Tang, Y., Blake, D. R., Blake, N. J., Vay, S. A., Collatz, G. J., Baker, I., Berry, J. A., Montzka, S. A., Sweeney, C., Schnoor, J. L., Stanier, C. O., Science, 332, 1085-1088, 2008. Hattori, S., Toyoda, A., Toyoda, S., Ishino, S., Ueno, Y., Yoshida, N. Anal. Chem., 87, 477-484, 2015. Ogawa, T., Noguchi, K., Saito, M., Nagahata, Y., Kato, H., Ohtaki, A., Nakayama, H., Dohmae, N., Matsushita, Y., Odaka, M., Yohda, M., Nyunoya, H., Katayama, Y. J. Am. Chem. Soc., 135, 3818-3825, 2013. Kamezaki, K., Hattori, S., Ogawa, T., Toyoda, S., Kato, H., Katayama, Y., Yoshida, N. Environ. Sci. Technol., 50, 3537-3544, 2016.

Determination of Trace Concentration in TMD Detectors using PGAA

NASA Astrophysics Data System (ADS)

Tomandl, I.; Viererbl, L.; Kudějová, P.; Lahodová, Z.; Klupák, V.; Fikrle, M.

2015-05-01

Transmutation detectors could be alternative to the traditional activation detector method for neutron fluence dosimetry at power nuclear reactors. This new method require an isotopically highly-sensitive, non-destructive in sense of compactness as well as isotopic content, precise and standardly used analytical method for trace concentration determination. The capability of Prompt Gamma-ray Activation Analysis (PGAA) for determination of trace concentrations of transmuted stable nuclides in the metallic foils of Ni, Au, Cu and Nb, which were irradiated for 21 days in the reactor core at the LVR-15 research reactor in Řež, is reported. The PGAA measurements of these activation foils were performed at the PGAA facility at Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRMII) in Garching.

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

NASA Astrophysics Data System (ADS)

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

1996-07-01

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

Trace determination of zinc by substoichiometric isotope dilution analysis

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

Sandhya, D.; Priya, S.; Subramanian, M.O.S.

1996-09-01

A radiometric method based on substoichiometric isotope dilution analysis using 1,10-phenanthroline and a substoichiometric amount of eosin was developed for determining trace amounts of zinc. Evaluation of various metal ion interferences shows that as little as 0.2 {mu}g Zn could be determined in an aqueous-phase volume of 60 mL. The method has been successfully applied to the determination of Zn in city waste incineration ash, cadmium metal, Fourts-B tablets, Boro-plus ointment, and magnesium alloy samples. 12 refs., 3 figs., 3 tabs.

Chemical composition measurements of the atmosphere of Jupiter with the Galileo Probe mass spectrometer

NASA Technical Reports Server (NTRS)

Niemann, H. B.; Atreya, S. K.; Carignan, G. R.; Donahue, T. M.; Haberman, J. A.; Harpold, D. N.; Hartle, R. E.; Hunten, D. M.; Kasprzak, W. T.; Mahaffy, P. R.;

Chemical composition measurements of the atmosphere of Jupiter with the Galileo Probe mass spectrometer.

PubMed

Niemann, H B; Atreya, S K; Carignan, G R; Donahue, T M; Haberman, J A; Harpold, D N; Hartle, R E; Hunten, D M; Kasprzak, W T; Mahaffy, P R; Owen, T C; Spencer, N W

1998-01-01

The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for 3He/4He, D/H, 13C/12C, 20Ne/22Ne, 38Ar/36Ar and for isotopes of both Kr and Xe.

Chemical composition measurements of the atmosphere of jupiter with the galileo probe mass spectrometer

NASA Astrophysics Data System (ADS)

Niemann, H. B.; Atreya, S. K.; Carignan, G. R.; Donahue, T. M.; Haberman, J. A.; Harpold, D. N.; Hartle, R. E.; Hunten, D. M.; Kasprzak, W. T.; Mahaffy, P. R.; Owen, T. C.; Spencer, N. W.

The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for ^3He/^4He, D/H, ^13C/^12C, ^20Ne/^22Ne, ^38Ar/^36Ar and for isotopes of both Kr and Xe.

SIMS Investigations on Growth and Sector Zoning in Natural Hydrothermal Quartz: Isotopic and Trace Element Analyses

NASA Astrophysics Data System (ADS)

May, E.; Vennemann, T. W.; Baumgartner, L. P.; Meisser, N.

2014-12-01

Quartz is the most abundant mineral in the Earth's crust and is found in virtually every geological context. Despite its ubiquity and the detailed studies on the conditions of quartz crystallization, some questions concerning its growth and sector zoning with regard to trace element incorporation and oxygen isotope fractionations and the implications thereof for interpretations on the conditions of formation remain (e.g., Jourdan et al., 2009). This study presents new in-situ measurements of trace element and oxygen isotope ratios on natural hydrothermal quartz from an extensional gold-bearing quartz vein in the western Swiss Alps. The temperature of formation of the veins is estimated by quartz-hematite oxygen isotope thermometry to be about 360°C. A detailed SEM-CL study of this sample shows cyclic lamellar growth, alternating with phases of dissolution that are directly followed by macro-mosaic growth of the quartz, before returning to a cyclic lamellar growth again. Trace element concentrations (measured for Na, K, Li, Al, and Ti) notably showed Al/Si variations of three orders of magnitude and coupled Al and Li variations, likely substituting for Si in different growth zones with lower values in macro-mosaic zones precipitating after the period of dissolution. The oxygen isotope composition of the crystal, in contrast, is homogeneous through all growth zones (δ18O values between 15.6‰ and 16.2‰) indicating that the fluid must have been buffered by the host-rock and/or the source of the fluid remained the same despite the period of quartz dissolution. Furthermore, the temperature during crystallization of the quartz crystal has likely also remained similar. The fact that no variations are measured in oxygen isotope compositions but some variations in trace element contents may suggest that changes in pressure were important during the formation of this quartz crystal. Give the pressure effects on the solubility of quartz (Fournier and Potter, 1982), both the cyclic character of quartz growth and perhaps also the changes in Al/Si may be related to pressure variations caused by seismic activity during retrograde Alpine metamorphism. A-L. Jourdan et al. (2009) Mineralogical Magazine, 73, 615-632. R.O. Fournier and R.W. Potter (1982) Geochimica et Cosmochimica Acta, 46, 1969-1973.

Evolution of the Campanian Ignimbrite Magmatic System II: Trace Element and Th Isotopic Evidence for Open-System Processes

NASA Astrophysics Data System (ADS)

Bohrson, W. A.; Spera, F. J.; Fowler, S.; Belkin, H.; de Vivo, B.

2005-12-01

The Campanian Ignimbrite, a large volume (~200 km3 DRE) trachytic to phonolitic ignimbrite was deposited at ~39.3 ka and represents the largest of a number of highly explosive volcanic events in the region near Naples, Italy. Thermodynamic modeling of the major element evolution using the MELTS algorithm (see companion contribution by Fowler et al.) provides detailed information about the identity of and changes in proportions of solids along the liquid line of descent during isobaric fractional crystallization. We have derived trace element mass balance equations that explicitly accommodate changing mineral-melt bulk distribution coefficients during crystallization and also simultaneously satisfy energy and major element mass conservation. Although major element patterns are reasonably modeled assuming closed system fractional crystallization, modeling of trace elements that represent a range of behaviors (e.g. Zr, Nb, Th, U, Rb, Sm, Sr) yields trends for closed system fractionation that are distinct from those observed. These results suggest open-system processes were also important in the evolution of the Campanian magmatic system. Th isotope data yield an apparent isochron that is ~20 kyr younger than the age of the deposit, and age-corrected Th isotope data indicate that the magma body was an open-system at the time of eruption. Because open-system processes can profoundly change isotopic characteristics of a magma body, these results illustrate that it is critical to understand the contribution that open-system processes make to silicic magma bodies prior to assigning relevance to age or timescale information derived from isotope systematics. Fluid-magma interaction has been proposed as a mechanism to change isotopic and elemental characteristics of magma bodies, but an evaluation of the mass and thermal constraints on such a process suggest large-scale fluid-melt interaction at liquidus temperatures is unlikely. In the case of the magma body associated with the Campanian Ignimbrite, the most likely source of open-system signatures is assimilation of partial melts of compositionally heterogeneous basement composed of older cumulates and intrusive equivalents of volcanic activity within the Campanian region. Additional trace element modeling, explicitly evaluating the mass and energy balance effects that fluid, solids, and melt have on trace element evolution, will further elucidate the contributions of open vs. closed system processes within the Campanian magma body.

Isotope Tracing of Long-Term Cadmium Fluxes in an Agricultural Soil.

PubMed

Salmanzadeh, Mahdiyeh; Hartland, Adam; Stirling, Claudine H; Balks, Megan R; Schipper, Louis A; Joshi, Chaitanya; George, Ejin

2017-07-05

Globally widespread phosphate fertilizer applications have resulted in long-term increases in the concentration of cadmium (Cd) in soils. The accumulation of this biotoxic, and bioaccumulative metal presents problems for the management of soil-plant-animal systems, because the magnitude and direction of removal fluxes (e.g., crop uptake, leaching) have been difficult to estimate. Here, Cd isotopic compositions (δ 114/110 Cd) of archived fertilizer and soil samples from a 66 year-long agricultural field trial in Winchmore, New Zealand, were used to constrain the Cd soil mass balance between 1959 and 2015 AD, informing future soil Cd accumulation trajectories. The isotopic partitioning of soil Cd sources in this system was aided by a change in phosphate source rocks in 1998 AD, and a corresponding shift in fertilizer isotope composition. The dominant influence of mixing between isotopically distinct Cd end-members was confirmed by a Bayesian modeling approach. Furthermore, isotope mass balance modeling revealed that Cd removal processes most likely increased in magnitude substantially between 2000 and 2015 AD, implying an increase in Cd bioaccumulation and/or leaching over that interval. Natural-abundance stable isotopes are introduced here as a powerful tool for tracing the fate of Cd in agricultural soils, and potentially the wider environment.

The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

NASA Astrophysics Data System (ADS)

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

2014-01-01

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

Elucidating Water Contamination by Fracturing Fluids and Formation Waters from Gas Wells: Integrating Isotopic and Geochemical Tracers

EPA Pesticide Factsheets

The objective of this presentation is to evaluate the potential and applicability of different geochemical and isotopic tracers for tracing the impacts of fracturing fluids and co-produced waters on water resources.

Multi-element compound specific stable isotope analysis of volatile organic compounds at trace levels in groundwater samples

NASA Astrophysics Data System (ADS)

Herrero-Martín, Sara; Nijenhuis, Ivonne; Schmidt, Marie; Wolfram, Diana; Richnow, Hans. H.; Gehre, Matthias

2013-04-01

Groundwater pollution remains one of the major environmental and health concerns. A thorough understanding of sources, sinks and transformation processes of groundwater contaminants is needed to improve risk management evaluation, and to design efficient remediation and water treatment strategies. Isotopic tools provide unique information for an in-depth understanding of the fate of organic chemicals in the environment. During the last decades compound specific isotope analysis (CSIA) of complex mixtures, using gas chromatography-isotope ratio mass spectrometry (GC-IRMS), has gained popularity for the characterization and risk assessment of hazardous waste sites and for isotope forensics of organic contaminants. Multi-element isotope fingerprinting of organic substances provides a more robust framework for interpretation than the isotope analysis of only one element. One major challenge for application of CSIA is the analysis of trace levels of organic compounds in environmental matrices. It is necessary to inject 1 nmol carbon or 8 nmol hydrogen on column, to obtain an accurate and precise measurement of the isotope ratios, which is between two and three orders of magnitude larger than the amount of compound needed for conventional analysis of compound concentrations. Therefore, efficient extraction and pre-concentration techniques have to be integrated with GC-IRMS. Further research is urgently needed in this field, to evaluate the potential of novel and environmental-friendly sample pre-treatment techniques for CSIA to lower the detection limits and extending environmental applications. In this study, the novel coupling of a headspace autosampler (HS) with a programmed temperature vaporizer (PTV), allowing large volume injection of headspace samples, is proposed to improve the sensitivity of CSIA. This automatic, fast and solvent free strategy provides a significant increase on the sensitivity of GC-based methods maintaining the simple headspace instrumentation. The method was developed for the multi-element isotope analysis (carbon and hydrogen) of priority volatile organic groundwater pollutants (methyl tert-butyl ether (MTBE), benzene, toluene, ethylbenzene and o-xylene (BTEX)), and for carbon isotope analysis of chlorinated benzenes and ethenes. The extraction and injection conditions were optimized in terms of maximum sensitivity and minimum isotope effects. During the injection of the headspace sample, the liner is maintained at a low temperature, such that the compounds are retained in a hydrophobic insert packing while the water vapor is eliminated through the split line. With the optimized conditions, it was possible to inject up to 5mL headspace sample with no significant carbon or hydrogen isotopic effects except for the most hydrophobic substance (MTBE), which was subject to a small and reproducible isotope fractionation for hydrogen. The increment on method sensitivity was at least 20 fold in comparison with conventional static headspace analysis. The environmental applicability of the HS-PTV-GC-IRMS method was evaluated by the analysis of groundwater samples from different contaminated field sites, containing BTEX and chlorinated volatile organic contaminants in the low µg/L range. The results obtained demonstrate that this pre-concentration technique is highly promising to enhance the limits of detection of current CSIA methods and broaden its possibilities.

Stages of weathering mantle formation from carbonate rocks in the light of rare earth elements (REE) and Sr-Nd-Pb isotopes

NASA Astrophysics Data System (ADS)

Hissler, Christophe; Stille, Peter

2015-04-01

Weathering mantles are widespread and include lateritic, sandy and kaolinite-rich saprolites and residuals of partially dissolved rocks. These old regolith systems have a complex history of formation and may present a polycyclic evolution due to successive geological and pedogenetic processes that affected the profile. Until now, only few studies highlighted the unusual high content of associated trace elements in weathering mantles originating from carbonate rocks, which have been poorly studied, compared to those developing on magmatic bedrocks. For instance, these enrichments can be up to five times the content of the underlying carbonate rocks. However, these studies also showed that the carbonate bedrock content only partially explains the soil enrichment for all the considered major and trace elements. Up to now, neither soil, nor saprolite formation has to our knowledge been geochemically elucidated. Therefore, the aim of this study was to examine more closely the soil forming dynamics and the relationship of the chemical soil composition to potential sources. REE distribution patterns and Sr-Nd-Pb isotope ratios have been used because they are particularly well suited to identify trace element migration, to recognize origin and mixing processes and, in addition, to decipher possible anthropogenic and/or "natural" atmosphere-derived contributions to the soil. Moreover, leaching experiments have been applied to identify mobile phases in the soil system and to yield information on the stability of trace elements and especially on their behaviour in these Fe-enriched carbonate systems. All these geochemical informations indicate that the cambisol developing on such a typical weathering mantle ("terra fusca") has been formed through weathering of a condensed Bajocian limestone-marl facies. This facies shows compared to average world carbonates important trace element enrichments. Their trace element distribution patterns are similar to those of the soil suggesting their close genetic relationships. Sr-Nd-Pb isotope data allow to identify four principal components in the soil: a silicate-rich pool at close to the surface, a leachable REE enriched pool at the bottom of the soil profile, the limestone facies on which the weathering profile developed and an anthropogenic, atmosphere-derived component detected in the soil leachates of the uppermost soil horizon. The leachable phases are mainly secondary carbonate-bearing REE phases such as bastnaesite. The isotope data and trace element distribution patterns indicate that at least four geological and environmental events impacted the chemical and isotopical compositions of the soil system since the Cretaceous.

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

NASA Astrophysics Data System (ADS)

Carte, J.; Fantle, M. S.

2017-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2003-12-01

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

Ultra-Trace and Vapor Detection of Explosives and Narcotics Finalist for R&D 100 Award

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

Ewing, Robert

An instrument more sensitive than a canine’s nose identifies explosives and narcotics vapors in real time and at levels previously undetectable than any other sampling technology. The instrument is one among five PNNL-developed technologies in the running for an R&D 100 Award. Known as VP-IDENT, the tool coupled with a mass spectrometer, is ideal for aviation security, cargo screening, and broader counter-terrorism and national security activities where discovering dangerous substances is of utmost importance. Listen as researcher Robert Ewing explains.

Ultra-Trace and Vapor Detection of Explosives and Narcotics Finalist for R&D 100 Award

ScienceCinema

Ewing, Robert

2018-06-13

An instrument more sensitive than a canine’s nose identifies explosives and narcotics vapors in real time and at levels previously undetectable than any other sampling technology. The instrument is one among five PNNL-developed technologies in the running for an R&D 100 Award. Known as VP-IDENT, the tool coupled with a mass spectrometer, is ideal for aviation security, cargo screening, and broader counter-terrorism and national security activities where discovering dangerous substances is of utmost importance. Listen as researcher Robert Ewing explains.

Foraminiferal Stable Isotope Geochemistry At The Micrometer Scale: Is It A Dream Or Reality?

NASA Astrophysics Data System (ADS)

Misra, S.; Shuttleworth, S.; Lloyd, N. S.; Sadekov, A.; Elderfield, H.

2012-12-01

Over last few decades trace metals and stable isotope compositions of foraminiferal shells became one of the major tools to study past oceans and associated climate change. Empirical calibrations of δ11B, δ18O, Mg/Ca, Cd/Ca, Ba/Ca shells compositions have linked them to various environmental parameters such as seawater pH, temperature, salinity and productivity. Despite their common use as proxies, little is known about mechanisms of trace metals incorporation into foraminiferal calcite. Trace metals partition coefficients for foraminiferal calcite is significantly different from inorganic calcite precipitates underlining strong biological control on metal transport to the calcification sites and their incorporation into the calcite. Microscale distribution of light elements isotopes (e.g. Li, B, Mg) could potentially provide unique inside into these biomineralization processes improving our understanding of foraminiferal geochemistry. In this work we explore potentials of using recent advances in analytical geochemistry by employing laser ablation and multi-collector ICP-MS to study microscale distribution of Mg isotopes across individual foraminiferal shells and δ11B, and δ7Li analyses of individual shell chambers. The analytical setup includes an Analyte.G2 193nm excimer laser ablation system with two volume ablation cell connected to a Thermo Scientific NEPTUNE Plus MC-ICP-MS with Jet Interface option. We will discuss method limitations and advantages for foraminiferal geochemistry as well as our data on Mg isotopes distribution within shells of planktonic foraminifera.

The cleaning of burned and contaminated archaeological maize prior to 87Sr/86Sr analysis

USGS Publications Warehouse

Benson, Larry V.; Taylor, Howard E.; Plowman, Terry I.; Roth, David A.; Antweiler, Ronald C.

2010-01-01

Accurate trace-metal and strontium-isotope analyses of archaeological corn cobs require that metal contaminants be removed prior to chemical analysis. Archaeological cobs are often coated with construction debris, dust, or soil which contains mineral particles. In addition, most archaeological cobs are partially or completely burned and the burned parts incorporate mineral debris in their hardened residual structures. Unburned cobs are weak ion exchangers and most metals within a cob are not firmly bound to cob organic matter; therefore, immersing cobs in acids and rinsing them in deionized water to remove mineral contaminants may result in the undesirable loss of metals, including strontium, from the cob.In this paper we show that some cob metal-pair ratios are not substantially changed when the cob is “cleaned” with deionized water, if the water-cob contact time does not exceed five minutes. Additionally, we introduce a method for eliminating mineral contaminants in both burned and unburned cobs, thus rendering them acceptable for strontium-isotope analysis. However, the decontamination procedure results in the rapid non-stoichiometric leaching of trace metals from the unburned cobs and it is possible that most metals will be extracted from the cobs during the lengthy decontamination process. Trace metals, in particular Al and Ca, should be analyzed in order to determine the presence and level of mineral contamination after cleaning.

[Trophic niche partitioning of pelagic sharks in Central Eastern Pacific inferred from stable isotope analysis.

PubMed

Li, Yun Kai; Gao, Xiao di; Wang, Lin Yu; Fang, Lin

2018-01-01

As the apex predators of the open ocean ecosystems, pelagic sharks play important roles in stabilizing the marine food web through top-down control. Stable isotope analysis is a powerful tool to investigate the feeding ecology. The carbon and nitrogen isotope ratios can be used to trace food source and evaluate the trophic position of marine organisms. In this study, the isotope values of 130 pelagic sharks from 8 species in Central Eastern Pacific were analyzed and their trophic position and niche were calculated to compare the intra/inter-specific resource partitioning in the Central Eastern Pacific ecosystem. The results exhibited significant differences in both carbon and nitrogen isotope values among the shark species. The trophic levels ranged from 4.3 to 5.4 in the Central Eastern Pacific shark community. The trophic niche of blue sharks and shortfin mako sharks showed no overlap with the other shark species, exhibiting unique ecological roles in the open ocean food web. These data highlighted the diverse roles among pelagic sharks, supporting previous findings that this species is not trophically redundant and the trophic niche of pelagic sharks can not be simply replaced by those of other top predator species.

Characterization of frictional melting processes in subduction zone faults by trace element and isotope analyses

NASA Astrophysics Data System (ADS)

Ishikawa, T.; Ujiie, K.

2017-12-01

Pseudotachylytes found in exhumed accretionary complexes, which are considered to be formed originally at seismogenic depths, are of great importance for elucidating frictional melting and concomitant dynamic weakening of the fault during earthquake in subduction zones. However, fluid-rich environment of the subduction zone faults tends to cause extensive alteration of the pseudotachylyte glass matrix in later stages, and thus it has been controversial that pseudotachylytes are rarely formed or rarely preserved. Chemical analysis of the fault rocks, especially on fluid-immobile trace elements and isotopes, can be a useful means to identify and quantify the frictional melting occurred in subduction zone faults. In this paper, we report major and trace element and Sr isotope compositions for pseudotachylyte-bearing dark veins and surrounding host rocks from the Mugi area of the Shimanto accretionary complex (Ujiie et al., J. Struct. Geol. 2007). Samples were collected from a rock chip along the microstructure using a micro-drilling technique, and then analyzed by ICP-MS and TIMS. Major element compositions of the dark veins showed a clear shift from the host rock composition toward the illite composition. The dark veins, either unaltered or completely altered, were also characterized by extreme enrichment in some of the trace elements such as Ti, Zr, Nb and Th. These results are consistent with disequilibrium melting of the fault zone. Model calculations revealed that the compositions of the dark veins can be produced by total melting of clay-rich matrix in the source rock, leaving plagioclase and quartz grains almost unmolten. The calculations also showed that the dark veins are far more enriched in melt component than that expected from the source rock compositions, suggesting migration and concentration of frictional melt during the earthquake faulting. Furthermore, Sr isotope data of the dark veins implied the occurrence of frictional melting in multiple stages. These results demonstrate that trace element and isotope analyses are useful not only to detect preexistence of pseudotachylytes but also to evaluate the frictional melting in subduction zone faults quantitatively.

Planetary atmospheres minor species sensor balloon flight test to near space

NASA Astrophysics Data System (ADS)

Peale, Robert E.; Fredricksen, Christopher J.; Muraviev, Andrei V.; Maukonen, Douglas; Quddusi, Hajrah M.; Calhoun, Seth; Colwell, Joshua E.; Lachenmeier, Timothy A.; Dewey, Russell G.; Stern, Alan; Padilla, Sebastian; Bode, Rolfe

2015-05-01

The Planetary Atmospheres Minor Species Sensor (PAMSS) is an intracavity laser absorption spectrometer that uses a mid-infrared quantum cascade laser in an open external cavity for sensing ultra-trace gases with parts-per-billion sensitivity. PAMSS was flown on a balloon by Near Space Corporation from Madras OR to 30 km on 17 July 2014. Based on lessons learned, it was modified and was flown a second time to 32 km by World View Enterprises from Pinal AirPark AZ on 8 March 2015. Successes included continuous operation and survival of software, electronics, optics, and optical alignment during extreme conditions and a rough landing. Operation of PAMSS in the relevant environment of near space has significantly elevated its Technical Readiness Level for trace-gas sensing with potential for planetary and atmospheric science in harsh environments.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

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

PubMed

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

2008-01-01

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

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

PubMed

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

2016-02-15

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

Water quality conditions and food web structure in Chequamegon Bay

EPA Science Inventory

Abstract: Stable isotopes of carbon and nitrogen are powerful tools for tracing human- and watershed-derived nutrients and energy in coastal ecosystems. We used carbon and nitrogen stable isotope analysis to identify externally- and internally-produced nutrients and energy suppor...

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

NASA Astrophysics Data System (ADS)

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

2014-01-01

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

Highly selective micro-sequential injection lab-on-valve (muSI-LOV) method for the determination of ultra-trace concentrations of nickel in saline matrices using detection by electrothermal atomic absorption spectrometry.

PubMed

Long, Xiangbao; Miró, Manuel; Jensen, Rikard; Hansen, Elo Harald

2006-10-01

A highly selective procedure is proposed for the determination of ultra-trace level concentrations of nickel in saline aqueous matrices exploiting a micro-sequential injection Lab-On-Valve (muSI-LOV) sample pretreatment protocol comprising bead injection separation/pre-concentration and detection by electrothermal atomic absorption spectrometry (ETAAS). Based on the dimethylglyoxime (DMG) reaction used for nickel analysis, the sample, as contained in a pH 9.0 buffer, is, after on-line merging with the chelating reagent, transported to a reaction coil attached to one of the external ports of the LOV to assure sufficient reaction time for the formation of Ni(DMG)(2) chelate. The non-ionic coordination compound is then collected in a renewable micro-column packed with a reversed-phase copolymeric sorbent [namely, poly(divinylbenzene-co-N-vinylpyrrolidone)] containing a balanced ratio of hydrophilic and lipophilic monomers. Following elution by a 50-muL methanol plug in an air-segmented modality, the nickel is finally quantified by ETAAS. Under the optimized conditions and for a sample volume of 1.8 mL, a retention efficiency of 70 % and an enrichment factor of 25 were obtained. The proposed methodology showed a high tolerance to the commonly encountered alkaline earth matrix elements in environmental waters, that is, calcium and magnesium, and was successfully applied for the determination of nickel in an NIST standard reference material (NIST 1640-Trace elements in natural water), household tap water of high hardness and local seawater. Satisfying recoveries were achieved for all spiked environmental water samples with maximum deviations of 6 %. The experimental results for the standard reference material were not statistically different to the certified value at a significance level of 0.05.

Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

NASA Technical Reports Server (NTRS)

Mahaffy, P.; Niemann, Hasso (Technical Monitor)

2001-01-01

Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

Effects of Iron and Nitrogen Limitation on Sulfur Isotope Fractionation during Microbial Sulfate Reduction

PubMed Central

Ono, Shuhei; Bosak, Tanja

2012-01-01

Sulfate-reducing microbes utilize sulfate as an electron acceptor and produce sulfide that is depleted in heavy isotopes of sulfur relative to sulfate. Thus, the distribution of sulfur isotopes in sediments can trace microbial sulfate reduction (MSR), and it also has the potential to reflect the physiology of sulfate-reducing microbes. This study investigates the relationship between the availability of iron and reduced nitrogen and the magnitude of S-isotope fractionation during MSR by a marine sulfate-reducing bacterium, DMSS-1, a Desulfovibrio species, isolated from salt marsh in Cape Cod, MA. Submicromolar levels of iron increase sulfur isotope fractionation by about 50% relative to iron-replete cultures of DMSS-1. Iron-limited cultures also exhibit decreased cytochrome c-to-total protein ratios and cell-specific sulfate reduction rates (csSRR), implying changes in the electron transport chain that couples carbon and sulfur metabolisms. When DMSS-1 fixes nitrogen in ammonium-deficient medium, it also produces larger fractionation, but it occurs at faster csSRRs than in the ammonium-replete control cultures. The energy and reducing power required for nitrogen fixation may be responsible for the reverse trend between S-isotope fractionation and csSRR in this case. Iron deficiency and nitrogen fixation by sulfate-reducing microbes may lead to the large observed S-isotope effects in some euxinic basins and various anoxic sediments. PMID:23001667

Timescale of Petrogenetic Processes Recorded in the Mount Perkins Magma System, Northern Colorado River Extension Corridor, Arizona

NASA Technical Reports Server (NTRS)

Danielson, Lisa R.; Metcalf, Rodney V.; Miller, Calvin F.; Rhodes Gregory T.; Wooden, J. L.

2013-01-01

The Miocene Mt. Perkins Pluton is a small composite intrusive body emplaced in the shallow crust as four separate phases during the earliest stages of crustal extension. Phase 1 (oldest) consists of isotropic hornblende gabbro and a layered cumulate sequence. Phase 2 consists of quartz monzonite to quartz monzodiorite hosting mafic microgranitoid enclaves. Phase 3 is composed of quartz monzonite and is subdivided into mafic enclave-rich zones and enclave-free zones. Phase 4 consists of aphanitic dikes of mafic, intermediate and felsic compositions hosting mafic enclaves. Phases 2-4 enclaves record significant isotopic disequilibrium with surrounding granitoid host rocks, but collectively enclaves and host rocks form a cogenetic suite exhibiting systematic variations in Nd-Sr-Pb isotopes that correlate with major and trace elements. Phases 2-4 record multiple episodes of magma mingling among cogenetic hybrid magmas that formed via magma mixing and fractional crystallization at a deeper crustal. The mafic end-member was alkali basalt similar to nearby 6-4 Ma basalt with enriched OIB-like trace elements and Nd-Sr-Pb isotopes. The felsic end-member was a subalkaline crustal-derived magma. Phase 1 isotropic gabbro exhibits elemental and isotopic compositional variations at relatively constant SiO2, suggesting generation of isotropic gabbro by an open-system process involving two mafic end-members. One end-member is similar in composition to the OIB-like mafic end-member for phases 2-4; the second is similar to nearby 11-8 Ma tholeiite basalt exhibiting low epsilon (sub Nd), and depleted incompatible trace elements. Phase 1 cumulates record in situ fractional crystallization of an OIB-like mafic magma with isotopic evidence of crustal contamination by partial melts generated in adjacent Proterozoic gneiss. The Mt Perkins pluton records a complex history in a lithospheric scale magma system involving two distinct mantle-derived mafic magmas and felsic magma sourced in the crust. Mixing and fractional crystallization of these magmas at various levels in the crust generated a suite of intermediate composition magmas. U-Pb zircon SHRIMP ages of phase 1 (15.7 +/- 0.2 Ma), phase 3 (15.8 +/- 0.2 Ma) and phase 4 (15.4 +/- 0.3 Ma) document a 100-300k year timescale for petrogenetic processes recorded in the Mt Perkins magma system.

Using Carbon-14 Isotope Tracing to Investigate Molecular Structure Effects of the Oxygenate Dibutyl Maleate on Soot Emissions from a DI Diesel Engine

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

Buchholz, B A; Mueller, C J; Upatnieks, A

2004-01-07

The effect of oxygenate molecular structure on soot emissions from a DI diesel engine was examined using carbon-14 ({sup 14}C) isotope tracing. Carbon atoms in three distinct chemical structures within the diesel oxygenate dibutyl maleate (DBM) were labeled with {sup 14}C. The {sup 14}C from the labeled DBM was then detected in engine-out particulate matter (PM), in-cylinder deposits, and CO{sub 2} emissions using accelerator mass spectrometry (AMS). The results indicate that molecular structure plays an important role in determining whether a specific carbon atom either does or does not form soot. Chemical-kinetic modeling results indicate that structures that produce CO{submore » 2} directly from the fuel are less effective at reducing soot than structures that produce CO before producing CO{sub 2}. Because they can follow individual carbon atoms through a real combustion process, {sup 14}C isotope tracing studies help strengthen the connection between actual engine emissions and chemical-kinetic models of combustion and soot formation/oxidation processes.« less

Mineralization, watershed geochemistry, and metals in fish from a Subarctic River, Alaska

USGS Publications Warehouse

Gough, L.P.; Wang, B.; Crock, J.G.; Seal, R.R.; Weber-Scannell, P.

2005-01-01

We report on the levels of trace metals and metalloids in Arctic grayling (Thymallus arcticus), an important freshwater sport and subsistence fish in the Fortymile River, east-central Alaska. Functional biogeochemical baseline values and (or) ranges are presented for 38 major- and trace-elements in the muscle (fillet) and liver of 34 fish collected from 11 sampling sites in the watershed. In addition, we present N-, C-, and S-isotopic data for muscle samples. These data are the first to be reported for Arctic grayling in this region of Alaska. Geometric means for total Hg in muscle and liver tissue are 0.069 and 0.062 ppm, respectively. These levels are more than an order of magnitude below the FDA permissible value for methylmercury in fish fillets. In general, we noted little variation in the elemental concentrations in muscle tissue among samples at each of the 11 fish-sampling sites. No definitive link could be attributed between biogeochemical patterns and regional lithology. Stomach-content chemistry varied widely (relative muscle tissue or liver) and generally reflected sediment chemistry - a component of the ingested material. Stomach-content material was examined for the occurrence and frequency of macroinvertebrates and their chemical composition in three fish. Results showed considerable diversity, with 9 to 15 invertebrate taxa of which both aquatic and terrestrial individuals were found. The N-isotopic compositions of muscle fillet samples are homogeneous (??15N = 7.6 - 9.7 permil), reflecting a restricted, low trophic (primary predator) position for the grayling. C and S isotopic compositions (??13C and ??34S) of fillet samples range from -33.1 to -25.8 permil and -8.4 to 8.2 permil, respectively, suggesting heterogeneity of food sources (both aquatic and terrestrial). Copyright ASCE 2005.

Collaborative Study of Analysis of High Resolution Infrared Atmospheric Spectra Between NASA Langley Research Center and the University of Denver

NASA Technical Reports Server (NTRS)

Goldman, Aaron

1999-01-01

The Langley-D.U. collaboration on the analysis of high resolution infrared atmospheric spectra covered a number of important studies of trace gases identification and quantification from field spectra, and spectral line parameters analysis. The collaborative work included: Quantification and monitoring of trace gases from ground-based spectra available from various locations and seasons and from balloon flights. Studies toward identification and quantification of isotopic species, mostly oxygen and Sulfur isotopes. Search for new species on the available spectra. Update of spectroscopic line parameters, by combining laboratory and atmospheric spectra with theoretical spectroscopy methods. Study of trends of atmosphere trace constituents. Algorithms developments, retrievals intercomparisons and automatization of the analysis of NDSC spectra, for both column amounts and vertical profiles.

Stable isotope biogeochemistry of seabird guano fertilization: results from growth chamber studies with maize (Zea mays).

PubMed

Szpak, Paul; Longstaffe, Fred J; Millaire, Jean-François; White, Christine D

2012-01-01

Stable isotope analysis is being utilized with increasing regularity to examine a wide range of issues (diet, habitat use, migration) in ecology, geology, archaeology, and related disciplines. A crucial component to these studies is a thorough understanding of the range and causes of baseline isotopic variation, which is relatively poorly understood for nitrogen (δ(15)N). Animal excrement is known to impact plant δ(15)N values, but the effects of seabird guano have not been systematically studied from an agricultural or horticultural standpoint. This paper presents isotopic (δ(13)C and δ(15)N) and vital data for maize (Zea mays) fertilized with Peruvian seabird guano under controlled conditions. The level of (15)N enrichment in fertilized plants is very large, with δ(15)N values ranging between 25.5 and 44.7‰ depending on the tissue and amount of fertilizer applied; comparatively, control plant δ(15)N values ranged between -0.3 and 5.7‰. Intraplant and temporal variability in δ(15)N values were large, particularly for the guano-fertilized plants, which can be attributed to changes in the availability of guano-derived N over time, and the reliance of stored vs. absorbed N. Plant δ(13)C values were not significantly impacted by guano fertilization. High concentrations of seabird guano inhibited maize germination and maize growth. Moreover, high levels of seabird guano greatly impacted the N metabolism of the plants, resulting in significantly higher tissue N content, particularly in the stalk. The results presented in this study demonstrate the very large impact of seabird guano on maize δ(15)N values. The use of seabird guano as a fertilizer can thus be traced using stable isotope analysis in food chemistry applications (certification of organic inputs). Furthermore, the fertilization of maize with seabird guano creates an isotopic signature very similar to a high-trophic level marine resource, which must be considered when interpreting isotopic data from archaeological material.

Interrogating pollution sources in a mangrove food web using multiple stable isotopes.

PubMed

Souza, Iara da C; Arrivabene, Hiulana P; Craig, Carol-Ann; Midwood, Andrew J; Thornton, Barry; Matsumoto, Silvia T; Elliott, Michael; Wunderlin, Daniel A; Monferrán, Magdalena V; Fernandes, Marisa N

2018-06-01

Anthropogenic activities including metal contamination create well-known problems in coastal mangrove ecosystems but understanding and linking specific pollution sources to distinct trophic levels within these environments is challenging. This study evaluated anthropogenic impacts on two contrasting mangrove food webs, by using stable isotopes (δ 13 C, δ 15 N, 87 Sr/ 86 Sr, 206 Pb/ 207 Pb and 208 Pb/ 207 Pb) measured in sediments, mangrove trees (Rhizophora mangle, Laguncularia racemosa, Avicennia schaueriana), plankton, shrimps (Macrobranchium sp.), crabs (Aratus sp.), oysters (Crassostrea rhizophorae) and fish (Centropomus parallelus) from both areas. Strontium and Pb isotopes were also analysed in water and atmospheric particulate matter (PM). δ 15 N indicated that crab, shrimp and oyster are at intermediate levels within the local food web and fish, in this case C. parallelus, was confirmed at the highest trophic level. δ 15 N also indicates different anthropogenic pressures between both estuaries; Vitória Bay, close to intensive human activities, showed higher δ 15 N across the food web, apparently influenced by sewage. The ratio 87 Sr/ 86 Sr showed the primary influence of marine water throughout the entire food web. Pb isotope ratios suggest that PM is primarily influenced by metallurgical activities, with some secondary influence on mangrove plants and crabs sampled in the area adjacent to the smelting works. To our knowledge, this is the first demonstration of the effect of anthropogenic pollution (probable sewage pollution) on the isotopic fingerprint of estuarine-mangrove systems located close to a city compared to less impacted estuarine mangroves. The influence of industrial metallurgical activity detected using Pb isotopic analysis of PM and mangrove plants close to such an impacted area is also notable and illustrates the value of isotopic analysis in tracing the impact and species affected by atmospheric pollution. Copyright © 2018 Elsevier B.V. All rights reserved.

Using Archean and Paleoproterozoic Shales and Tillites as a Window into Crustal Evolution and Surface Conditions

NASA Astrophysics Data System (ADS)

Bindeman, I. N.; Bekker, A.; Zakharov, D. O.

2014-12-01

Precambrian shales and tillites have been insufficiently studied so far. We present oxygen and hydrogen isotope data for 103 bulk shale and tillites that were collected from drillholes on all continents from 3.2 to 1.4Ga. These samples have also been analyzed for total organic and inorganic carbon, total sulfur, δ13Corg values and by XRF for major and trace elements to calculate chemical index of alteration (CIA). Having uncompromised fresh samples from drillcores is a must for this kind of investigation. We have a particularly good coverage for the ca. 2.7-2.2 Ga time interval when Earth experienced 3-4 Snowball Earth glaciations associated with the rapid rise in atmospheric O2 and fluctuations in CO2, thus affecting weathering cycle and attainment of isotopic fractionation. All units have similar to Phanerozoic ranges in δ13Corg values (-23 to -33‰ PDB) and Corg content (0.1 to 10 wt. %). Compared to Phanerozoic shales, Precambrian shales have comparable ranges in δ18O values (+7 to +20‰), with slightly decreasing means with increasing age, and identical δ17O-δ18O slope (0.528). Shales in some drill holes display wide δ18O ranges over short stratigraphic intervals suggesting significant variability in the provenance. We however observe a significant, several permil downward shift and decrease in the range of δ18O values (7-9‰) in 2.2-2.5 Ga shales from several continents that are associated with the Paleoproterozoic glaciations. Scattered negative correlation of CIA with δ18O, for some of these shales broadly associated with the Paleoproterozoic glaciations suggest contact with glacial meltwater having ultra-low-δ18O values during deposition or diagenesis of these shales. The δD values of shales range from -50 to -75‰, and are comparable to Phanerozoic values, with the exception of the ~2.5-2.2 Ga shales that reach to -100‰. We also compare O isotope values of ultra-low-δ18O, +8 to -27‰ SMOW subglacial hydrothermal rocks recently discovered in Karelia (Russia), quartz amygdules in mafics and their relations to our global shale dataset. The overall conclusion is that despite first-order changes in areal mass, exposed surface conditions, pCO2, pO2 affecting chemical/physical weathering cycle, it was not dramatically different before and after the rise of atmospheric oxygen at ~2.3-2.4 Ga.

Volatile element content of the heterogeneous upper mantle

NASA Astrophysics Data System (ADS)

Shimizu, K.; Saal, A. E.; Hauri, E. H.; Forsyth, D. W.; Kamenetsky, V. S.; Niu, Y.

2014-12-01

The physical properties of the asthenosphere (e.g., seismic velocity, viscosity, electrical conductivity) have been attributed to either mineral properties at relevant temperature, pressure, and water content or to the presence of a low melt fraction. We resort to the geochemical studies of MORB to unravel the composition of the asthenosphere. It is important to determine to what extent the geochemical variations in axial MORB do represent a homogeneous mantle composition and variations in the physical conditions of magma generation and transport; or alternatively, they represent mixing of melts from a heterogeneous upper mantle. Lavas from intra-transform faults and off-axis seamounts share a common mantle source with axial MORB, but experience less differentiation and homogenization. Therefore they provide better estimates for the end-member volatile budget of the heterogeneous upper mantle. We present major, trace, and volatile element data (H2O, CO2, Cl, F, S) as well as Sr, Nd, and Pb isotopic compositions [1, 2] of basaltic glasses (MgO > 6.0 wt%) from the NEPR seamounts, Quebrada-Discovery-Gofar transform fault system, and Macquarie Island. The samples range from incompatible trace element (ITE) depleted (DMORB: Th/La<0.035) to enriched (EMORB: Th/La>0.07) spanning the entire range of EPR MORB. The isotopic composition of the samples correlates with the degree of trace element enrichment indicating long-lived mantle heterogeneity. Once shallow-level processes (degassing, crystallization, and crustal assimilation) have been considered, we conducted a two-component (DMORB- and EMORB-) mantle melting-mixing model. Our model reproduces the major, trace and volatile element contents and isotopic composition of our samples and suggests that (1) 90% of the upper mantle is highly depleted in ITE (DMORB source) with only 10% of an enriched component (EMORB source), (2) the EMORB source is peridotitic rather than pyroxenitic, and (3) NMORB do not represent an actual mantle source, but the product of magma mixing between D- and E-MORB. Finally we use the volatile to trace element ratios of our samples to estimate the volatile element budget of the end-member components of the upper mantle. [1] Niu, Y. et al. (2002) EPSL, 199, 327-345. [2] Kamenetsky, V. S. et al. (2000) J. Petrology, 41, 411-430.

Biomarker analysis of hemoglobin adducts of acrylamide and glycidamide enantiomers for mid-term internal exposure assessment by isotope dilution ultra-high performance liquid chromatography tandem mass spectrometry.

PubMed

Zhang, Yu; Wang, Qiao; Zhang, Gong; Jia, Wei; Ren, Yiping; Wu, Yongning

2018-02-01

Hemoglobin (Hb) adducts of acrylamide (AA) and its oxidative metabolite glycidamide (GA) are important biomarkers for evaluating the mid-term exposure of acrylamide toxicity in vivo. Taking pentafluoro-2-methylphenyl isothiocyanates of N-(2-carbamoylethyl)valine (AAVal-PFPTH) and N-(2-carbamoyl-2-hydroxyethy)valine (GAVal-PFPTH) as target analytes, we developed an isotope dilution ultra-high performance liquid chromatograph tandem mass spectrometry (UHPLC-MS/MS) method for the simultaneous determination of AA and GA hemoglobin (Hb) adducts under the electroscopy ionization negative (ESI‾) mode in the present work. Among them, the enantiomer pair of GA-Hb adducts was firstly identified and successfully separated at baseline level. The method achieved high sensitivity with the LOD and LOQ ranging 1.43-5.05pmol/g Hb and 4.78-16.82pmol/g Hb, respectively. The recovery rates with low, intermediate and high spiking levels were calculated as 97.0-105.2%, 97.4-106.4% and 100.3-111.2%, respectively. Acceptable within-laboratory reproducibility (RSD < 13.7%) substantially supported the robustness of current UHPLC-MS/MS method, which was successfully applied to measure the hemoglobin adducts of acrylamide and glycidamide enantiomers in blood of both rats and humans. A linear exposure assessment model was developed for estimating the daily exposure to acrylamide in humans via considering acrylamide hemoglobin adducts as variables, indicating a novel connect between biomarker-based internal exposure and dietary-based external exposure. Overall, the present instrumental analysis and related internal exposure assessment model provide a substantially methodological support for profiling the internal biological exposure and estimating the external dietary exposure to acrylamide. Copyright © 2017 Elsevier B.V. All rights reserved.

Stable isotope dilution ultra-high performance liquid chromatography-tandem mass spectrometry quantitative profiling of tryptophan-related neuroactive substances in human serum and cerebrospinal fluid.

PubMed

Hényková, Eva; Vránová, Hana Přikrylová; Amakorová, Petra; Pospíšil, Tomáš; Žukauskaitė, Asta; Vlčková, Magdaléna; Urbánek, Lubor; Novák, Ondřej; Mareš, Jan; Kaňovský, Petr; Strnad, Miroslav

2016-03-11

Many compounds related to L-tryptophan (L-TRP) have interesting biological or pharmacological activity, and their abnormal neurotransmission seems to be linked to a wide range of neurodegenerative and psychiatric diseases. A high-throughput method based on ultra-high performance liquid chromatography connected to electrospray tandem mass spectrometry (UHPLC-ESI-MS/MS) was developed for the quantitative analysis of L-TRP and 16 of its metabolites in human serum and cerebrospinal fluid (CSF), representing both major and minor routes of L-TRP catabolism. The combination of a fast LC gradient with selective tandem mass spectrometry enabled accurate analysis of almost 100 samples in 24h. The standard isotope dilution method was used for quantitative determination. The method's lower limits of quantification for serum and cerebrospinal fluid ranged from 0.05 to 15nmol/L and 0.3 to 45nmol/L, respectively. Analytical recoveries ranged from 10.4 to 218.1% for serum and 22.1 to 370.0% for CSF. The method's accuracy ranged from 82.4 to 128.5% for serum matrix and 90.7 to 127.7% for CSF matrix. All intra- and inter-day coefficients of variation were below 15%. These results demonstrate that the new method is capable of quantifying endogenous serum and CSF levels of a heterogeneous group of compounds spanning a wide range of concentrations. The method was used to determine the physiological levels of target analytes in serum and CSF samples from 18 individuals, demonstrating its reliability and potential usefulness in large-scale epidemiological studies. Copyright © 2016 Elsevier B.V. All rights reserved.

Ultra-Low Level Plutonium Isotopes in the NIST SRM 4355A (Peruvian Soil-1)

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

Inn, Kenneth G.; LaRosa, Jerome; Nour, Svetlana

2009-05-31

For more than 20 years, countries and their agencies which monitor discharge sites and storage facilities have relied on the National Institute of Standards and Technology (NIST) Standard Reference Material (SRM) 4355 Peruvian Soil reference material. Its low fallout contamination makes it an ideal soil blank for measurements associated with terrestrial pathway to man studies. Presently, SRM 4355 is out of stock, and a new batch of the Peruvian soil is currently under development as future NIST SRM 4355A. Both environmental radioanalytical laboratories and mass spectrometry communities will benefit from this SRM. The former must assess their laboratory contamination andmore » measurement detection limits by measurement of blank sample material. The Peruvian Soil is so low in anthropogenic radionuclides that it is a suitable virtual blank. On the other hand, mass spectrometric laboratories have high sensitivity instruments that are capable of quantitative isotopic measurements at low plutonium levels of the SRM 4355 (first Peruvian Soil SRM) that provided the mass spectrometric community with the calibration, quality control, and testing material needed for methods development, and legal defensibility. The quantification of the ultra-low plutonium content in the SRM 4355A was a considerable challenge for the mass spectrometric laboratories. Careful blank control and correction, isobaric interferences, instrument stability, peak assessment, and detection assessment were necessary. Furthermore, a systematic statistical evaluation of the measurement results and considerable discussions with the mass spectroscopy metrologists were needed to derive the certified values and uncertainties. SRM 4355A will provide the mass spectrometric community with the quality control and testing material needed for higher sensitivity methods development, and legal defensibility.« less

Ultra-low level plutonium isotopes in the NIST SRM 4355A (Peruvian Soil-1).

PubMed

Inn, Kenneth G W; LaRosa, Jerome; Nour, Svetlana; Brooks, George; LaMont, Steve; Steiner, Rob; Williams, Ross; Patton, Brad; Bostick, Debbie; Eiden, Gregory; Petersen, Steve; Douglas, Matthew; Beals, Donna; Cadieux, James; Hall, Greg; Goldberg, Steve; Vogt, Stephan

2009-05-01

For more than 20 years, countries and their agencies which monitor radionuclide discharge sites and storage facilities have relied on the National Institute of Standards and Technology (NIST) Standard Reference Material (SRM) 4355 Peruvian Soil. Its low fallout contamination makes it an ideal soil blank for measurements associated with terrestrial-pathway-to-man studies. Presently, SRM 4355 is out of stock, and a new batch of the Peruvian soil is currently under development as future NIST SRM 4355A. Both environmental radioanalytical laboratories and mass spectrometry communities will benefit from the use of this SRM. The former must assess their laboratory procedural contamination and measurement detection limits by measurement of blank sample material. The Peruvian Soil is so low in anthropogenic radionuclide content that it is a suitable virtual blank. On the other hand, mass spectrometric laboratories have high sensitivity instruments that are capable of quantitative isotopic measurements at low plutonium levels in the SRM 4355 (first Peruvian Soil SRM) that provided the mass spectrometric community with the calibration, quality control, and testing material needed for methods development and legal defensibility. The quantification of the ultra-low plutonium content in the SRM 4355A was a considerable challenge for the mass spectrometric laboratories. Careful blank control and correction, isobaric interferences, instrument stability, peak assessment, and detection assessment were necessary. Furthermore, a systematic statistical evaluation of the measurement results and considerable discussions with the mass spectroscopy metrologists were needed to derive the certified values and uncertainties. The one sided upper limit of the 95% tolerance with 95% confidence for the massic (239)Pu content in SRM 4355A is estimated to be 54,000 atoms/g.

The plutonium isotopic composition of marine biota on Enewetak Atoll: a preliminary assessment.

PubMed

Hamilton, Terry F; Martinelli, Roger E; Kehl, Steven R; McAninch, Jeffrey E

2008-10-01

We have determined the level and distribution of gamma-emitting radionuclides, plutonium activity concentrations, and 240Pu/239Pu atom ratios in tissue samples of giant clam (Tridacna gigas and Hippopus hippopus), a top snail (Trochus nilaticas) and sea cucumber (Holothuria atra) collected from different locations around Enewetak Atoll. The plutonium isotopic measurements were performed using ultra-high sensitivity accelerator mass spectrometry (AMS). Elevated levels of plutonium were observed in the stomachs (includes the stomach lining) of Tridacna clam (0.62 to 2.98 Bq kg(-1), wet wt.), in the soft parts (edible portion) of top snails (0.25 to 1.7 Bq kg(-1)), wet wt.) and, to a lesser extent, in sea cucumber (0.015 to 0.22 Bq kg(-1), wet wt.) relative to muscle tissue concentrations in clam (0.006 to 0.021 Bq kg(-1), wet wt.) and in comparison with previous measurements of plutonium in fish. These data and information provide a basis for re-evaluating the relative significance of dietary intakes of plutonium from marine foods on Enewetak Atoll and, perhaps most importantly, demonstrate that discrete 240Pu239Pu isotope signatures might well provide a useful investigative tool to monitor source-term attribution and consequences on Enewetak Atoll. One potential application of immediate interest is to monitor and assess the health and ecological impacts of leakage of plutonium (as well as other radionuclides) from a low-level radioactive waste repository on Runit Island relative to background levels of fallout contamination in Enewetak Atoll lagoon.

Trace element and isotopic composition of apatite in carbonatites from the Blue River area (British Columbia, Canada) and mineralogy of associated silicate rocks

NASA Astrophysics Data System (ADS)

Mitchell, Roger; Chudy, Thomas; McFarlane, Christopher R. M.; Wu, Fu-Yuan

2017-08-01

Apatites from the Verity, Fir, Gum, Howard Creek and Felix carbonatites of the Blue River (British Columbia, Canada) area have been investigated with respect to their paragenesis, cathodoluminescence, trace element and Sr-Nd isotopic composition. Although all of the Blue River carbonatites were emplaced as sills prior to amphibolite grade metamorphism and have undergone deformation, in many instances magmatic textures and mineralogy are retained. Attempts to constrain the U-Pb age of the carbonatites by SIMS, TIMS and LA-ICP-MS studies of zircon and titanite were inconclusive as all samples investigated have experienced significant Pb loss during metamorphism. The carbonatites are associated with undersaturated calcite-titanite amphibole nepheline syenite only at Howard Creek although most contain clasts of disaggregated phoscorite-like rocks. Apatite from each intrusion is characterized by distinct, but wide ranges, in trace element composition. The Sr and Nd isotopic compositions define an array on a 87Sr/86Sr vs²Nd diagram at 350 Ma indicating derivation from depleted sub-lithospheric mantle. This array could reflect mixing of Sr and Nd derived from HIMU and EM1 mantle sources, and implies that depleted mantle underlies the Canadian Cordillera. Although individual occurrences of carbonatites in the Blue River region are mineralogically and geochemically similar they are not identical and thus cannot be considered as rocks formed from a single batch of parental magma at the same stage of magmatic evolution. However, a common origin is highly probable. The variations in the trace element content and isotopic composition of apatite from each occurrence suggest that each carbonatite represents a combination of derivation of the parental magma(s) from mineralogically and isotopically heterogeneous depleted mantle sources coupled with different stages of limited differentiation and mixing of these magmas. We do not consider these carbonatites as primary direct partial melts of the sub-lithospheric mantle which have ascended from the asthenosphere without modification of their composition.

[Simultaneous determination of delta-9-tetrahydrocannabinol cannabidiol and cannabinol in edible oil using ultra performance liquid chromatography-tandem mass spectrometry].

PubMed

Zhang, Aizhi; Wang, Quanlin; Mo, Shijie

2010-11-01

A method for the simultaneous determination of delta-9-tetrahydrocannabinol (THC), cannabidiol (CBD) and cannabinol (CBN) in edible oil was developed using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The target compounds were extracted with methanol, purified by an LC-Alumina-N solid phase extraction cartridge, separated and detected by the UPLC-MS/MS. Quantitative analysis was corrected by an isotope internal standard method using delta-9-THC-D3 as internal standard. Average recoveries for the target compounds varied from 68.0% to 101.6% with the relative standard deviations ranging from 7.0% to 20.1% at three spiked levels. The limits of detection (LOD) of the method were from 0.06-0.17 microg/kg and the limits of quantification (LOQ) were in the range of 0.20-0.52 microg/kg. The results showed that the method is able to meet the requirements for the simultaneous determination of THC, CBD and CBN in edible oil.

Optical molecular fluorescence determination of ultra-trace beryllium in occupational and environmental samples using highly alkaline conditions

PubMed Central

Adams, Lori; Agrawal, Anoop; Cronin, John P.; Ashley, Kevin

2017-01-01

Exposures to beryllium (Be), even at extremely low levels, can cause severe health effects in a percentage of those exposed; consequently, occupational exposure limits (OELs) promulgated for this element are the lowest established for any element. This work describes the advantages of using highly alkaline dye solutions for determination of Be in occupational hygiene and environmental samples by means of an optical molecular fluorescence technique after sample extraction in 1–3% (w˖w−1) aqueous ammonium bifluoride (NH4HF2). Improved attributes include the ability to further enhance the detection limits of Be in extraction solutions of high acidity with minimal dilution, which is particularly beneficial when NH4HF2 solutions of higher concentration are used for extraction of Be from soil samples. Significant improvements in Be method detection limits (MDLs) are obtained at levels many-fold below those reported previously for this methodology. Notably, MDLs for Be of <0.01 ng l−1 / 0.1 ng per sample have been attained, which are superior to MDLs routinely reported for this element by means of the most widely used ultra-trace elemental measurement technique, inductively coupled plasma mass spectrometry (ICP-MS). Very low MDLs for Be are essential in consideration of reductions in OELs for this element in workplace air by health organizations and regulatory agencies in the USA and internationally. Applications of enhanced Be measurements to air filter samples, surface wipe samples, soils and newly-designed occupational air sampler inserts are illustrated. PMID:28626294

Method for determination of levoglucosan in snow and ice at trace concentration levels using ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry.

PubMed

You, Chao; Song, Lili; Xu, Baiqing; Gao, Shaopeng

2016-02-01

A method is developed for determination of levoglucosan at trace concentration levels in complex matrices of snow and ice samples. This method uses an injection mixture comprising acetonitrile and melt sample at a ratio of 50/50 (v/v). Samples are analyzed using ultra-performance liquid chromatography system combined with triple tandem quadrupole mass spectrometry (UPLC-MS/MS). Levoglucosan is analyzed on BEH Amide column (2.1 mm × 100 mm, 1.7 um), and a Z-spray electrospray ionization source is used for levoglucosan ionization. The polyether sulfone filter is selected for filtrating insoluble particles due to less impact on levoglucosan. The matrix effect is evaluated by using a standard addition method. During the method validation, limit of detection (LOD), linearity, recovery, repeatability and reproducibility were evaluated using standard addition method. The LOD of this method is 0.11 ng mL(-1). Recoveries vary from 91.2% at 0.82 ng mL(-1) to 99.3% at 4.14 ng mL(-1). Repeatability ranges from 17.9% at a concentration of 0.82 ng mL(-1) to 2.8% at 4.14 ng mL(-1). Reproducibility ranges from 15.1% at a concentration of 0.82 ng mL(-1) to 1.9% at 4.14 ng mL(-1). This method can be implemented using less than 0.50 mL sample volume in low and middle latitude regions like the Tibetan Plateau. Copyright © 2015 Elsevier B.V. All rights reserved.

Source tracing of natural organic matter bound mercury in boreal forest runoff with mercury stable isotopes.

PubMed

Jiskra, Martin; Wiederhold, Jan G; Skyllberg, Ulf; Kronberg, Rose-Marie; Kretzschmar, Ruben

2017-10-18

Terrestrial runoff represents a major source of mercury (Hg) to aquatic ecosystems. In boreal forest catchments, such as the one in northern Sweden studied here, mercury bound to natural organic matter (NOM) represents a large fraction of mercury in the runoff. We present a method to measure Hg stable isotope signatures of colloidal Hg, mainly complexed by high molecular weight or colloidal natural organic matter (NOM) in natural waters based on pre-enrichment by ultrafiltration, followed by freeze-drying and combustion. We report that Hg associated with high molecular weight NOM in the boreal forest runoff has very similar Hg isotope signatures as compared to the organic soil horizons of the catchment area. The mass-independent fractionation (MIF) signatures (Δ 199 Hg and Δ 200 Hg) measured in soils and runoff were in agreement with typical values reported for atmospheric gaseous elemental mercury (Hg 0 ) and distinctly different from reported Hg isotope signatures in precipitation. We therefore suggest that most Hg in the boreal terrestrial ecosystem originated from the deposition of Hg 0 through foliar uptake rather than precipitation. Using a mixing model we calculated the contribution of soil horizons to the Hg in the runoff. At moderate to high flow runoff conditions, that prevailed during sampling, the uppermost part of the organic horizon (Oe/He) contributed 50-70% of the Hg in the runoff, while the underlying more humified organic Oa/Ha and the mineral soil horizons displayed a lower mobility of Hg. The good agreement of the Hg isotope results with other source tracing approaches using radiocarbon signatures and Hg : C ratios provides additional support for the strong coupling between Hg and NOM. The exploratory results from this study illustrate the potential of Hg stable isotopes to trace the source of Hg from atmospheric deposition through the terrestrial ecosystem to soil runoff, and provide a basis for more in-depth studies investigating the mobility of Hg in terrestrial ecosystems using Hg isotope signatures.

Major, trace element and isotope geochemistry (Sr-Nd-Pb) of interplinian magmas from Mt. Somma-Vesuvius (Southern Italy)

USGS Publications Warehouse

Somma, R.; Ayuso, R.A.; de Vivo, B.; Rolandi, G.

2001-01-01

Major, trace element and isotopic (Sr, Nd, Pb) data are reported for representative samples of interplinian (Protohistoric, Ancient Historic and Medieval Formations) activity of Mt. Somma-Vesuvius volcano during the last 3500 years. Tephra and lavas exhibit significant major, trace element and isotopic variations. Integration of these data with those obtained by previous studies on the older Somma suites and on the latest activity, allows to better trace a complete petrological and geochemical evolution of the Mt. Somma-Vesuvius magmatism. Three main groups of rocks are recognized. A first group is older than 12.000 yrs, and includes effusive-explosive activity of Mt. Somma. The second group (8000-2700 yrs B.P.) includes the products emitted by the Ottaviano (8000 yrs. B.P.) and Avellino (3550 yrs B.P.) plinian eruptions and the interplinian activity associated with the Protohistoric Formation. Ancient Historic Formation (79-472 A.D.), Medieval Formation (472-1139 A.D.) and Recent interplinian activity (1631-1944 A.D.) belong to the third group of activity (79-1944 A.D.). The three groups of rocks display distinct positive trends of alkalis vs. silica, which become increasingly steeper with age. In the first group there is an increase in silica and alkalis with time, whereas an opposite tendency is observed in the two younger groups. Systematic variations are also evident among the incompatible (Pb, Zr, Hf, Ta, Th, U, Nb, Rb, Cs, Ba) and compatible elements (Sr, Co, Cr). REE document variable degrees of fractionation, with recent activity displaying higher La/Yb ratios than Medieval and Ancient Historic products with the same degree of evolution. N-MORB normalized multi-element diagrams for interplinian rocks show enrichment in Rb, Th, Nb, Zr and Sm (> *10 N-MORB). Sr isotope ratios are variable, with Protohistoric rocks displaying 87Sr/86Sr= 0.70711-0.70810, Ancient Historic 87Sr/86Sr=0.70665-0.70729, and Medieval 87Sr/86Sr=0.70685-0.70803. Neodymium isotopic compositions in the interplinian rocks show a tendency to become slightly more radiogenic with age, from the Protohistoric (143Nd/144Nd=0.51240-0.51247) to Ancient Historic (143Nd/144Nd=0.51245-0.51251). Medieval interplinian activity (143Nd/144Nd: 0.51250-0.51241) lacks meaningful internal trends. All the interplinian rocks have virtually homogeneous compositions of 207Pb/204Pb and 208Pb/204Pb in acid-leached residues (207Pb/204Pb ???15.633 to 15.687, 208Pb/204Pb ???38.947 to 39.181). Values of 206Pb/204Pb are very distinctive, however, and discriminate among the three interplinian cycles of activity (Protohistoric: 18.929-18.971, Ancient Historic: 19.018-19.088, Medieval: 18.964-19.053). Compositional trends of major, trace element and isotopic compositions clearly demonstrate strong temporal variations of the magma types feeding the Somma-Vesuvius activity. These different trends are unlikely to be related only to low pressure evolutionary processes, and reveal variations of parental melt composition. Geochemical data suggest a three component mixing scheme for the interplinian activity. These involve HIMU-type and DMM-type mantle and Calabrian-type lower crust. Interaction between these components has taken place in the source; however, additional quantitative constraints must be acquired in order to better discriminate between magma characteristics inherited from the sources and those acquired during shallow level evolution.

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.

Energy and lighting

NASA Astrophysics Data System (ADS)

Berman, Samuel

1985-11-01

Advances in research for new types of lighting with increased efficacies (lumens/watt) are discussed in the following areas: (1) high-frequency, solid-state ballasts, (2) isotopic enhancement of mercury isotopes, (3) magnetic augmentation, (4) electrodeless, ultra-high frequency, (5) tuned phosphors, (6) two-photon phosphors, (7) heat mirrors, and (8) advanced control circuits to take advantage of daylight and occupancy. As of 1985, improvements in efficacy have been accomplished on an economic basis to save energy for (1) high frequency ballasts (25%), (2) isotopic enhancement (5%), and (8) advanced control circuits (up to 50%). Most of these advances depend on a deeper understanding of the weakly ionized plasma as a radiating and diffusing medium.

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

DOE PAGES

Knowles, Justin R.; Skutnik, Steven E.; Glasgow, David C.; ...

2016-06-23

Rapid non-destructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the High Flux Isotope Reactor Neutron Activation Analysis laboratory has developed a generalized non-destructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and capitalizes off of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a holistic characterization of isotopic identification,more » mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% error have been conducted on standards of 235U and 239Pu as low as 12 nanograms in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 229 nanograms of fissile mass with less than 12% error. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. Furthermore, it is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation sources, and account for increasingly complex sample matrices.« less

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

NASA Astrophysics Data System (ADS)

Knowles, Justin; Skutnik, Steven; Glasgow, David; Kapsimalis, Roger

2016-10-01

Rapid nondestructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the Oak Ridge National Laboratory High Flux Isotope Reactor Neutron Activation Analysis facility has developed a generalized nondestructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and makes use of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a complete characterization of isotopic identification, mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% recovery bias have been conducted on standards of 235U and 239Pu as low as 12 ng in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 198 ng of fissile mass with less than 7% recovery bias. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. It is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation facilities, and account for increasingly complex sample matrices.

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

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

Knowles, Justin R.; Skutnik, Steven E.; Glasgow, David C.

Rapid non-destructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the High Flux Isotope Reactor Neutron Activation Analysis laboratory has developed a generalized non-destructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and capitalizes off of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a holistic characterization of isotopic identification,more » mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% error have been conducted on standards of 235U and 239Pu as low as 12 nanograms in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 229 nanograms of fissile mass with less than 12% error. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. Furthermore, it is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation sources, and account for increasingly complex sample matrices.« less

Study of the cosmogenic activation in NaI(Tl) crystals within the ANAIS experiment

NASA Astrophysics Data System (ADS)

Villar, P.; Amaré, J.; Cebrián, S.; Coarasa, I.; García, E.; Martínez, M.; Oliván, M. A.; Ortigoza, Y.; Ortiz de Solórzano, A.; Puimedón, J.; Sarsa, M. L.; Villar, J. A.

2018-03-01

The direct detection of galactic dark matter particles requires ultra-low background conditions. NaI(Tl) crystals are applied in the search for these dark matter particles through their interactions in the detector by measuring the scintillation signal produced. The production of long-lived isotopes in materials due to the exposure to cosmic rays on Earth’s surface can be an hazard for these ultra-low background demanding experiments, typically performed underground. Therefore, production rates of cosmogenic isotopes in all the materials present in the experimental set-up, as well as the corresponding cosmic rays exposure history, must be both well-known in order to assess the relevance of this effect in the achievable sensitivity of a given experiment. Here, analysis of the cosmogenic studies developed from the ANAIS experiment NaI(Tl) detectors are presented. Installed inside a convenient shielding at the Canfranc Underground Laboratory just after finishing surface exposure to cosmic rays and thanks to the prompt data taking developed, identification and quantification of isotopes with half-lives of the order of tens of days were allowed, and thanks to the long-term operation of the detectors long-lived isotopes have been also identified and quantified. Main results for the activation yields of iodine and tellurium isotopes, 22Na, 113Sn, 109Cd, and tritium are presented in this work, together with the estimate of the production rates for their activation by cosmic nucleons while on Earth’s surface based on a selection of excitation functions over the entire energy range of cosmic nucleons.

Bulk Chemistry and Oxygen Isotopic Compositions of Lunar Meteorites Dhofar 025 and Dhofar 026

NASA Astrophysics Data System (ADS)

Taylor, L. A.; Nazarov, M. A.; Cohen, B. A.; Warren, P. H.; Barsukova, L. D.; Clayton, R. N.; Mayeda, T. K.

2001-03-01

The major- and trace-element composition of highlands meteorites Dh25 and Dh26 show that both are dominated by a FAN component. Incompatible element depletion and low Ti abundances suggest a farside origin. O-isotopes are typical for lunar meteorites.

Ultra-Compact Transputer-Based Controller for High-Level, Multi-Axis Coordination

NASA Technical Reports Server (NTRS)

Zenowich, Brian; Crowell, Adam; Townsend, William T.

2013-01-01

The design of machines that rely on arrays of servomotors such as robotic arms, orbital platforms, and combinations of both, imposes a heavy computational burden to coordinate their actions to perform coherent tasks. For example, the robotic equivalent of a person tracing a straight line in space requires enormously complex kinematics calculations, and complexity increases with the number of servo nodes. A new high-level architecture for coordinated servo-machine control enables a practical, distributed transputer alternative to conventional central processor electronics. The solution is inherently scalable, dramatically reduces bulkiness and number of conductor runs throughout the machine, requires only a fraction of the power, and is designed for cooling in a vacuum.

Direct analysis of ultra-trace semiconductor gas by inductively coupled plasma mass spectrometry coupled with gas to particle conversion-gas exchange technique.

PubMed

Ohata, Masaki; Sakurai, Hiromu; Nishiguchi, Kohei; Utani, Keisuke; Günther, Detlef

2015-09-03

An inductively coupled plasma mass spectrometry (ICPMS) coupled with gas to particle conversion-gas exchange technique was applied to the direct analysis of ultra-trace semiconductor gas in ambient air. The ultra-trace semiconductor gases such as arsine (AsH3) and phosphine (PH3) were converted to particles by reaction with ozone (O3) and ammonia (NH3) gases within a gas to particle conversion device (GPD). The converted particles were directly introduced and measured by ICPMS through a gas exchange device (GED), which could penetrate the particles as well as exchange to Ar from either non-reacted gases such as an air or remaining gases of O3 and NH3. The particle size distribution of converted particles was measured by scanning mobility particle sizer (SMPS) and the results supported the elucidation of particle agglomeration between the particle converted from semiconductor gas and the particle of ammonium nitrate (NH4NO3) which was produced as major particle in GPD. Stable time-resolved signals from AsH3 and PH3 in air were obtained by GPD-GED-ICPMS with continuous gas introduction; however, the slightly larger fluctuation, which could be due to the ionization fluctuation of particles in ICP, was observed compared to that of metal carbonyl gas in Ar introduced directly into ICPMS. The linear regression lines were obtained and the limits of detection (LODs) of 1.5 pL L(-1) and 2.4 nL L(-1) for AsH3 and PH3, respectively, were estimated. Since these LODs revealed sufficiently lower values than the measurement concentrations required from semiconductor industry such as 0.5 nL L(-1) and 30 nL L(-1) for AsH3 and PH3, respectively, the GPD-GED-ICPMS could be useful for direct and high sensitive analysis of ultra-trace semiconductor gas in air. Copyright © 2015 Elsevier B.V. All rights reserved.

An optical method for carbon dioxide isotopes and mole fractions in small gas samples: tracing microbial respiration from soil, litter, and lignin.

Treesearch

Steven J. Hall; Wenjuan Huang; Kenneth Hammel

2017-01-01

RATIONALE: Carbon dioxide isotope (Δ13C value) measurements enable quantification of the sources of soil microbial respiration, thus informing ecosystem C dynamics. Tunable diode lasers (TDLs) can precisely measure CO2 isotopes at low cost and high throughput, but are seldom used for small samples (≤5 mL). We developed a...

Technical Report on the Behavior of Trace Elements, Stable Isotopes, and Radiogenic Isotopes During the Processing of Uranium Ore to Uranium Ore Concentrate

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

Marks, N. E.; Borg, L. E.; Eppich, G. R.

2015-07-09

The goals of this SP-1 effort were to understand how isotopic and elemental signatures behave during mining, milling, and concentration and to identify analytes that might preserve geologic signatures of the protolith ores. The impurities that are preserved through the concentration process could provide useful forensic signatures and perhaps prove diagnostic of sample origin.

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.

Laser ablation inductively coupled plasma mass spectrometry for direct isotope ratio measurements on solid samples

NASA Astrophysics Data System (ADS)

Pickhardt, Carola; Dietze, Hans-Joachim; Becker, J. Sabine

2005-04-01

Isotope ratio measurements have been increasingly used in quite different application fields, e.g., for the investigation of isotope variation in nature, in geoscience (geochemistry and geochronology), in cosmochemistry and planetary science, in environmental science, e.g., in environmental monitoring, or by the application of the isotope dilution technique for quantification purposes using stable or radioactive high-enriched isotope tracers. Due to its high sensitivity, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is today a challenging mass spectrometric technique for the direct determination of precise and accurate isotope ratios in solid samples. In comparison to laser ablation quadrupole ICP-MS (LA-ICP-QMS), laser ablation coupled to a double-focusing sector field ICP-MS (LA-ICP-SFMS) with single ion detection offers a significant improvement of sensitivity at low mass resolution, whereby isotope ratios can be measured with a precision to 0.1% relative standard deviation (R.S.D.). In LA-ICP-SFMS, many disturbing isobaric interferences of analyte and molecular ions can be separated at the required mass resolution (e.g., 40Ar16O+ and 56Fe+ for iron isotope ratio measurements). The precision on isotope ratio measurements was improved by one order of magnitude via the simultaneous detection of mass-separated ion currents of isotopes using multiple ion collectors in LA-ICP-MS (LA-MC-ICP-MS). The paper discusses the state of the art, the challenges and limits in isotope ratio measurements by LA-ICP-MS using different instrumentations at the trace and ultratrace level in different fields of application as in environmental and biological research, geochemistry and geochronology with respect to their precision and accuracy.

Arctic Ocean Cyclostratigraphy: An Alternative to Marine Oxygen Isotope curves as measures of Cryospheric and Sea-Level History

NASA Astrophysics Data System (ADS)

Cronin, T. M.; Marzen, R.; O'Regan, M.; Dwyer, G. S.

2016-12-01

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed "vital effects". A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ18O and δ13C in a range of values that are depleted from equilibrium. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO2(aq)-HCO3- inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO3- inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ18O-δ13C correlation. With this model, we are not only able to fit deep sea coral data, but also explain the stable isotope vital effects of other calcifying organisms. This fully kinetic model of stable isotope vital effects and the underlying calcification dynamics may also help us better understand mechanisms of other paleoceanographic tracers in biogenic carbonates, including boron isotopes and trace metal proxies.

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

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

NASA Astrophysics Data System (ADS)

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

2015-08-01

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

Is most of the Tommotian missing in the White-Inyo region eastern California

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

Corsetti, F.A.

Integration of carbon-isotope chemostratigraphic data with trace fossil assemblages suggests that a significant hiatus may be present within the Lower Member of the Deep Spring Formation, potentially impacting the placement of the Neoproterozoic-Cambrian boundary in eastern California and western Nevada. A positive carbon-isotopic excursion of 4% PDB is present in the lowermost Lower Deep Spring, and is associated with Zone 1 trace fossils (latest Vendian) and small shelly fossils of disputed age (latest Proterozoic or Tommotian). A negative isotopic excursion is observed throughout the remaining Deep Spring Formation, and is associated with Zone 3 trace fossils (latest Tommotian-Atdabanian in age).more » The positive excursion in the lowermost Deep Spring is tentatively correlated with the pronounced isotopic maximum in the latest Vendian (possibly Nemakit-Daldyn) of the Siberian Platform (cycle 1 of Kirshvink et al., 1991). The negative excursion is correlated with a similar trend in the latest Tommotian-Atdabanian of the Siberian Platform (cycle 4 of Kirshvink et al., 1991). Thus, a hiatus, potentially encompassing most of the Tommotian, is postulated to be present within the Lower Member of the Deep Spring Formation. Although the fossil and isotopic data are consistent with the presence of a break in the section, sedimentological field evidence for the hiatus is somewhat cryptic. The recognition of this hiatus may impact the global significance of the presumed Tommotian small shelly fossils of the White-Inyo region, as well as the placement of the Neoproterozoic-Cambrian boundary in this sequence.« less

ATTA - A New Method of Ultrasensitive Trace-Isotope Analysis

NASA Astrophysics Data System (ADS)

Lu, Z.-T.; Bailey, K.; Chen, C. Y.; Du, X.; Li, Y. M.; O'Connor, T. P.; Young, L.; Winkler, G.

2000-10-01

We have developed a new method of ultrasensitive trace-isotope analysis based upon the technique of laser manipulation of neutral atoms [1]. This new method allows us to count individual 85Kr and 81Kr atoms present in a natural krypton sample with isotopic abundances in the range of 10-11 and 10-13, respectively. Isotope analysis of 81Kr can be used to date polar ice, and 85Kr is a tracer used in monitoring nuclear wastes. In this experiment metastable Kr atoms were produced in a discharge, decelerated via the Zeeman slowing technique, and captured by a Magneto-Optical Trap where the atoms were counted by measuring their fluorescence. At present our system is capable of counting, in average, one 81Kr atom for about 12 minutes with a total efficiency of 2x10-7. We are currently working to improve our system efficiency by applying cryogenic cooling to the Kr atoms in the discharge region and by recirculating the gas in the vacuum system. This method can be used to analyze many other isotope tracers for a wide range of applications including measuring solar neutrino flux, searching for exotic particles, tracing atmospheric and oceanic currents, archeological and geological dating, medical diagnostics, monitoring fission products in the environment for nuclear waste management, etc. This work is supported by the U.S. Department of Energy, Nuclear Physics Division; L.Young is supported by the Office of Basic Energy Sciences, Division of Chemical Sciences (Contract W-31-109-ENG-38). [1] C.Y. Chen et. al., Science 286, 1139 (1999).

Using Nd and Sr isotopes to trace dust and volcanic inputs to soils on French Guadeloupe Island

NASA Astrophysics Data System (ADS)

Guo, J.; Pereyra, Y.; Ma, L.; Gaillardet, J.; Sak, P. B.; Bouchez, J.

2017-12-01

Soil is at the central part of the Critical Zone for its important roles in sustaining ecosystems and agriculture. At French Guadeloupe, a tropical humid volcanic island, previous studies have shown that the mineral nutrient elements such as K, Na, Ca, and Mg are highly depleted in the surface soil. And mineral nutrients introduced by dusts are an important mineral nutrient source for vegetation growth in this area. It is important to understand and quantify the sources of the mineral dust added to surface soils. Nd isotope ratios, due to their distinct signatures between two unique end-members in soils for this area: the young volcanic areas like Guadeloupe and the dust source region from the old continental shields like Sahara Desert, can be a robust tracer to understand this critical process. Nevertheless, Sr isotope ratios can trace the inputs of marine aerosols. Here we present a new Nd isotope study on Guadeloupe soil depth profiles, combined with previous Sr isotope data, to fingerprint the sources of dust and volcanic inputs into soils. Soil samples from three surface profiles (0 - 1000cm deep) at different locations of the Guadeloupe Island were systematically analyzed. The results show distinct depth variations for Nd isotope signature along profiles. For all profiles, deep soils are relatively consisted with bedrock value (ɛNd: 5.05). But in surface soils (0-600cm), unlike Sr isotope ratios that are significantly modified by marine aerosol input, Nd isotope ratios show similar decrease (to ɛNd:-10) and frequent fluctuations toward the surface, suggesting dust is the dominant source of Nd in these soils. This conclusion is further supported by REE and other trace element data. Thus, with a simplified two end-member model, Sahara dust contributes the Nd percentages in soils varying from 10.7% at the deepest profiles to 69.5% on surface, showing a significant amount of Nd on the surface soil came from dust source. The deep soil profiles are also characterized by the presence of Nd isotope spikes with negative values, suggesting dust signatures at depth. Such a feature could be related to the presence of a paleo-soil surface at the spike depth that was buried by later volcanic eruption. Both Nd and Sr isotopes hence show dust and volcanic inputs are important factors for soil developments on French Guadeloupe Island.

An innovative application of stable isotopes (δ2H and δ18O) for tracing pollutant plumes in groundwater.

PubMed

Negrel, Philippe; Ollivier, Patrick; Flehoc, Christine; Hube, Daniel

2017-02-01

The identification of the sources of contaminants present in groundwater at industrial sites is primordial to address environmental and industrial issues. However, available tools are often inadequate or expensive. Here, we present the data of stable isotopes (δ 18 O and δ 2 H) of the water molecule at an industrial site where electrochemistry plant occurs impacting the groundwater quality. High ClO 3 and ClO 4 contents and 2 H enrichment have been measured in groundwater. Recharge of aquifer relates to infiltration of rainwater and by subsurface inflow. On-site, industrial products are generated by electrolysis. We show that the electrolysis process leads to a large 2 H enrichment (+425‰) in solutions. In the absence of hydrothermal water input containing H 2 S, we demonstrate that the relationship between δ 18 O and δ 2 H can be easily used in a way to trace the origin of the ClO 3 and ClO 4 in groundwater. Isotopes evidenced first a leakage from end-product storage tanks or during the production process itself. Then, an accumulation and release of ClO 3 and ClO 4 from soil is demonstrated. Our study successfully shows that stable isotopes are a powerful and low cost tool for tracing pollutant plumes in an industrial context using electrolysis process. Copyright © 2016 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.

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.

Foreword [Special Issue on Superheavy Elements

DOE PAGES

Düllmann, Christoph E.; Herzberg, Rolf -Dietmar; Nazarewicz, Witold; ...

2015-12-07

Reflecting the breadth of research opportunities in the field of superheavy element research, this special issue covers the range of topics in a comprehensive way, including synthesis of superheavy isotopes, nuclear structure, atomic shell structure, and chemical properties. The contributions detail the status of the field and lay out perspectives for the future. The prospects are bright: new isotopes are awaiting discovery, completing the landscape of superheavy nuclei and bridging the currently existing gap between nuclei synthesized in cold fusion reactions and those from 48Ca induced fusion reactions. The possibility that the limits of nuclear structure studies can be pushedmore » even further in mass and charge has greatly motivated a number of new facilities. Advances in experimental techniques will allow studies on isotopes produced significantly below the 1 pb level. Chemical studies progressing to elements never studied to date are already being prepared. Ultra-fast chemistry setups are under development and it will be fascinating to see them at work, elucidating the influence of relativistic effects on superheavy elements. The richness of chemical systems available for transactinides will expand further, giving access to new chemical systems, giving more information on the architecture of the periodic table.« less

Rubidium-traced white-light etalon calibrator for radial velocity measurements at the cm s-1 level

NASA Astrophysics Data System (ADS)

Stürmer, Julian; Seifahrt, Andreas; Schwab, Christian; Bean, Jacob L.

2017-04-01

We report on the construction and testing of a vacuum-gap Fabry-Pérot etalon calibrator for high precision radial velocity spectrographs. Our etalon is traced against a rubidium frequency standard to provide a cost effective, yet ultra precise wavelength reference. We describe here a turn-key system working at 500 to 900 nm, ready to be installed at any current and next-generation radial velocity spectrograph that requires calibration over a wide spectral bandpass. Where appropriate, we have used off-the-shelf, commercial components with demonstrated long-term performance to accelerate the development timescale of this instrument. Our system combines for the first time the advantages of passively stabilized etalons for optical and near-infrared wavelengths with the laser-locking technique demonstrated for single-mode fiber etalons. We realize uncertainties in the position of one etalon line at the 10 cm s-1 level in individual measurements taken at 4 Hz. When binning the data over 10 s, we are able to trace the etalon line with a precision of better than 3 cm s-1. We present data obtained during a week of continuous operation where we detect (and correct for) the predicted, but previously unobserved shrinking of the etalon Zerodur spacer corresponding to a shift of 13 cm s-1 per day.

The measurement of trace elements in interplanetary dust and cometary particles by ultra-high sensitivity INAA

NASA Technical Reports Server (NTRS)

Zolensky, M. E.; Lindstrom, David J.; Lindstrom, Richard M.; Lindstrom, M. M.

1989-01-01

Today the major elemental composition of interplanetary dust particles (IDPs) is routinely determined in many laboratories. These and mineralogical studies have revealed the presence of at least two major types of IDPs, chondritic and refractory. Preliminary results of a successful attempt to determine abundances of a large suite of trace elements from both chondritic and refractory IDPs are reported. The analytical procedure can be used in the grain-by-grain analysis of returned cometary samples. Chondritic and refractory IDPs are characterized by standard scanning electron microscopy and energy dispersive x ray spectroscopy (SEM-EDX) techniques. With this system, detection limits for many elements are well below picogram levels, and some approach femtogram levels. This technique is non-destructive, although some sample handling is required, so particles can be analyzed by other techniques after instrument neutron activation analysis (INAA) is completed. Data is presently being reduced from the analyses of 7 IDPs. These are U2015E10, U2015F1, W7029-A2, W7029-A3, W7013A8, LACl (all chondritic) and 705 (refractory). So far, 17 different major and trace elements were detected and measured in these particles, including rare earths and some very volatile elements (Br and Zn).

Habitat Use and Trophic Structure in a Highly Migratory Predatory Fish Identified with Geochemical Proxies in Scales

NASA Astrophysics Data System (ADS)

Seeley, M.; Walther, B. D.

2016-02-01

Atlantic tarpon, Megalops atlanticus, are highly migratory euryhaline predators that occupy different habitats throughout ontogeny. Specifically, Atlantic tarpon are known to inhabit oligohaline waters, although the frequency and duration of movements across estuarine gradients into these waters are relatively unknown. This species supports over a two billion dollar industry within the Gulf of Mexico and is currently listed as vulnerable under the International Union for the Conservation of Nature (IUCN). A new non-lethal method for reconstructing migrations across estuaries relies on trace element and stable isotope compositions of growth increments in scales. We analyzed Atlantic tarpon scales from the Texas coast to validate this method using inductively coupled plasma mass spectrometry (ICP-MS) for trace elements and isotope ratio mass spectrometry (IR-MS) for stable isotope ratios. Multiple scales were also taken from the same individual to confirm the consistency of elemental uptake within the same individual. Results show that scale Ba:Ca, Sr:Ca and δ13C are effective proxies for salinity, while enrichments in δ15N are consistent with known ontogenetic trophic shifts. In addition, chemical transects across multiple scales from the same individual were highly consistent, suggesting that any non-regenerated scale removed from a fish can provide equivalent time series. Continuous life history profiles of scales were obtained via laser ablation transects of scale cross-sections to quantify trace element concentrations from the core (youngest increments) to the edge (oldest increments). Stable isotope and trace element results together indicate that behavior is highly variable between individuals, with some but not all fish transiting estuarine gradients into oligohaline waters. Our findings will provide novel opportunities to investigate alternative non-lethal methods to monitor fish migrations across chemical gradients.

Isotopic and trace element geochemistry of the Seligdar magnesiocarbonatites (South Yakutia, Russia): Insights regarding the mantle evolution beneath the Aldan-Stanovoy shield

NASA Astrophysics Data System (ADS)

Doroshkevich, Anna G.; Prokopyev, Ilya R.; Izokh, Andrey E.; Klemd, Reiner; Ponomarchuk, Anton V.; Nikolaeva, Irina V.; Vladykin, Nikolay V.

2018-04-01

The Paleoproterozoic Seligdar magnesiocarbonatite intrusion of the Aldan-Stanovoy shield in Russia underwent extensive postmagmatic hydrothermal alteration and metamorphic events. This study comprises new isotopic (Sr, Nd, C and O) data, whole-rock major and trace element compositions and trace element characteristics of the major minerals to gain a better understanding of the source and the formation process of the carbonatites. The Seligdar carbonatites have high concentrations of P2O5 (up to 18 wt%) and low concentrations of Na, K, Sr and Ba. The chondrite-normalized REE patterns of these carbonatites display significant enrichments of LREE relative to HREE with an average La/Ybcn ratio of 95. Hydrothermal and metamorphic overprints changed the trace element characteristics of the carbonatites and their minerals. These alteration processes were responsible for Sr loss and the shifting of the Sr isotopic compositions towards more radiogenic values. The altered carbonatites are further characterized by distinct 18O- and 13C-enrichments compared to the primary igneous carbonatites. The alteration most likely resulted from both the percolation of crustal-derived hydrothermal fluids and subsequent metamorphic processes accompanied by interaction with limestone-derived CO2. The narrow range of negative εNd(T) values indicates that the Seligdar carbonatites are dominated by a homogenous enriched mantle source component that was separated from the depleted mantle during the Archean.

Stable isotopes to trace food web stressors: Is space the final frontier?

EPA Science Inventory

To support community decision-making, we need to evaluate sources of stress and impact at a variety of spatial scales, whether local or watershed-based. Increasingly, we are using stable isotope-based approaches to determine those scales of impact, and using these approaches in v...

A quantitative evaluation of spurious results in the infrared spectroscopic measurement of CO2 isotope ratios

NASA Astrophysics Data System (ADS)

Mansfield, C. D.; Rutt, H. N.

2002-02-01

The possible generation of spurious results, arising from the application of infrared spectroscopic techniques to the measurement of carbon isotope ratios in breath, due to coincident absorption bands has been re-examined. An earlier investigation, which approached the problem qualitatively, fulfilled its aspirations in providing an unambiguous assurance that 13C16O2/12C16O2 ratios can be confidently measured for isotopic breath tests using instruments based on infrared absorption. Although this conclusion still stands, subsequent quantitative investigation has revealed an important exception that necessitates a strict adherence to sample collection protocol. The results show that concentrations and decay rates of the coincident breath trace compounds acetonitrile and carbon monoxide, found in the breath sample of a heavy smoker, can produce spurious results. Hence, findings from this investigation justify the concern that breath trace compounds present a risk to the accurate measurement of carbon isotope ratios in breath when using broadband, non-dispersive, ground state absorption infrared spectroscopy. It provides recommendations on the length of smoking abstention required to avoid generation of spurious results and also reaffirms, through quantitative argument, the validity of using infrared absorption spectroscopy to measure CO2 isotope ratios in breath.

Trace metal pollution and carbon and nitrogen isotope tracing through the Yongdingxin River estuary in Bohai Bay, Northern China.

PubMed

Sun, Conghui; Wei, Qi; Ma, Lixia; Li, Li; Wu, Guanghong; Pan, Ling

2017-02-15

A tide gate was built in 2010 to prevent seawater from moving upstream into the Yongdingxin River estuary in Bohai Bay, Northern China. We analysed the concentrations of Hg, Cd, Pb, TOC, TN, δ 13 C and δ 15 N and studied their variations in the surface layer and vertical profiles of sediment cores collected from the Yongdingxin River estuary. Contamination factors and geo-accumulation indices were calculated for each metal, which revealed high levels of contamination for Hg and Cd in the sediments, likely from anthropogenic sources. δ 13 C and δ 15 N were used as natural tracers to determine the sources of TOC and TN. The results revealed that sewage was the main source of TOC, while TN may have more than one source in the Yongdingxin River estuary. Sewage dominated trace metal pollution in the Yongdingxin River estuary. Our results provide a baseline for trace metal contamination in an estuary facing a large water project. Copyright © 2016 Elsevier Ltd. All rights reserved.

Trace matrix solid phase dispersion using a molecular sieve as the sorbent for the determination of flavonoids in fruit peels by ultra-performance liquid chromatography.

PubMed

Cao, Wan; Hu, Shuai-Shuai; Ye, Li-Hong; Cao, Jun; Pang, Xiao-Qing; Xu, Jing-Jing

2016-01-01

A simple, rapid, and highly selective trace matrix solid phase dispersion (MSPD) technique, coupled with ultra-performance liquid chromatography-ultraviolet detection, was proposed for extracting flavonoids from orange fruit peel matrices. Molecular sieve SBA-15 was applied for the first time as a solid support in trace MSPD. Parameters, such as the type of dispersant, mass ratio of the sample to the dispersant, grinding time, and elution pH, were optimized in detail. The optimal extraction conditions involved dispersing a powdered fruit peel sample (25 mg) into 25mg of SBA-15 and then eluting the target analytes with 500 μL of methanol. A satisfactory linearity (r(2) > 0.9990) was obtained, and the calculated limits of detection reached 0.02-0.03 μg/mL for the compounds. The results showed that the method developed was successfully applied to determine the content of flavonoids in complex fruit peel matrices. Copyright © 2015 Elsevier Ltd. All rights reserved.

Stable carbon and nitrogen isotope composition of aquatic and terrestrial plants of the San Francisco Bay estuarine system

USGS Publications Warehouse

Cloern, J.E.; Canuel, E.A.; Harris, D.

2002-01-01

We report measurements of seasonal variability in the C-N stable isotope ratios of plants collected across the habitat mosaic of San Francisco Bay, its marshes, and its tributary river system. Analyses of 868 plant samples were binned into 10 groups (e.g., terrestrial riparian, freshwater phytoplankton, salt marsh) to determine whether C-N isotopes can be used as biomarkers for tracing the origins of organic matter in this river-marsh-estuary complex. Variability of ??13C and ??15N was high (???5-10???) within each plant group, and we identified three modes of variability: (1) between species and their microhabitats, (2) over annual cycles of plant growth and senescence, and (3) between living and decomposing biomass. These modes of within-group variability obscure any source-specific isotopic signatures, confounding the application of C-N isotopes for identifying the origins of organic matter. A second confounding factor was large dissimilarity between the ??13C-??15N of primary producers and the organic-matter pools in the seston and sediments. Both confounding factors impede the application of C-N isotopes to reveal the food supply to primary consumers in ecosystems supporting diverse autotrophs and where the isotopic composition of organic matter has been transformed and become distinct from that of its parent plant sources. Our results support the advice of others: variability of C-N stable isotopes within all organic-matter pools is high and must be considered in applications of these isotopes to trace trophic linkages from primary producers to primary consumers. Isotope-based approaches are perhaps most powerful when used to complement other tools, such as molecular biomarkers, bioassays, direct measures of production, and compilations of organic-matter budgets.

Geochemical and isotopic (Nd-Pb-Sr-O) variations bearing on the genesis of volcanic rocks from Vesuvius, Italy

USGS Publications Warehouse

Ayuso, R.A.; de Vivo, B.; Rolandi, G.; Seal, R.R.; Paone, A.

1998-01-01

Alkaline volcanism produced by Monte Somma-Vesuvius volcano includes explosive plinian and subplinian activity in addition to effusive lava flows. Pumice, scoria, and lava (150 samples) exhibit major- and trace-element gradients as a function of SiO2 (58.9-47.2 wt%) and MgO (0-7.8 wt%); Mg value are ???50. Internally gradational chemical groups or cycles are distinguished by age: (1) 25 000 to 14 000 yr B.P.; (2) 8000 yr B.P. to A.D. 79; and (3) A.D. 79 to 1944. A small number of lavas, dikes and scora were also analysed from the Somma formation (~ 35 000 to 25 000 yr B.P.). Within each group, contents of Na2O + K2O increas with decreasing MgO along distinct rocks. Nb/Y values are variable from 0.66 to 3.14 (at SiO2 ??? 50 wt%) generally in the range of alkaline and ultra-alkaline rocks. Variations in contents of some majro elements (e.g., P and Ti), and trace elements (e.g., Th, Nb, Ta, Zr, Hf, Pb, La, and Sc), as well as contrasting trends in ratios of various elements (e.g., Ta/Yb, Hf/U, Th/Ta, Th/Hf, Th/Yb, etc.) are also generally consistent with the group subdivisions. For example, Th/Hf increases from ??? 5 to ??? 10 with decreasing age for the Vesuvius system as a whole, yielding similar compositions in the least evolved rocks (low-silica, high-MgO, imcompatible element-poor) erupted at the end of each cycle. Internal variations within individual eruptions also systematically changed generally towards a common mafic composition at the end of each cycle, thus reflecting the dominanit volume in the magma chamber. At the start of a new eruptive cycle, the rocks are relatively enriched in incompatible elements; younger groups also contain higher abundances than other groups. N-MORB-normalized multielement diagrams exhibit selective enrichments of Sr, K, Rb, Th, and the light rare-earth elements; deep Nb and Ta negative anomalies commonly seen in rocks generated at orogenic margins are absent in the light rare-earth elements; deep Nb and Ta netgative anomalies commonly seen in rocks generated at orogenic margins are absent in our samples. Sr isotopic compositions are known to be variable within some of the units, in agreement with our data (87Sr/86Sr ~ 0.70699 to 0.70803) and with contributions from several isotopic components. Isotopic compositions for ??18O (7.3 to 10.2%), Pb for mineral separates and whole rocks (206Pb/204Pb ~ 18.947 to 19.178, 207Pb/204/Pb ~ 15.617 to 15.769, 208Pb/204Pb ~38.915 to 39.345), and Nd (143Nd ~ 0.51228 to 0.51251) also show variability. Oxygen isotope data show that pumices have higher ??18O values than cogenetic lavas, and that ??18O values and SiO2 are correlated. Radiogenic and stable isotope data plot within range of isotopic compositions for the Roman comagmatic province. Fractional crystallization cannot account for the radiogenic isotopic compositions of the Vesuvius magmas. We favor instead the combined effects of heterogeneous magma sources, together with isotopic exchange near the roof of the magma chamber. We suggest that metasomatized continental mantle lithosphere is the principal source of the magmas. This kind of enriched mantle was melted and reactivated in an area of continental extension (incipient rift setting) without direct reliance on contemporaneous subduction processes but possibly with input from mantle sources that resemble those that produce ocean island basalts.

Environmental and biomedical applications of natural metal stable isotope variations

USGS Publications Warehouse

Bullen, T.D.; Walczyk, T.

2009-01-01

etal stable isotopes are now being used to trace metal contaminants in the environment and as indicators of human systemic function where metals play a role. Stable isotope abundance variations provide information about metal sources and the processes affecting metals in complex natural systems, complementing information gained from surrogate tracers, such as metal abundance ratios or biochemical markers of metal metabolism. The science is still in its infancy, but the results of initial studies confirm that metal stable isotopes can provide a powerful tool for forensic and biomedical investigations.

Cometary and interstellar dust grains - Analysis by ion microprobe mass spectrometry and other techniques

NASA Technical Reports Server (NTRS)

Zinner, Ernst

1991-01-01

A survey of microanalytical measurements on interplanetary dust particles (IDPs) and interstellar dust grains from primitive meteorites is presented. Ion-microprobe mass spectrometry with its capability to determine isotopic compositions of many elements on a micron spatial scale has played a special role. Examples are measurements of H, N, and O isotopes and refractory trace elements in IDPs; C, N, Mg, and Si isotopes in interstellar SiC grains; and C and N isotopes and H, N, Al, and Si concentrations in interstellar graphite grains.

Mass Spectral Investigations on Toxins. 2. Simultaneous Detection and Quantification of Ultra-Trace Levels of Simple Trichothecenes in Environmental and Fermentation Samples by Gas Chromatographic/Negative Ion Chemical Ionization-Mass Spectrometric Techniques

DTIC Science & Technology

1987-01-01

due to interferences in the pollen. However, the identity of the interferents is presently unknown. A dried papaya leaf was treated with 10 ml of warm...Known amounts of DON, DAS, and T-2 were spiked on a blank (trichothecene-free) papaya leaf and left exposed in a bottle for 1 year. At the end of the year...Simple Trichothecenes from Leaf Sample after Prolonged Exposure ............... 35 12 Sample Analysis .............................. .... 37 6 MASS

Compound-Specific Isotope Analysis of Diesel Fuels in a Forensic Investigation

NASA Astrophysics Data System (ADS)

Muhammad, Syahidah; Frew, Russell; Hayman, Alan

2015-02-01

Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin i.e. the very subtle differences in isotopic values between the samples.

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.

Compound-specific isotope analysis of diesel fuels in a forensic investigation

PubMed Central

Muhammad, Syahidah A.; Frew, Russell D.; Hayman, Alan R.

2015-01-01

Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin, i.e., the very subtle differences in isotopic values between the samples. PMID:25774366

Magma evolution as seen through zircon geochemistry: an example from the Southern Adamello Batholith, N. Italy

NASA Astrophysics Data System (ADS)

Broderick, C.; Schaltegger, U.; Gerdes, A.; Frick, D.; Guenther, D.; Brack, P.

2012-04-01

Zircon is an ubiquitous accessory mineral often used for U-Pb geochronology but is also an important recorder of geochemical information. The trace element and isotopic characteristics of zircon yield potential for tracking changes in an evolving magma through time. With recent advances in U-Pb zircon geochronology, 10-100 ka to Ma timescales are observed for incremental pluton construction (Michel et al., 2008, Schaltegger et al., 2009). In observed 100 ka timescales of zircon crystallization, can zircon record the processes that produce trace element variations in a magma? This study focuses on the Val Fredda Complex (VFC) in the southern tip of the 43 to 33 Ma Adamello batholith, N. Italy. The VFC displays complex relationships among mafic melts that were injected into solidifying felsic magmas. Single zircon crystals were dated using CA-ID-TIMS. With permil uncertainties on 206Pb/238U zircon dates, zircons reveal complexities within single populations. The mafic units crystallized potential autocrystic zircons over a duration of 100 - 150ka, whereas the felsic units record up to 200ka of zircon crystallization. In order to understand these complex zircon populations, we analyzed Hf isotopes and trace elements, on the same volume of zircon used for U-Pb dating, following the TIMS-TEA method (Schoene et al., 2010). This detailed zircon study will allow us to look at how magmas are evolving with time. Hf isotopes of VFC mafic zircons reveal distinct ɛHf values between the three mafic units and their ɛHf values remain consistent through time, whereas the VFC felsic units record more complexity in their ɛHf values. We observe changes such as increasing and slight decreases in ɛHf with time which suggest different processes are occurring to produce the different felsic units. Trace element ratios in zircon reveal differences which allow us to make distinctions between felsic and mafic units (e.g. Th/U, (Lu/Gd)N, REEs). The VFC records 200 ka of zircon crystallization and our data suggests that zircons do in fact reflect changes in isotopic and in trace element signatures on 100 ka timescales. Although we observe changes in our trace elements, the TIMS-TEA method provides an average of trace element concentrations from a zircon volume, dominated by more marginal growth zones. Therefore we will compare our data with in situ methods to determine how our trace element data compares with trace elements across zircon profiles. We acknowledge funding of FNS in the frame of ProDoc Adamello 4-D. Michel et al., 2008, Geol. 36 : 459-462 ; Schaltegger et al., 2009, Earth Planet. Sci.Lett. 286: 208-218; Schoene et al., 2010, Geochim. Cosmochim. Acta 74, 7144-7159.

Ion microscopy with resonant ionization mass spectrometry : time-of-flight depth profiling with improved isotopic precision.

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

Pellin, M. J.; Veryovkin, I. V.; Levine, J.

2010-01-01

There are four generally mutually exclusive requirements that plague many mass spectrometric measurements of trace constituents: (1) the small size (limited by the depth probed) of many interesting materials requires high useful yields to simply detect some trace elements, (2) the low concentrations of interesting elements require efficient discrimination from isobaric interferences, (3) it is often necessary to measure the depth distribution of elements with high surface and low bulk contributions, and (4) many applications require precise isotopic analysis. Resonant ionization mass spectrometry has made dramatic progress in addressing these difficulties over the past five years.

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.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Utility of γH2AX as a molecular marker of DNA double-strand breaks in nuclear medicine: applications to radionuclide therapy employing auger electron-emitting isotopes.

PubMed

Mah, Li-Jeen; Orlowski, Christian; Ververis, Katherine; El-Osta, Assam; Karagiannis, Tom C

2011-01-01

There is an intense interest in the development of radiopharmaceuticals for cancer therapy. In particular, radiopharmaceuticals which involve targeting radionuclides specifically to cancer cells with the use of monoclonal antibodies (radioimmunotherapy) or peptides (targeted radiotherapy) are being widely investigated. For example, the ultra-short range Auger electron-emitting isotopes, which are discussed in this review, are being considered in the context of DNAtargeted radiotherapy. The efficient quantitative evaluation of the levels of damage caused by such potential radiopharmaceuticals is required for assessment of therapeutic efficacy and determination of relevant doses for successful treatment. The DNA double-strand break surrogate marker, γH2AX, has emerged as a useful biomonitor of damage and thus effectiveness of treatment, offering a highly specific and sensitive means of assessment. This review will cover the potential applications of γH2AX in nuclear medicine, in particular radionuclide therapy.

Application of isotope dilution inductively coupled plasma mass spectrometry to the analysis of marine sediments

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

McLaren, J.W.; Beauchemin, D.; Berman, S.S.

1987-02-15

Isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the determination of 11 trace elements (Cr, Ni, Zn, Sr, Mo, Cd, Sn, Sb, Tl, Pb, and U) in the marine sediment reference materials MESS-1 and BCSS-1. Accuracy and, especially, precision are better than those that can be easily achieved by other ICP-MS calibration strategies, as long as isotopic equilibration is achieved and the isotopes used for the ratio measurement are free of isobaric interferences by molecular species. The measurement of the isotope ratios on unspiked samples provides a sensitive diagnostic of such interferences.

Rapid processing of 85Kr/Kr ratios using Atom Trap Trace Analysis

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

Zappala, J. C.; Bailey, K.; Mueller, P.

In this paper, we report a methodology for measuring 85Kr/Kr isotopic abundances using Atom Trap Trace Analysis (ATTA) that increases sample measurement throughput by over an order of magnitude to six samples per 24 h. The noble gas isotope 85Kr (half-life = 10.7 years) is a useful tracer for young groundwater in the age range of 5–50 years. ATTA, an efficient and selective laser-based atom counting method, has recently been applied to 85Kr/Kr isotopic abundance measurements, requiring 5–10 μL of krypton gas at STP extracted from 50 to 100 L of water. Previously, a single such measurement required 48 h.more » In conclusion, our new method demonstrates that we can measure 85Kr/Kr ratios with 3–5% relative uncertainty every 4 h, on average, with the same sample requirements.« less

Rapid processing of 85Kr/Kr ratios using Atom Trap Trace Analysis

DOE PAGES

Zappala, J. C.; Bailey, K.; Mueller, P.; ...

2017-03-11

In this paper, we report a methodology for measuring 85Kr/Kr isotopic abundances using Atom Trap Trace Analysis (ATTA) that increases sample measurement throughput by over an order of magnitude to six samples per 24 h. The noble gas isotope 85Kr (half-life = 10.7 years) is a useful tracer for young groundwater in the age range of 5–50 years. ATTA, an efficient and selective laser-based atom counting method, has recently been applied to 85Kr/Kr isotopic abundance measurements, requiring 5–10 μL of krypton gas at STP extracted from 50 to 100 L of water. Previously, a single such measurement required 48 h.more » In conclusion, our new method demonstrates that we can measure 85Kr/Kr ratios with 3–5% relative uncertainty every 4 h, on average, with the same sample requirements.« less

Rn-222 tracing and stable isotope measurements of biogenic gas fluxes from methane saturated sediments

NASA Technical Reports Server (NTRS)

Martens, Christopher S.; Green, C. D.; Blair, Neal; Chanton, J. P.

1985-01-01

Transport of reduced biogenic gases from anoxic sediments and soils to the atmosphere can be quantitatively studied through measurement of radon-222/radium-226 disequilibrium. In previous work, seasonal variations in biogenic gas transport mechanisms, net fluxes and overall composition were documented. Now presented are direct field measurements of radon-222 activity in gases exiting organic rich sediments which show their usefulness for tracing of the stripping of dissolved biogenic gases from within the sediment column and transport via bubble ebullition. Methane is depleted in deuterium during the summer as compared with winter months and is in general lighter than in most marine sediments signaling the probable importance of acetate as an important precursor molecule. The significant seasonal isotopic variations observed illustrate the importance of understanding mechanisms and rates of biogenic gas production in order to interpret observed tropospheric isotopic data.

Remembering Fukushima: PNNL Monitors Radiation from Nuclear Disaster

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

Miley, Harry

Senior Scientist Harry Miley describes how his work in ultra-trace, nuclear detection technology picked up the first reading of radiological materials over the U.S. following the nuclear power plant explosion in Japan.

Remembering Fukushima: PNNL Monitors Radiation from Nuclear Disaster

ScienceCinema

Miley, Harry

2018-02-07

Senior Scientist Harry Miley describes how his work in ultra-trace, nuclear detection technology picked up the first reading of radiological materials over the U.S. following the nuclear power plant explosion in Japan.

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

Compositional variations at ultra-structure length scales in coral skeleton

NASA Astrophysics Data System (ADS)

Meibom, Anders; Cuif, Jean-Pierre; Houlbreque, Fanny; Mostefaoui, Smail; Dauphin, Yannicke; Meibom, Karin L.; Dunbar, Robert

2008-03-01

Distributions of Mg and Sr in the skeletons of a deep-sea coral ( Caryophyllia ambrosia) and a shallow-water, reef-building coral ( Pavona clavus) have been obtained with a spatial resolution of 150 nm, using the NanoSIMS ion microprobe at the Muséum National d'Histoire Naturelle in Paris. These trace element analyses focus on the two primary ultra-structural components in the skeleton: centers of calcification (COC) and fibrous aragonite. In fibrous aragonite, the trace element variations are typically on the order of 10% or more, on length scales on the order of 1-10 μm. Sr/Ca and Mg/Ca variations are not correlated. However, Mg/Ca variations in Pavona are strongly correlated with the layered organization of the skeleton. These data allow for a direct comparison of trace element variations in zooxanthellate and non-zooxanthellate corals. In both corals, all trace elements show variations far beyond what can be attributed to variations in the marine environment. Furthermore, the observed trace element variations in the fibrous (bulk) part of the skeletons are not related to the activity of zooxanthellae, but result from other biological activity in the coral organism. To a large degree, this biological forcing is independent of the ambient marine environment, which is essentially constant on the growth timescales considered here. Finally, we discuss the possible detection of a new high-Mg calcium carbonate phase, which appears to be present in both deep-sea and reef-building corals and is neither aragonite nor calcite.

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.

Stable Isotope Mixing Models as a Tool for Tracking Sources of Water and Water Pollutants

EPA Science Inventory

One goal of monitoring pollutants is to be able to trace the pollutant to its source. Here we review how mixing models using stable isotope information on water and water pollutants can help accomplish this goal. A number of elements exist in multiple stable (non-radioactive) i...

Analyzing the movement of an invasive weevil (Polydrusus sericeus) using stable Isotopes

Treesearch

Joanne Lund; Paula Marquardt; William Jr. Mattson

2010-01-01

To better understand the response of insect populations to increasing CO2 and O3, we used ratios of stable carbon isotopes (d 13C) to trace the movement of an invasive insect in mixed tree communities grown under different air quality conditions. Polydrusus sericeus is a non-native...

Advances in the application of amino acid nitrogen isotopic analysis in ecological and biogeochemical studies

USDA-ARS?s Scientific Manuscript database

Compound-specific isotopic analysis of amino acids (CSIA-AA) has emerged in the last decade as a powerful approach for tracing the origins and fate of nitrogen in ecological and biogeochemical studies. This approach is based on the empirical knowledge that source AAs (i.e., phenylalanine), fractiona...

Trace elements biomonitoring in a historical mining district (les Malines, France).

PubMed

Saunier, Jean-Baptiste; Losfeld, Guillaume; Freydier, Rémi; Grison, Claude

2013-11-01

The aim of this study is to investigate the trace elements (TE) contents of potential biomonitors in a historical Zn-Pb mining district: apiary products (honey, royal-jelly and beeswax) lichen and moss were sampled and analysed. In spite of high TE concentrations in mining waste and soil, apiary products are free of TE contamination originating from historical mining. Lichen/moss show high TE levels, which suggest atmospheric input of local dust. Pb isotopes analysis proved the origin of TE found in lichen/moss to be mainly mining waste. These results help discuss the choice of relevant organisms for monitoring TE in the environment and bring additional data on the potential impacts of brownfields left after mining, especially on food products from apiaries. Copyright © 2013 Elsevier Ltd. All rights reserved.

Advanced Nanoporous Materials for Micro-Gravimetric Sensing to Trace-Level Bio/Chemical Molecules

PubMed Central

Xu, Pengcheng; Li, Xinxin; Yu, Haitao; Xu, Tiegang

2014-01-01

Functionalized nanoporous materials have been developed recently as bio/chemical sensing materials. Due to the huge specific surface of the nano-materials for molecular adsorption, high hopes have been placed on gravimetric detection with micro/nano resonant cantilevers for ultra-sensitive sensing of low-concentration bio/chemical substances. In order to enhance selectivity of the gravimetric resonant sensors to the target molecules, it is crucial to modify specific groups onto the pore-surface of the nano-materials. By loading the nanoporous sensing material onto the desired region of the mass-type transducers like resonant cantilevers, the micro-gravimetric bio/chemical sensors can be formed. Recently, such micro-gravimetric bio/chemical sensors have been successfully applied for rapid or on-the-spot detection of various bio/chemical molecules at the trace-concentration level. The applicable nanoporous sensing materials include mesoporous silica, zeolite, nanoporous graphene oxide (GO) and so on. This review article focuses on the recent achievements in design, preparation, functionalization and characterization of advanced nanoporous sensing materials for micro-gravimetric bio/chemical sensing. PMID:25313499

Collaborative Study for Analysis of High Resolution Infrared Atmospheric Spectra Between NASA Langley Research Center and the University of Denver

NASA Technical Reports Server (NTRS)

Goldman, A.

2002-01-01

The Langley-D.U. collaboration on the analysis of high resolultion infrared atmospheric spectra covered a number of important studies of trace gases identification and quantification from field spectra, and spectral line parameters analysis. The collaborative work included: 1) Quantification and monitoring of trace gases from ground-based spectra available from various locations and seasons and from balloon flights; 2) Identification and preliminary quantification of several isotopic species, including oxygen and Sulfur isotopes; 3) Search for new species on the available spectra, including the use of selective coadding of ground-based spectra for high signal to noise; 4) Update of spectroscopic line parameters, by combining laboratory and atmospheric spectra with theoretical spectroscopy methods; 5) Study of trends and correlations of atmosphere trace constituents; and 6) Algorithms developments, retrievals intercomparisons and automatization of the analysis of NDSC spectra, for both column amounts and vertical profiles.

Chemically individual armoured bioreporter bacteria used for the in vivo sensing of ultra-trace toxic metal ions.

PubMed

Zhang, Zhijun; Ju, Enguo; Bing, Wei; Wang, Zhenzhen; Ren, Jinsong; Qu, Xiaogang

2017-07-25

A chemically engineered armour is developed for simultaneously improving bioreporter bacterial vitality and shielding infectivity. The armour can help bacteria to resist various insults and even immune phagocytosis. Meanwhile, the bacterial infectivity has proven to be greatly shielded as well. Most importantly, the original bacterial biosensing activity is well preserved, which is competent for sensing trace arsenic in water, serum, and even in vivo.

Apollo 16 returned lunar samples - Lithophile trace-element abundances

NASA Technical Reports Server (NTRS)

Philpotts, J. A.; Schuhmann, S.; Kouns, C. W.; Lum, R. K. L.; Bickel, A. L.; Schnetzler, C. C.

1973-01-01

Lithium, K, Rb, Sr, Ba, rare-earth, Zr, and Hf abundances have been determined by mass-spectrometric isotope-dilution for Apollo 16 soils, anorthosite 61016, and 'basalt' 68415 whole-rock and separated pyroxene and plagioclase. Our sample of 61016 is similar to some other lunar anorthosites in lithophile trace-element concentrations but at a slightly lower level. It was probably accumulated from a little differentiated basalt. Basalt 68415 might be a homogeneous mixture of KREEP and anorthosite material; it appears to have crystallized under conditions as reducing as those holding for mare-basalts. The soil fines cover only a limited compositional range. No obvious chemical differences were noted between the Descartes and Cayley formations. Most of the compositional variation of the soils can be accounted for in terms of the addition of plagioclase. The existence of very high alumina basalt as an independent magma-type appears debatable in view of its KREEP-like lithophile trace-element relative concentrations and the observed lunar radioactivity distribution.

Analysis of gas membrane ultra-high purification of small quantities of mono-isotopic silane

DOE PAGES

de Almeida, Valmor F.; Hart, Kevin J.

2017-01-03

A small quantity of high-value, crude, mono-isotopic silane is a prospective gas for a small-scale, high-recovery, ultra-high membrane purification process. This is an unusual application of gas membrane separation for which we provide a comprehensive analysis of a simple purification model. The goal is to develop direct analytic expressions for estimating the feasibility and efficiency of the method, and guide process design; this is only possible for binary mixtures of silane in the dilute limit which is a somewhat realistic case. In addition, analytic solutions are invaluable to verify numerical solutions obtained from computer-aided methods. Hence, in this paper wemore » provide new analytic solutions for the purification loops proposed. Among the common impurities in crude silane, methane poses a special membrane separation challenge since it is chemically similar to silane. Other potential problematic compounds are: ethylene, diborane and ethane (in this order). Nevertheless, we demonstrate, theoretically, that a carefully designed membrane system may be able to purify mono-isotopic, crude silane to electronics-grade level in a reasonable amount of time and expenses. We advocate a combination of membrane materials that preferentially reject heavy impurities based on mobility selectivity, and light impurities based on solubility selectivity. We provide estimates for the purification of significant contaminants of interest. In this study, we suggest cellulose acetate and polydimethylsiloxane as examples of membrane materials on the basis of limited permeability data found in the open literature. We provide estimates on the membrane area needed and priming volume of the cell enclosure for fabrication purposes when using the suggested membrane materials. These estimates are largely theoretical in view of the absence of reliable experimental data for the permeability of silane. And finally, future extension of this work to the non-dilute limit may apply to the recovery of silane from rejected streams of natural silicon semi-conductor processes.« less

Analysis of gas membrane ultra-high purification of small quantities of mono-isotopic silane

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

de Almeida, Valmor F.; Hart, Kevin J.

A small quantity of high-value, crude, mono-isotopic silane is a prospective gas for a small-scale, high-recovery, ultra-high membrane purification process. This is an unusual application of gas membrane separation for which we provide a comprehensive analysis of a simple purification model. The goal is to develop direct analytic expressions for estimating the feasibility and efficiency of the method, and guide process design; this is only possible for binary mixtures of silane in the dilute limit which is a somewhat realistic case. In addition, analytic solutions are invaluable to verify numerical solutions obtained from computer-aided methods. Hence, in this paper wemore » provide new analytic solutions for the purification loops proposed. Among the common impurities in crude silane, methane poses a special membrane separation challenge since it is chemically similar to silane. Other potential problematic compounds are: ethylene, diborane and ethane (in this order). Nevertheless, we demonstrate, theoretically, that a carefully designed membrane system may be able to purify mono-isotopic, crude silane to electronics-grade level in a reasonable amount of time and expenses. We advocate a combination of membrane materials that preferentially reject heavy impurities based on mobility selectivity, and light impurities based on solubility selectivity. We provide estimates for the purification of significant contaminants of interest. In this study, we suggest cellulose acetate and polydimethylsiloxane as examples of membrane materials on the basis of limited permeability data found in the open literature. We provide estimates on the membrane area needed and priming volume of the cell enclosure for fabrication purposes when using the suggested membrane materials. These estimates are largely theoretical in view of the absence of reliable experimental data for the permeability of silane. And finally, future extension of this work to the non-dilute limit may apply to the recovery of silane from rejected streams of natural silicon semi-conductor processes.« less

Analysis of Gas Membrane Ultra-High Purification of Small Quantities of Mono-Isotopic Silane

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

de Almeida, Valmor F.; Hart, Kevin J.

A small quantity of high-value, crude, mono-isotopic silane is a prospective gas for a small-scale, high-recovery, ultra-high membrane purification process. This is an unusual application of gas membrane separation for which we provide a comprehensive analysis of a simple purification model. The goal is to develop direct analytic expressions for estimating the feasibility and efficiency of the method, and guide process design; this is only possible for binary mixtures of silane in the dilute limit which is a somewhat realistic case. Among the common impurities in crude silane, methane poses a special membrane separation challenge since it is chemically similarmore » to silane. Other potential problematic surprises are: ethylene, diborane and ethane (in this order). Nevertheless, we demonstrate, theoretically, that a carefully designed membrane system may be able to purify mono-isotopic, crude silane to electronics-grade level in a reasonable amount of time and expenses. We advocate a combination of membrane materials that preferentially reject heavy impurities based on mobility selectivity, and light impurities based on solubility selectivity. We provide estimates for the purification of significant contaminants of interest. To improve the separation selectivity, it is advantageous to use a permeate chamber under vacuum, however this also requires greater control of in-leakage of impurities in the system. In this study, we suggest cellulose acetate and polydimethylsiloxane as examples of membrane materials on the basis of limited permeability data found in the open literature. We provide estimates on the membrane area needed and priming volume of the cell enclosure for fabrication purposes when using the suggested membrane materials. These estimates are largely theoretical in view of the absence of reliable experimental data for the permeability of silane. Last but not least, future extension of this work to the non-dilute limit may apply to the recovery of silane from rejected streams of natural silicon semi-conductor processes.« less

Isotope scattering and phonon thermal conductivity in light atom compounds: LiH and LiF

DOE PAGES

Lindsay, Lucas R.

2016-11-08

Engineered isotope variation is a pathway toward modulating lattice thermal conductivity (κ) of a material through changes in phonon-isotope scattering. The effects of isotope variation on intrinsic thermal resistance is little explored, as varying isotopes have relatively small differences in mass and thus do not affect bulk phonon dispersions. However, for light elements isotope mass variation can be relatively large (e.g., hydrogen and deuterium). Using a first principles Peierls-Boltzmann transport equation approach the effects of isotope variance on lattice thermal transport in ultra-low-mass compound materials LiH and LiF are characterized. The isotope mass variance modifies the intrinsic thermal resistance viamore » modulation of acoustic and optic phonon frequencies, while phonon-isotope scattering from mass disorder plays only a minor role. This leads to some unusual cases where values of isotopically pure systems ( 6LiH, 7Li 2H and 6LiF) are lower than the values from their counterparts with naturally occurring isotopes and phonon-isotope scattering. However, these differences are relatively small. The effects of temperature-driven lattice expansion on phonon dispersions and calculated κ are also discussed. This work provides insight into lattice thermal conductivity modulation with mass variation and the interplay of intrinsic phonon-phonon and phonon-isotope scattering in interesting light atom systems.« less

Tracing the sources and cycling of phosphorus in river sediments using oxygen isotopes: Methodological adaptations and first results from a case study in France.

PubMed

Pistocchi, Chiara; Tamburini, Federica; Gruau, Gerard; Ferhi, André; Trevisan, Dominique; Dorioz, Jean-Marcel

2017-03-15

An essential aspect of eutrophication studies is to trace the ultimate origin of phosphate ions (P-PO 4 ) associated with the solid phase of river sediments, as certain processes can make these ions available for algae. However, this is not a straightforward task because of the diversity of allochthonous and autochthonous sources that can supply P-PO 4 to river sediments as well as the existence of in-stream processes that can change the speciation of these inputs and obscure the original sources. Here, we present the results of a study designed to explore the potentials, limitations and conditions for the use of the oxygen isotope composition of phosphate (δ 18 Op) extracted from river sediments for this type of tracing. We first tested if the method commonly applied to soils to purify P-PO 4 and to measure their δ 18 Op concentrations could be adapted to sediments. We then applied this method to a set of sediments collected in a river along a gradient of anthropogenic pressure and compared their isotopic signatures with those from samples that are representative of the potential P-PO 4 inputs to the river system (soils and riverbank material). The results showed that following some adaptations, the purification method could be successfully transposed to river sediments with a high level of P-PO 4 purification (>97%) and high δ 18 Op measurement repeatability and accuracy (<0.4‰). The values for the potential allochthonous sources varied from 11.8 to 18.3‰, while the δ 18 Op value for the river sediments ranged from 12.2 to 15.8‰. Moreover, a sharp increase (>3‰) in the sediment δ 18 Op value immediately downstream from the discharge point revealed the strong impact of municipal wastewater. The calculation of the theoretical equilibrium δ 18 O p values using the river water temperature and δ 18 O w showed that the downstream sediments were in equilibrium, which was not the case for the upstream sediments. This difference could be related to the contrast between the short residence time of the transfer system in the catchment head, which can preserve the isotopic variability of the source materials, and the longer residence times and higher P bioavailability in the lower catchment, possibly fostering the recycling of P-PO 4 by the biota and the equilibration of the oxygen isotope signature in P-PO 4 . These results demonstrate the potential of the isotopic approach to assess the sources and in-stream turnover of sedimentary P in river systems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Oxygen Isotopes in Intra-Back Arc Basalts from the Andean Southern Volcanic Zone

NASA Astrophysics Data System (ADS)

Parks, B. H.; Wang, Z.; Saal, A. E.; Frey, F. A.; Blusztajn, J.

2013-12-01

The chemical compositions of volcanic rocks from the Andean Southern Volcanic Zone (SVZ) reflect complex and dynamic interactions among the subducting oceanic lithosphere, the mantle wedge, and the overlying continental crust. Oxygen isotope ratios of olivine phenocrysts can be a useful means to identifying their relative contributions to the arc magmatism. In this study, we report high-precision oxygen-isotope ratios of olivine phenocrysts in a set of intra-back arc basalts from the SVZ. The samples were collected from monogenetic cinder cones east of the volcanic front (35-39 degrees S), and have been geochemically well-characterized with major and trace element contents, and Sr-Nd-Pb isotope compositions. Compared to lavas from the volcanic front, these intra-back arc lavas have similar radiogenic isotope, and a more alkalic and primitive (higher MgO content) chemical composition. We determined the oxygen-isotope ratios using the CO2-laser-fluorination method set up at the Department of Geology and Geophysics, Yale University following the techniques reported in Wang et al (2011). The samples were analyzed with standards of Gore Mountain Garnet (5.77×0.12‰ 1σ; Valley et al., 1995) and Kilbourne Hole Olivine (5.23×0.07‰ 1σ; Sharp, 1990) in order to account for minor changes in the vacuum line during analyses. The obtained δ18OSMOW values of olivine phenocrysts from the intra-back arc basalts vary from 4.98×0.01 to 5.34×0.01‰. This range, surprisingly, is similar to the δ18O values of olivines from mantle peridotites (5.2×0.2‰). Preliminary results indicate significant correlations of 87Sr/86Sr, 143Nd/144Nd and trace element ratios of the basaltic matrix with the δ18O values of olivine phenocrysts, indicating at least three components involved in the formation of the arc volcanism. By comparing the δ18O with the variations of major and trace element contents (e.g., MgO, TiO2 and Ni), and trace element ratios (e.g. Ba/Nb), we evaluate the effects of fractionation crystallization, crustal contamination, the extent of slab flux, metasomatism, and melting of the mantle wedge on the intra-back arc lavas from the SVZ.

Isotopic and trace element characteristics of an unusual refractory inclusion from Essebi

NASA Technical Reports Server (NTRS)

Deloule, E.; Kennedy, A. K.; Hutcheon, I. D.; Elgoresy, A.

1993-01-01

The isotopic and chemical properties of Ca-Al-rich inclusions (CAI) provide important clues to the early solar nebula environment. While the abundances of refractory major and trace elements are similar to those expected for high temperature condensates, the variety of textural, chemical, and isotopic signatures indicate most CAI experienced complex, multi-stage histories involving repeated episodes of condensation, evaporation, and metamorphism. Evidence of multiple processes is especially apparent in an unusual refractory inclusion from Essebi (URIE) described by El Goresy et al. The melilite (mel)-rich core of URIE contains polygonal framboids of spinel (sp) and hibonite (hb) or sp and fassaite (fas) and is surrounded by a rim sequence consisting of five layers. In contrast to rims on Allende, the mineralogy of the URIE rim layers becomes increasingly refractory from the core outwards, ending in a layer of spinel-Al2O3 solid solution + Sc-rich fassaite. The chemical and mineralogical features of URIE are inconsistent with crystallization from a homogeneous melt, and El Goresy et al. proposed a multi-step history involving condensation of sp + hb and aggregation into framboids, capture of framboids by a refractory silicate melt droplet, condensation of rim layers, and alteration of mel to calcite and feldspathoid. The PANURGE ion probe was used to investigate the isotopic and trace element characteristics of URIE to develop a more complete picture of the multiple processes leading to formation and metamorphism.

Geochemical and Isotopic (Sr, U) Tracing of Weathering Processes Controlling the Recent Geochemical Evolution of Soil Solutions in the Strengbach Catchment (Vosges, France)

NASA Astrophysics Data System (ADS)

Chabaux, F. J.; Prunier, J.; Pierret, M.; Stille, P.

2012-12-01

The characterization of the present-day weathering processes controlling the chemical composition of waters and soils in natural ecosystems is an important issue to predict and to model the response of ecosystems to recent environmental changes. It is proposed here to highlight the interest of a multi-tracer geochemical approach combining measurement of major and trace element concentrations along with U and Sr isotopic ratios to progress in this topic. This approach has been applied to the small granitic Strengbah Catchment, located in the Vosges Mountain (France), used and equipped as a hydro-geochemical observatory since 1986 (Observatoire Hydro-Géochimique de l'Environnement; http://ohge.u-strasbg.fr). This study includes the analysis of major and trace element concentrations and (U-Sr) isotope ratios in soil solutions collected within two soil profiles located on two experimental plots of this watershed, as well as the analysis of soil samples and vegetation samples from these two plots The depth variation of elemental concentration of soil solutions confirms the important influence of the vegetation cycling on the budget of Ca, K, Rb and Sr, whereas Mg and Si budget in soil solutions are quasi exclusively controlled by weathering processes. Variation of Sr, and U isotopic ratios with depth also demonstrates that the sources and biogeochemical processes controlling the Sr budget of soil solutions is different in the uppermost soil horizons and in the deeper ones, and clearly influence by the vegetation cycling.

Assessment of relative Ti, Ta, and Nb (TiTaN) enrichments in global ocean island basalts

NASA Astrophysics Data System (ADS)

Peters, B.; Day, J. M.

2013-12-01

The relative sensitivity of trace element concentrations to processes governing solid-melt and solid-fluid interactions has made them particularly useful for tracing the effects of partial melting, fractional crystallization, metasomatism and similar processes on the composition of a parental melt to a rock or mineral. Radiogenic and stable isotope compositions, in contrast, can provide information on the long-term history and provenance of magmas. Despite the distinct information derived from relative and absolute abundances of trace elements compared with isotopes, numerous studies of ocean island basalts (OIB) have attempted to use trace elements as diagnostic geochemical tracers to understand parental magma compositions. In particular, attempts have been made to correlate 'TiTaN' (Ti, Ta and Nb) anomalies to the He-Os isotopic compositions of OIB based on contributions from recycled eclogite, a theoretical high-TiTaN reservoir, and peridotite, a theoretical high-3He/4He reservoir (Jackson, et al., 2008 G-cubed). These authors have proposed that TiTaN anomalies can be used as independent indicators for recycled oceanic crust and lithospheric mantle in OIB sources, a distinction previously reserved for isotopic data. However, TiTaN anomalies appear uncorrelated to OIB mantle source composition for three reasons. First, a new geochemical compilation of global OIB shows a wide range of Ti (Ti/Ti* = 0.28 - 2.35), Ta (Ta/Ta* = 0.11 - 93.42) and Nb (Nb/Nb* = 0.13 - 17.79) anomalies that do not correlated with each other or noble gas systematics, indicating that: (i) TiTaN anomalies alone do not correspond to the primitive source traced by high-3He/4He or the solar neon component and (ii) Ti, Ta and Nb anomalies may each reflect distinct processes or origins, rather than tracing a single source or process together. Second, positive Ti anomalies can be generated by low-degree (1-10%), non-modal batch partial melting of garnet lherzolite at temperatures and pressures thought to be typical for OIB in many settings (T = 1075 - 1420 °C; P = 1 - 3.5 GPa). Furthermore, Ti, Ta and Nb anomalies can be theoretically created by subjecting the same low-degree partial melt to shallow level assimilation-fractional crystallization processes. If TiTaN anomalies are derived from this ubiquitous process, it presents a challenge to their origin from recycled or deep mantle parental materials. Finally, because clinopyroxene can contain large positive Ti anomalies (up to Ti/Ti* ≈ 1000), clinopyroxene accumulation can result in apparent high positive Ti/Ti* anomalies in ankaramites or other clinopyroxene-bearing rocks, when in reality, these Ti anomalies have been generated independent of primary source composition. Current evidence suggests that TiTaN anomalies do not directly reflect distinct source components in OIB lavas. Even if Ti, Ta and/or Nb enrichments are systematically present in high-3He/4He OIB parental materials, it is unlikely they are preserved due to magma processing at shallow depths.

Single solid phase extraction method for the simultaneous analysis of polar and non-polar pesticides in urine samples by gas chromatography and ultra high pressure liquid chromatography coupled to tandem mass spectrometry.

PubMed

Cazorla-Reyes, Rocío; Fernández-Moreno, José Luis; Romero-González, Roberto; Frenich, Antonia Garrido; Vidal, José Luis Martínez

2011-07-15

A new multiresidue method has been developed and validated for the simultaneous extraction of more than two hundred pesticides, including non-polar and polar pesticides (carbamates, organochlorine, organophosphorous, pyrethroids, herbicides and insecticides) in urine at trace levels by gas and ultra high pressure liquid chromatography coupled to ion trap and triple quadrupole mass spectrometry, respectively (GC-IT-MS/MS, UHPLC-QqQ-MS/MS). Non-polar and polar pesticides were simultaneously extracted from urine samples by a simple and fast solid phase extraction (SPE) procedure using C(18) cartridges as sorbent, and dichloromethane as elution solvent. Recovery was in the range of 60-120%. Precision values expressed as relative standard deviation (RSD) were lower than 25%. Identification and confirmation of the compounds were performed by the use of retention time windows, comparison of spectra (GC-amenable compounds) or the estimation of the ion ratio (LC-amenable compounds). For GC-amenable pesticides, limits of detection (LODs) ranged from 0.001 to 0.436 μg L(-1) and limits of quantification (LOQs) from 0.003 to 1.452 μg L(-1). For LC-amenable pesticides, LODs ranged from 0.003 to 1.048 μg L(-1) and LOQs ranged from 0.011 to 3.494 μg L(-1). Finally, the optimized method was applied to the analysis of fourteen real samples of infants from agricultural population. Some pesticides such as methoxyfenozide, tebufenozide, piperonyl butoxide and propoxur were found at concentrations ranged from 1.61 to 24.4 μg L(-1), whereas methiocarb sulfoxide was detected at trace levels in two samples. Copyright © 2011 Elsevier B.V. All rights reserved.

A SIMS study of lunar 'komatiitic glasses' - Trace element characteristics and possible origin

NASA Technical Reports Server (NTRS)

Shearer, C. K.; Papike, J. J.; Galbreath, K. C.; Wentworth, S. J.; Shimizu, N.

1990-01-01

In Apollo 16 regolith breccias, Wentworth and McKay (1988) identified a suite of minute (less than 120 microns) 'komatiitic glass beads'. The wide major element compositional range, and ultra-Mg-prime character of the glasses suggest a variety of possible origins from complex impact processes to complex volcanic processes involving rather unusual and primitive magmatism. The extent of trace element depletion or enrichment in these glasses appears to be correlated to the siderophile character of the element (ionization potential or experimentally determined silicate melt/Fe metal partition coefficients. The ultra-Mg-prime glasses are depleted in Co relative to a bulk Moon Mg/Co exhibited by many lunar samples (volcanic glasses, basalts, regolith breccia, estimated upper mantle). The low Co and high incompatible element concentrations diminish the possibility that these glasses are a product of lunar komatiitic volcanism or impact, excavation, and melting of a very high Mg-prime plutonic unit.

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

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Mechora, Špela; Stibilj, Vekoslava

2014-05-01

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

Carbon Isotopic Heterogeneity of Graphite in the San Juan Mass of the Campo Del Cielo IAB Iron Meteorite

NASA Technical Reports Server (NTRS)

Maruoka, T.; Kurat, G.; Zinner, E.; Varela, M. E.; Ametrano, S. J.

2003-01-01

The origin of IAB iron meteorites is still a matter of debate. It is generally believed that iron meteorites originated from molten cores in small planetesimals because the fractionation trend of trace elements (e.g., Ir, Ge, Ga, etc. vs. Ni) for most iron meteorites can be more or less explained by fractional crystallization from metal melts. However, this process cannot produce trace element characteristics of the IAB (and other) iron meteorites. To explain these trace element abundance patterns, several models have been proposed. Although most of these models require a high temperature, clear evidence has recently been obtained for a sub-solidus formation of IAB iron meteorites from noble gas analyses. Moreover, heterogeneous distributions of some trace elements in metal and other phases also suggest a low temperature origin of at least some IAB iron meteorites. Here we use the carbon isotopic compositions of graphite to constrain the origin of IAB iron meteorites. Our data confirm a possible low temperature origin of IAB iron meteorites.

Can Biomass Burning Explain Isotopically Light Fe in Marine Aerosols?

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Inductively coupled plasma mass spectrometry for stable isotope metabolic tracer studies of living systems

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

Luong, Elise

1999-05-10

This dissertation focuses on the development of methods for stable isotope metabolic tracer studies in living systems using inductively coupled plasma single and dual quadrupole mass spectrometers. Sub-nanogram per gram levels of molybdenum (Mo) from human blood plasma are isolated by the use of anion exchange alumina microcolumns. Million-fold more concentrated spectral and matrix interferences such as sodium, chloride, sulfate, phosphate, etc. in the blood constituents are removed from the analyte. The recovery of Mo from the alumina column is 82 ± 5% (n = 5). Isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) is utilized for the quantitative ultra-tracemore » concentration determination of Mo in bovine and human blood samples. The average Mo concentration in reference bovine serum determined by this method is 10.2 ± 0.4 ng/g, while the certified value is 11.5 ± 1.1 ng/g (95% confidence interval). The Mo concentration of one pool of human blood plasma from two healthy male donors is 0.5 ± 0.1 ng/g. The inductively coupled plasma twin quadrupole mass spectrometer (ICP-TQMS) is used to measure the carbon isotope ratio from non-volatile organic compounds and bio-organic molecules to assess the ability as an alternative analytical method to gas chromatography combustion isotope ratio mass spectrometry (GC-combustion-IRMS). Trytophan, myoglobin, and β-cyclodextrin are chosen for the study, initial observation of spectral interference of 13C + with 12C 1H + comes from the incomplete dissociation of myoglobin and/or β-cyclodextrin.« less

Development of an Ultra-Low Background Liquid Scintillation Counter for Trace Level Analysis

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

Erchinger, Jennifer L.; Orrell, John L.; Aalseth, Craig E.

2015-09-01

Low-level liquid scintillation counting (LSC) has been established as one of the radiation detection techniques useful in elucidating environmental processes and environmental monitoring around nuclear facilities. The Ultra-Low Background Liquid Scintillation Counter (ULB-LSC) under construction in the Shallow Underground Laboratory at Pacific Northwest National Laboratory aims to further reduce the MDAs and/or required sample processing. Through layers of passive shielding in conjunction with an active veto and 30 meters water equivalent overburden, the background reduction is expected to be 10 to 100 times below typical analytic low-background liquid scintillation systems. Simulations have shown an expected background of around 14 countsmore » per day. A novel approach to the light collection will use a coated hollow light guide cut into the inner copper shielding. Demonstration LSC measurements will show low-energy detection, spectral deconvolution, and alpha/beta discrimination capabilities, from trials with standards of tritium, strontium-90, and actinium-227, respectively. An overview of the system design and expected demonstration measurements will emphasize the potential applications of the ULB-LSC in environmental monitoring for treaty verification, reach-back sample analysis, and facility inspections.« less

Mercury stable isotope fractionation in a tropical ecosystem including human hair: New insights for an isotope balance

NASA Astrophysics Data System (ADS)

Laffont, Laure; Sonke, Jeroen; Maurice, Laurence; Behra, Philippe

2010-05-01

Mercury contamination is an environmental problem in the Amazon basin still relevant today as impacts on human health are poorly studied. In Bolivia, indigenous people have elevated methylmercury concentrations (between 2719 and 23701 ng.g-1) in their hair. This highly toxic molecule is formed after methylation of inorganic Hg released by chemical and physical weathering and from human activities. The aim of our study is to propose a first isotope balance in a Bolivian Amazon ecosystem, through variations in Hg isotopic compositions. The discovery of mass-independent fracionation (MIF) of odd-isotopes in our organic samples (fish and human hair) opened a new way of research in tracing the sources and the processes involved in the cycle of Hg. Four types of samples are studied: liquid Hg0 from gold mining, sediment samples, fish coming from the Beni River basin (from the main channel and an associated floodplain lake) and hair from gold miners and fish-eating native populations. Hg isotopic compositions were analyzed on a Thermo-Finnigan Neptune MC-ICP-MS at the LMTG after sample digestion by HCl/HNO3 or by H2O2/HNO3 for fish samples, at 120°C. The δ202Hg values (relative to NIST 3133) are signicantly different with respect to the external precision on UM-Almaden#2 of 0.18 ‰ (2σ, n = 42): -0.34 ± 0.02 ‰ for liquid mercury, between -1.33 and -0.81 ‰ for bottom and floodplain sediments (n=18), between -0.87 and 2.22 ‰ for miners hair (n=26), +1.29 ± 0.41 ‰ for native hair (n=13) and between -0.91 and -0.21 ‰ for fish samples (n=53). A large mass-independent isotope fractionation (MIF) was observed for odd isotope ratios in all hair samples and fish samples whereas weak anomalies were measured for sediment samples: - ∆199Hg anomaly: -0.12 to -0.04 ‰ for sediment, -0.22 to +0.63 ‰ for fish samples and +0.13 to +1.63 ‰ for hair - ∆201Hg anomaly: -0.12 to -0.02 ‰ for sediment, -0.21 to +0.43 ‰ for fish samples and +0.06 to +1.25 ‰ for hair. Both anomalies ∆201Hg vs. ∆199Hg are linearly correlated with a slope of +1.12‰ for native hair and a mass dependant fractionation (MDF) of ~+2‰ has been evidenced between native communities hair and fish species constituting their diet. For the same fish species, MIF anomalies differ with floodplain lakes and drainage basins suggesting that the methylmercury (MMHg) analysed in fish caught in floodplain lake reflects the photodemethylation process while in the Beni R. mainstream the negative anomalies confirm that this photochemical reactions are limited. Within the aquatic food chain of an hydrosystem, it appears that MIF anomalies can trace the fish ecology and the aquatic photochemical processes, while mass dependent fractionation can trace the trophic level as a result of excretion and metabolic processes involving mercury in the body.

Nitrogen Fate in a Phreatic Fluviokarst Watershed: a Stable Isotope, Sediment Tracing, and Numerical Modeling Approach

NASA Astrophysics Data System (ADS)

Husic, A.; Fox, J.; Ford, W. I., III; Agouridis, C.; Currens, J. C.; Taylor, C. J.

2017-12-01

Sediment tracing tools provide an insight into provenance, fate, and transport of sediment and, when coupled to stable isotopes, can elucidate in-stream biogeochemical processes. Particulate nitrogen fate in fluviokarst systems is a relatively unexplored area of research partially due to the complex hydrodynamics at play in karst systems. Karst topography includes turbulent conduits that transport groundwater and contaminants at speeds more typical of open channel flows than laminar Darcian flows. While it is accepted that karst hydro-geomorphology represents a hybrid surface-subsurface system for fluid, further investigation is needed to determine whether, and to what extent, karst systems behave like surface agricultural streams or porous media aquifers with respect to their role in nitrogen cycling. Our objective is to gain an understanding of in-conduit nitrogen processes and their effect on net nitrogen-exports from karst springs to larger waterbodies. The authors apply water, sediment, carbon, and nitrogen tracing techniques to analyze water for nitrate, sediment carbon and nitrogen, and stable sediment nitrogen isotope (δ15N). Thereafter, a new numerical model is formulated that: simulates dissolved inorganic nitrogen and sediment nitrogen transformations in the phreatic karst conduit; couples carbon turnover and nitrogen transformations in the model structure; and simulates the nitrogen stable isotope mass balance for the dissolved and sediment phases. Nitrogen tracing data results show a significant increase in δ15N of sediment nitrogen at the spring outlet relative to karst inputs indicating the potential for isotope fractionation during dissolved N uptake by bed sediments in the conduit and during denitrification within bed sediments. The new numerical modeling structure is then used to reproduce the data results and provide an estimate of the relative dominance of N uptake and denitrification within the surficial sediments of the karst conduit system. For the first time to our knowledge, results shed light on sediment processes that help control nutrient retention in phreatic karst conduits and tend to suggest that the karst systems behave as an intermediate N conveyor relative to surface agricultural streams and porous media aquifers.

Trace elements and isotope data of the Um Garayat gold deposit, Wadi Allaqi district, Egypt

NASA Astrophysics Data System (ADS)

Zoheir, Basem; Emam, Ashraf; Pitcairn, Iain K.; Boskabadi, Arman; Lehaye, Yann; Cooper, Matthew J.

2018-04-01

Trace element composition of sulfides and O, C, Sr and S isotopic data are assessed to constrain the evolution and potential fluid and metal sources of the Um Garayat gold deposit. Ore microscopy and BSE investigations of quartz veins show blocky arsenopyrite and pyrite replaced in part by pyrrhotite, chalcopyrite, sphalerite, galena, and gersdorffite. Free-milling gold occurs commonly in close association with the late sulfides, and along fractures in pyrite. On the other hand, recrystallized pyrite is disseminated in host metavolcaniclastic/metasedimentary rocks that commonly contain carbonaceous material. In situ LA-ICP-MS analysis of sulfides shows the recrystallized pyrite enriched in most trace elements, while blocky pyrite contains only some traces of arsenic. Detected concentrations of gold (up to 17 ppm) were only reported in arsenopyrite disseminated in quartz veins. The δ34S values of blocky pyrite and pyrrhotite in quartz veins define a narrow range (1.6 to 3.7‰), suggesting a homogenous sulfur source which is consistent with the dominantly mafic host rocks. The recrystallized pyrite has a distinctive sulfur isotope composition (δ34S - 9.3 to - 10.6‰), which is rather comparable to diagenetic sulfides. Hydrothermal carbonate in quartz veins and wallrock have nearly constant values of δ18O (10.5 to 11.9‰) and δ13C (- 4.2 to - 5.5‰). Based on constraints from mineral assemblages and chlorite thermometry, data of six samples indicate that carbonate precipitation occurred at 280 °C from a homogenous hydrothermal fluid with δ18OH2O 4.4 ± 0.7‰ and δ13C = 3.7 ± 0.8‰. Strontium isotope values of two samples (87Sr/86Sr = 0.7024 and 0.7025) are similar to the initial 87Sr/86Sr ratios of island arc metabasalts ( 710 Ma) in the South Eastern Desert. The generally homogenous sulfur, C, O, Sr isotope data are suggestive of metamorphogenic fluids, likely produced from dominantly mafic volcanic rocks at the greenschist-amphibolite facies transition.

Investigation into MIS 11 in the U.S. Great Basin Using Trace Elements and Stable Isotopes from two Lehman Caves Stalagmites

NASA Astrophysics Data System (ADS)

Neary, A.; McGee, D.; Tal, I.; Shakun, J. D.

2015-12-01

Marine Isotope Stage 11 (MIS 11) represents a long interglacial period of high temperatures and muted orbital variability that occurred around 424-374 kya, and is referred to as a 'super-interglacial'. MIS 11 is marked by especially pronounced high latitude warming in the Northern Hemisphere from 410-400 ka and thus presents a natural experiment for investigating the response of Great Basin precipitation to high latitude temperatures.MIS 11 is recorded by stalagmites LC3 and BT1 from Lehman Caves in Great Basin National Park, Nevada. LC3 represents 378-413 ka, while BT1 has a bottom age of 410 ka. Ongoing U-Th dating will refine chronologies from these samples. We will present stable isotope (δ13C and δ18O) and trace element (Mg/Ca and Sr/Ca) data from these stalagmites to study changes in precipitation recorded in them. Previous studies have shown a relationship between Mg/Ca, Sr/Ca, δ13C and prior calcite precipitation, and thus infiltration rates, in the cave system (Cross et al., 2015; Steponaitis et al., 2015). Meanwhile, δ18O has been shown to reflect larger scale atmospheric circulation.We will compare the records to previously published trace element and stable isotope data from more recent interglacials (Lachniet et al., 2014; Cross et al., 2015; Steponaitis et al., 2015) to test whether extensive high-latitude warming during MIS 11 was marked by anomalous precipitation patterns in the Great Basin. As they are coeval, we will also test the reproducibility between the stalagmites.References cited:Cross M., et al. (2015) Great Basin hydrology, paleoclimate, and connections with the North Atlantic: A speleothem stable isotope and trace element record from Lehman Caves, NV. Quaternary Science Reviews, in press.Steponaitis E., et al. (2015) Mid-Holocene drying the U.S. Great Basin recorded in Nevada speleothems. Quaternary Science Reviews, in press.Lachniet M. S., et al. (2014) Orbital control of western North America atmospheric circulation and climate over two glacial cycles. Nature Communications 5, 1-8.

Potential of IRMS technology for tracing gamma-butyrolactone (GBL).

PubMed

Marclay, François; Pazos, Diego; Delémont, Olivier; Esseiva, Pierre; Saudan, Christophe

2010-05-20

Popularity of gamma-hydroxybutyric acid (GHB) is fairly stable among drug users, while the consumption of its chemical precursor, gamma-butyrolactone (GBL), is a growing phenomenon. Although conventional analytical methods allow to detect this substance in various matrices, linking a trace and a source is still a difficult challenge. However, as several synthesis pathways and chemical precursors exist for the production of GBL, its carbon isotopic signature may vary extensively. For that purpose, a method has been developed to determine the carbon isotopes content of GBL by means of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The delta(13)C-values of 19 bulk samples purchased worldwide were in the range from -23.1 to -45.8 per thousand (SD<0.3 per thousand). Furthermore, testing on the purification of GBL by distillation has not been found to be consistent with such a large range of delta(13)C-values, which are likely to result from the isotopic composition of the organic precursors used to produce GBL together with the kinetic isotope effect associated with the synthesis routes. Finally, inter- and intra-variability measurements of the delta(13)C-values demonstrated the high potential of IRMS for discriminating between seizures of GBL and for source determination.

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

NASA Astrophysics Data System (ADS)

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

2000-03-01

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

Impurity measurements in semiconductor materials using trace element accelerator mass spectrometry

NASA Astrophysics Data System (ADS)

McDaniel, F. D.; Datar, S. A.; Nigam, M.; Ravi Prasad, G. V.

2002-05-01

Accelerator mass spectrometry (AMS) is commonly used to determine the abundance ratios of long-lived isotopes such as 10B, 14C, 36Cl, 129I, etc. to their stable counterparts at levels as low as 10 -16. Secondary ion mass spectrometry (SIMS) is routinely used to determine impurity levels in materials by depth profiling techniques. Trace-element accelerator mass spectrometry (TEAMS) is a combination of AMS and SIMS, presently being used at the University of North Texas, for high-sensitivity (ppb) impurity analyses of stable isotopes in semiconductor materials. The molecular break-up characteristics of AMS are used with TEAMS to remove the molecular interferences present in SIMS. Measurements made with different substrate/impurity combinations demonstrate that TEAMS has higher sensitivity for many elements than other techniques such as SIMS and can assist with materials characterization issues. For example, measurements of implanted As in the presence of Ge in Ge xSi 1- x/Si is difficult with SIMS because of molecular interferences from 74GeH, 29Si 30Si 16O, etc. With TEAMS, the molecular interferences are removed and higher sensitivities are obtained. Measured substrates include Si, SiGe, CoSi 2, GaAs and GaN. Measured impurities include B, N, F, Mg, P, Cl, Cr, Fe, Ni, Co, Cu, Zn, Ge, As, Se, Mo, Sn and Sb. A number of measurements will be presented to illustrate the range and power of TEAMS.

Stable Isotope Biogeochemistry of Seabird Guano Fertilization: Results from Growth Chamber Studies with Maize (Zea Mays)

PubMed Central

Szpak, Paul; Longstaffe, Fred J.; Millaire, Jean-François; White, Christine D.

2012-01-01

Background Stable isotope analysis is being utilized with increasing regularity to examine a wide range of issues (diet, habitat use, migration) in ecology, geology, archaeology, and related disciplines. A crucial component to these studies is a thorough understanding of the range and causes of baseline isotopic variation, which is relatively poorly understood for nitrogen (δ15N). Animal excrement is known to impact plant δ15N values, but the effects of seabird guano have not been systematically studied from an agricultural or horticultural standpoint. Methodology/Principal Findings This paper presents isotopic (δ13C and δ15N) and vital data for maize (Zea mays) fertilized with Peruvian seabird guano under controlled conditions. The level of 15N enrichment in fertilized plants is very large, with δ15N values ranging between 25.5 and 44.7‰ depending on the tissue and amount of fertilizer applied; comparatively, control plant δ15N values ranged between −0.3 and 5.7‰. Intraplant and temporal variability in δ15N values were large, particularly for the guano-fertilized plants, which can be attributed to changes in the availability of guano-derived N over time, and the reliance of stored vs. absorbed N. Plant δ13C values were not significantly impacted by guano fertilization. High concentrations of seabird guano inhibited maize germination and maize growth. Moreover, high levels of seabird guano greatly impacted the N metabolism of the plants, resulting in significantly higher tissue N content, particularly in the stalk. Conclusions/Significance The results presented in this study demonstrate the very large impact of seabird guano on maize δ15N values. The use of seabird guano as a fertilizer can thus be traced using stable isotope analysis in food chemistry applications (certification of organic inputs). Furthermore, the fertilization of maize with seabird guano creates an isotopic signature very similar to a high-trophic level marine resource, which must be considered when interpreting isotopic data from archaeological material. PMID:22479435

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.

From position-specific isotope labeling towards soil fluxomics: a novel toolbox to assess the microbial impact on biogeochemical cycles

NASA Astrophysics Data System (ADS)

Apostel, C.; Dippold, M. A.; Kuzyakov, Y.

2015-12-01

Understanding the microbial impact on C and nutrient cycles is one of the most important challenges in terrestrial biogeochemistry. Transformation of low molecular weight organic substances (LMWOS) is a key step in all biogeochemical cycles because 1) all high molecular substances pass the LMWOS pool during their degradation and 2) only LMWOS can be taken up by microorganisms intact. Thus, the transformations of LMWOS are dominated by biochemical pathways of the soil microorganisms. Thus, understanding fluxes and transformations in soils requires a detailed knowledge on the microbial metabolic network and its control mechanism. Tracing C fate in soil by isotopes became on of the most applied and promising biogeochemistry tools but studies were nearly exclusively based on uniformly labeled substances. However, such tracers do not allow the differentiation of the intact use of the initial substances from its transformation to metabolites. The novel tool of position-specific labeling enables to trace molecule atoms separately and thus to determine the cleavage of molecules - a prerequisite for metabolic tracing. Position-specific labeling of basic metabolites and quantification of isotope incorporation in CO2 and bulk soil enabled following the basic metabolic pathways of microorganisms. However, the combination of position-specific 13C labeling with compound-specific isotope analysis of microbial biomarkers and metabolites like phospholipid fatty acids (PLFA) or amino sugars revealed new insights into the soil fluxome: First, it enables tracing specific anabolic pathways in diverse microbial communities in soils e.g. carbon starvation pathways versus pathways reflecting microbial growth. Second, it allows identification of specific pathways of individual functional microbial groups in soils in situ. Tracing metabolic pathways and understanding their regulating factors are crucial for soil C fluxomics i.e. the unravaling of the complex network of C transformations. Quantitative models to assess microbial group specific metabolic pathways can be generated and parameterized by this approach. The knowledge of submolecular C transformation steps and its regulating factors is essential for understanding C cycling and long-term C storage in soils.

Observations of Isotope Fractionation in Prestellar Cores: Interstellar Origin of Meteoritic Hot Spot?

NASA Technical Reports Server (NTRS)

Milam, S. N.; Charnley, S. B.

2011-01-01

Isotopically fractionated material is found in many solar system objects, including meteorites and comets. It is thought, in some cases, to trace interstellar material that was incorporated into the solar system without undergoing significant processing. Here, we show the results of models and observations of the nitrogen and carbon fractionation in proto-stellar cores.

Isotopic abundance in atom trap trace analysis

DOEpatents

Lu, Zheng-Tian; Hu, Shiu-Ming; Jiang, Wei; Mueller, Peter

2014-03-18

A method and system for detecting ratios and amounts of isotopes of noble gases. The method and system is constructed to be able to measure noble gas isotopes in water and ice, which helps reveal the geological age of the samples and understand their movements. The method and system uses a combination of a cooled discharge source, a beam collimator, a beam slower and magneto-optic trap with a laser to apply resonance frequency energy to the noble gas to be quenched and detected.

The Global Search for Abiogenic GHGs, via Methane Isotopes and Ethane

NASA Astrophysics Data System (ADS)

Malina, Edward; Muller, Jan-Peter; Walton, David; Potts, Dale

2015-04-01

The importance of Methane as an anthropogenic Green House Gas (GHG) is well recognized in the scientific community, and is second only to Carbon Dioxide in terms of influence on the Earth's radiation budget (Parker, et al, 2011) suggesting that the ability to apportion the source of the methane (whether it is biogenic, abiogenic or thermogenic) has never been more important. It has been proposed (Etiope, 2009) that it may be possible to distinguish between a biogenic methane source (e.g. bacteria fermentation) and an abiogenic source (e.g. gas seepage or fugitive emissions) via the retrieval of the abundances of methane isotopes (12CH4 and 13CH4) and through the ratio of ethane (C2H6) to methane (CH4) concentrations. Using ultra fine spectroscopy (<0.2cm-1 spectral resolution) from Fourier Transform Spectrometers (FTS) based on the SCISAT-1 (ACE-FTS) and GOSAT (TANSO-FTS) we are developing a retrieval scheme to map global emissions of abiogenic and biogenic methane, and provide insight into how these variations in methane might drive atmospheric chemistry, focusing on the lower levels of the atmosphere. Using HiTran2012 simulations, we show that it is possible to distinguish between methane isotopes using the FTS based instruments on ACE and GOSAT, and retrieve the abundances in the Short Wave Infra-red (SWIR) at 1.65μm, 2.3μm, 3.3μm and Thermal IR, 7.8μm wavebands for methane, and the 3.3μm and 7μm wavebands for ethane. Initially we use the spectral line database HITRAN to determine the most appropriate spectral waveband to retrieve methane isotopes (and ethane) with minimal water vapour, CO2 and NO2 impact. Following this, we have evaluated the detectability of these trace gases using the more sophisticated Radiative Transfer Models (RTMs) SCIATRAN, the Oxford RFM and MODTRAN 5 in the SWIR, in order to determine the barriers to retrieving methane isotopes in both ACE (limb profile) and GOSAT (nadir measurements) instruments, including a preliminary investigation into the effects of clouds, aerosols, surface reflectance on the retrieval of methane isotopes. The aim of these RTM simulations is to further narrow down the spectral regions (originally identified in the HITRAN assessment) where methane isotopes can/may be retrieved from orbit. The key outputs from the RTM study are absorption and radiance data, which allow us to identify the cleanest methane regions, and the likely SNR achievable in these regions. Finally we show some of the results of a study where we compare the output from each of the RTMs used in this study (SCIATRAN, ORFM and MODTRAN), in order to gain some confidence and insight into the strengths and weaknesses of the RTM outputs, using MODTRAN as a benchmark. References: Bernath, P. F. (2005). Atmospheric Chemistry Experiment (ACE): Mission overview. Geophys. Res. Lett. 32: L15S01. Etiope, G. (2009). Natural emissions of methane from geological seepage in Europe. Atmospheric Environment Journal. 2009 vol. 43(7) pp. 1430-1443. JAXA (2012). "Overview of the "IBUKI"(GOSAT)." Retrieved 05-03-2014, 2014, from http://www.jaxa.jp/countdown/f15/overview/ibuki_e.html. Parker, R, et al (2011). GOSAT "Proxy" Methane v4 - Updated March 2013. Accessed 11/04/14 at 08:13. URL: http://www.leos.le.ac.uk/GHG/data/styled/index.html.

Potential autotrophic metabolisms in ultra-basic reducing springs associated with present-day continental serpentinization

NASA Astrophysics Data System (ADS)

Morrill, P. L.; Miles, S.; Kohl, L.; Kavanagh, H.; Ziegler, S. E.; Brazelton, W. J.; Schrenk, M. O.

2013-12-01

Ultra-basic reducing springs at continental sites of serpentinization act as windows into the biogeochemistry of this subsurface exothermic environment rich in H2 and CH4 gases. Biogeochemical carbon transformations in these systems are of interest because serpentinization creates conditions that are amenable to abiotic and biotic reduction of carbon. However, little is known about the metabolic capabilities of the microorganisms that live in this environment. To determine the potential for autotrophic metabolisms, bicarbonate and CO substrate addition microcosm experiments were performed using water and sediment from an ultra-basic reducing spring in the Tablelands, Newfoundland, Canada, a site of present-day continental serpentinization. CO was consistently observed to be utilized in the Live but not the Killed controlled replicates amended with 10% 13C labelled CO and non-labelled (natural C isotope abundance) CO. In the Live CO microcosms with natural C isotope abundance, the residual CO became enriched in 13C (~10 ‰) consistent with a decrease in the fraction of CO remaining. In the Killed CO controlled replicates with natural C isotope abundance the CO showed little 13C enrichment (~1.3 ‰). The data from the Live CO microcosms were well described by a Rayleigh isotopic distillation model, yielding an isotopic enrichment factor for microbial CO uptake of 15.7 ×0.5 ‰ n=2. These data suggest that there was microbial CO utilization in these experiments. The sediment and water from the 13C-labelled and non-labelled, Live and Killed microcosms were extracted for phospholipid fatty acids (PLFAs) to determine changes in community composition between treatments as well as to determine the microbial uptake of CO. The difference in community composition between the Live and Killed microcosms was not readily resolvable based on PLFA distributions. Additionally, the microbial uptake of 13CO had minimal to no affect on the δ13C of the cellular biomarkers, with the exception of C16 saturated and a C16 monounsaturated PLFAs in one live microcosm which showed >2 ‰ and >10 ‰ enrichment, respectively, compared to the average δ13C values of the same PLFA in the 13C Killed controlled replicates. Therefore the uptake of CO had minimal effect on the overall biomass and community composition in the system. The 13C labelled bicarbonate anaerobic microcosm experiments showed little to no methane production. The methane detected in the 13C labelled Live experiments were not isotopically enriched in 13C compared to the CH4 in the labelled Killed controlled replicates. Therefore bicarbonate was not used as a substrate for microbial methanogenesis via the CO2 reduction pathway. These results are generally consistent with genomic and metagenomic data, which discovered the potential for a carbon fixation pathway involving carbon monoxide, but little evidence for archaea or methanogenesis in the ultra-basic springs in the Tablelands (Brazelton et al., 2012). Reference: Brazelton WJ, Nelson B, & Schrenk MO (2012) Frontiers in Microbiology 2:1-16.

Parallel labeling experiments for pathway elucidation and (13)C metabolic flux analysis.

PubMed

Antoniewicz, Maciek R

2015-12-01

Metabolic pathway models provide the foundation for quantitative studies of cellular physiology through the measurement of intracellular metabolic fluxes. For model organisms metabolic models are well established, with many manually curated genome-scale model reconstructions, gene knockout studies and stable-isotope tracing studies. However, for non-model organisms a similar level of knowledge is often lacking. Compartmentation of cellular metabolism in eukaryotic systems also presents significant challenges for quantitative (13)C-metabolic flux analysis ((13)C-MFA). Recently, innovative (13)C-MFA approaches have been developed based on parallel labeling experiments, the use of multiple isotopic tracers and integrated data analysis, that allow more rigorous validation of pathway models and improved quantification of metabolic fluxes. Applications of these approaches open new research directions in metabolic engineering, biotechnology and medicine. Copyright © 2015 Elsevier Ltd. All rights reserved.

The Nucleon-Mission: A New Approach to Cosmic Rays Investigation

NASA Technical Reports Server (NTRS)

Adams, James H., Jr.; Bashindzhagyan, G.; Bashindzhagyan, P.; Chilingarian, A.; Donnelly, J.; Drury, L.; Egorov, N.; Golubkov, S.; Grebenyuk, V.; Hasebe, N.;

Application of zinc isotope tracer technology in tracing soil heavy metal pollution

NASA Astrophysics Data System (ADS)

Norbu, Namkha; Wang, Shuguang; Xu, Yan; Yang, Jianqiang; Liu, Qiang

2017-08-01

Recent years the soil heavy metal pollution has become increasingly serious, especially the zinc pollution. Due to the complexity of this problem, in order to prevent and treat the soil pollution, it's crucial to accurately and quickly find out the pollution sources and control them. With the development of stable isotope tracer technology, it's able to determine the composition of zinc isotope. Based on the theory of zinc isotope tracer technique, and by means of doing some latest domestic and overseas literature research about the zinc isotope multi-receiving cups of inductively coupled plasma mass spectrometer (MC-ICP-MS) testing technology, this paper summarized the latest research results about the pollution tracer of zinc isotope, and according to the deficiencies and existing problems of previous research, made outlooks of zinc isotope fractionation mechanism, repository establishment and tracer multiple solutions.

Determination of Ultra-trace Rhodium in Water Samples by Graphite Furnace Atomic Absorption Spectrometry after Cloud Point Extraction Using 2-(5-Iodo-2-Pyridylazo)-5-Dimethylaminoaniline as a Chelating Agent.

PubMed

Han, Quan; Huo, Yanyan; Wu, Jiangyan; He, Yaping; Yang, Xiaohui; Yang, Longhu

2017-03-24

A highly sensitive method based on cloud point extraction (CPE) separation/preconcentration and graphite furnace atomic absorption spectrometry (GFAAS) detection has been developed for the determination of ultra-trace amounts of rhodium in water samples. A new reagent, 2-(5-iodo-2-pyridylazo)-5-dimethylaminoaniline (5-I-PADMA), was used as the chelating agent and the nonionic surfactant TritonX-114 was chosen as extractant. In a HAc-NaAc buffer solution at pH 5.5, Rh(III) reacts with 5-I-PADMA to form a stable chelate by heating in a boiling water bath for 10 min. Subsequently, the chelate is extracted into the surfactant phase and separated from bulk water. The factors affecting CPE were investigated. Under the optimized conditions, the calibration graph was linear in the range of 0.1-6.0 ng/mL, the detection limit was 0.023 ng/mL for rhodium and relative standard deviation was 3.67% ( c = 1.0 ng/mL, n = 11)．The method has been applied to the determination of trace rhodium in water samples with satisfactory results.

Barium isotopes in cold-water corals

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Variability in magnesium, carbon and oxygen isotope compositions, and trace element contents of brachiopod shells: implications for paleoceanographic studies

NASA Astrophysics Data System (ADS)

Rollion-Bard, Claire; Saulnier, Ségolène; Vigier, Nathalie; Schumacher, Aimryc; Chaussidon, Marc; Lécuyer, Christophe

2016-04-01

Magnesium content in the ocean is ≈ 1290 ppm and is one of the most abundant elements. It is involved in the carbon cycle via the dissolution and precipitation of carbonates, especially Mg-rich carbonates as dolomites. The Mg/Ca ratio of the ocean is believed to have changed through time. The causes of these variations, i.e. hydrothermal activity change or enhanced precipitation of dolomite, could be constrained using the magnesium isotope composition (δ26Mg) of carbonates. Brachiopods, as marine environmental proxies, have the advantage to occur worldwide in a depth range from intertidal to abyssal, and have been found in the geological record since the Cambrian. Moreover, as their shell is in low-Mg calcite, they are quite resistant to diagenetic processes. Here we report δ26Mg, δ18O, δ13C values along with trace element contents of one modern brachiopod specimen (Terebratalia transversa) and one fossil specimen (Terebratula scillae, 2.3 Ma). We combined δ26Mg values with oxygen and carbon isotope compositions and trace element contents to look for possible shell geochemical heterogeneities in order to investigate the processes that control the Mg isotope composition of brachiopod shells. We also evaluate the potential of brachiopods as a proxy of past seawater δ26Mg values. The two investigated brachiopod shells present the same range of δ26Mg variation (up to 2 ‰)). This variation cannot be ascribed to changes in environmental parameters, i.e. temperature or pH. As previously observed, the primary layer of calcite shows the largest degree of oxygen and carbon isotope disequilibrium relative to seawater. In contrast, the δ26Mg value of this layer is comparable to that of the secondary calcite layer value. In both T. scillae and T. transversa, negative trends are observable between magnesium isotopic compositions and oxygen and carbon isotopic compositions. These trends, combined to linear relationships between δ26Mg values and REE contents, are best explained by kinetic effects linked to changes in growth rate during the brachiopod life. The innermost calcite layer of T. transversa is in isotopic equilibrium for both oxygen and magnesium and could therefore be the best target for reconstructing past δ26Mg values of seawater.

Ultratrace determination of arsenic in water samples by electrothermal atomic absorption spectrometry after pre-concentration with Mg-Al-Fe ternary layered double hydroxide nano-sorbent.

PubMed

Abdolmohammad-Zadeh, Hossein; Jouyban, Abolghasem; Amini, Roghayeh

2013-11-15

A selective solid phase extraction method, based on nano-structured Mg-Al-Fe(NO3(-)) ternary layered double hydroxide as a sorbent, is developed for the pre-concentration of ultra-trace levels of arsenic (As) prior to determination by electrothermal atomic absorption spectrometry. It is found that both As(III) and As(V) could be quantitatively retained on the sorbent within a wide pH range of 4-12. Accordingly, the presented method is applied to determination of total inorganic As in aqueous solutions. Maximum analytical signal of As is achieved when the pyrolysis and atomization temperatures are close to 900 °C and 2300 °C, respectively. Several variables affecting the extraction efficiency including pH, sample flow rate, amount of nano-sorbent, elution conditions and sample volume are optimized. Under the optimized conditions, the limit of detection (3Sb/m) and the relative standard deviation are 4.6 pg mL(-1) and 3.9%, respectively. The calibration graph is linear in the range of 15.0-650 pg mL(-1) with a correlation coefficient of 0.9979, sorption capacity and pre-concentration factor are 8.68 mg g(-1) and 300, respectively. The developed method is validated by the analysis of a standard reference material (SRM 1643e) and is successfully applied to the determination of ultra-trace amounts of As in different water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Exploring water cycle dynamics by sampling multiple stable water isotope pools in a developed landscape in Germany

NASA Astrophysics Data System (ADS)

Orlowski, Natalie; Kraft, Philipp; Pferdmenges, Jakob; Breuer, Lutz

2016-09-01

A dual stable water isotope (δ2H and δ18O) study was conducted in the developed (managed) landscape of the Schwingbach catchment (Germany). The 2-year weekly to biweekly measurements of precipitation, stream, and groundwater isotopes revealed that surface and groundwater are isotopically disconnected from the annual precipitation cycle but showed bidirectional interactions between each other. Apparently, snowmelt played a fundamental role for groundwater recharge explaining the observed differences to precipitation δ values. A spatially distributed snapshot sampling of soil water isotopes at two soil depths at 52 sampling points across different land uses (arable land, forest, and grassland) revealed that topsoil isotopic signatures were similar to the precipitation input signal. Preferential water flow paths occurred under forested soils, explaining the isotopic similarities between top- and subsoil isotopic signatures. Due to human-impacted agricultural land use (tilling and compression) of arable and grassland soils, water delivery to the deeper soil layers was reduced, resulting in significant different isotopic signatures. However, the land use influence became less pronounced with depth and soil water approached groundwater δ values. Seasonally tracing stable water isotopes through soil profiles showed that the influence of new percolating soil water decreased with depth as no remarkable seasonality in soil isotopic signatures was obvious at depths > 0.9 m and constant values were observed through space and time. Since classic isotope evaluation methods such as transfer-function-based mean transit time calculations did not provide a good fit between the observed and calculated data, we established a hydrological model to estimate spatially distributed groundwater ages and flow directions within the Vollnkirchener Bach subcatchment. Our model revealed that complex age dynamics exist within the subcatchment and that much of the runoff must has been stored for much longer than event water (average water age is 16 years). Tracing stable water isotopes through the water cycle in combination with our hydrological model was valuable for determining interactions between different water cycle components and unravelling age dynamics within the study area. This knowledge can further improve catchment-specific process understanding of developed, human-impacted landscapes.

Robustness of fossil fish teeth for seawater neodymium isotope reconstructions under variable redox conditions in an ancient shallow marine setting

NASA Astrophysics Data System (ADS)

Huck, Claire E.; van de Flierdt, Tina; Jiménez-Espejo, Francisco J.; Bohaty, Steven M.; Röhl, Ursula; Hammond, Samantha J.

2016-03-01

Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth, and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources.

Investigation of Chemical and Physical Changes to Bioapatite During Fossilization Using Trace Element Geochemistry, Infrared Spectroscopy and Stable Isotopes

NASA Astrophysics Data System (ADS)

Suarez, C. A.; Kohn, M. J.

2013-12-01

Bioapatite in the form of vertebrate bone can be used for a wide variety of paleo-proxies, from determination of ancient diet to the isotopic composition of meteoric water. Bioapatite alteration during diagenesis is a constant barrier to the use of fossil bone as a paleo-proxy. To elucidate the physical and chemical alteration of bone apatite during fossilization, we analyzed an assortment of fossil bones of different ages for trace elements, using LA-ICP-MS, stable isotopes, and reflected IR spectroscopy. One set of fossil bones from the Pleistocene of Idaho show a diffusion recrystallization profile, however, rare earth element (REE) profiles indicate diffusion adsorption. This suggests that REE diffusion is controlled by changing (namely decreasing) boundary conditions (i.e. decreasing concentration of REE in surrounding pore fluids). Reflected IR analysis along this concentration profile reveal that areas high in U have lost type A carbonate from the crystal structure in addition to water and organics. Stable isotopic analysis of carbon and oxygen will determine what, if any, change in the isotopic composition of the carbonate component of apatite has occurred do to the diffusion and recrystallization process. Analysis of much older bone from the Cretaceous of China reveal shallow REE and U concentration profiles and very uniform reflected IR spectra with a significant loss of type A carbonate throughout the entire bone cortex. Analysis of stable isotopes through the bone cortex will be compared to the stable isotopes collected from the Pleistocene of Idaho.

Plume versus plate origin for the Shatsky Rise oceanic plateau (NW Pacific): Insights from Nd, Pb and Hf isotopes

NASA Astrophysics Data System (ADS)

Heydolph, Ken; Murphy, David T.; Geldmacher, Jörg; Romanova, Irina V.; Greene, Andrew; Hoernle, Kaj; Weis, Dominique; Mahoney, John

2014-07-01

Shatsky Rise, an early Cretaceous igneous oceanic plateau in the NW Pacific, comprises characteristics that could be attributed to either formation by shallow, plate tectonic-controlled processes or to an origin by a mantle plume (head). The plateau was drilled during Integrated Ocean Drilling Program (IODP) Expedition 324. Complementary to a recent trace element study (Sano et al., 2012) this work presents Nd, Pb and Hf isotope data of recovered lava samples cored from the three major volcanic edifices of the Shatsky Rise. Whereas lavas from the oldest edifice yield fairly uniform compositions, a wider isotopic spread is found for lavas erupted on the younger parts of the plateau, suggesting that the Shatsky magma source became more heterogeneous with time. At least three isotopically distinct components can be identified in the magma source: 1) a volumetrically and spatially most common, moderately depleted component of similar composition to modern East Pacific Ridge basalt but with low 3He/4He, 2) an isotopically very depleted component which could represent local, early Cretaceous (entrained) depleted upper mantle, and 3) an isotopically enriched component, indicating the presence of (recycled) continental material in the magma source. The majority of analyzed Shatsky lavas, however, possess Nd-Hf-Pb isotope compositions consistent with a derivation from an early depleted, non-chondritic reservoir. By comparing these results with petrological and trace element data of mafic volcanic rock samples from all three massifs (Tamu, Ori, Shirshov), we discuss the origin of Shatsky Rise magmatism and evaluate the possible involvement of a mantle plume (head).

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS for isotope analysis of long-lived radionuclides

NASA Astrophysics Data System (ADS)

Becker, J. Sabine

2005-04-01

For a few years now inductively coupled plasma mass spectrometry has been increasingly used for precise and accurate determination of isotope ratios of long-lived radionuclides at the trace and ultratrace level due to its excellent sensitivity, good precision and accuracy. At present, ICP-MS and also laser ablation ICP-MS are applied as powerful analytical techniques in different fields such as the characterization of nuclear materials, recycled and by-products (e.g., spent nuclear fuel or depleted uranium ammunitions), radioactive waste control, in environmental monitoring and in bioassay measurements, in health control, in geochemistry and geochronology. Especially double-focusing sector field ICP mass spectrometers with single ion detector or with multiple ion collector device have been used for the precise determination of long-lived radionuclides isotope ratios at very low concentration levels. Progress has been achieved by the combination of ultrasensitive mass spectrometric techniques with effective separation and enrichment procedures in order to improve detection limits or by the introduction of the collision cell in ICP-MS for reducing disturbing interfering ions (e.g., of 129Xe+ for the determination of 129I). This review describes the state of the art and the progress of ICP-MS and laser ablation ICP-MS for isotope ratio measurements of long-lived radionuclides in different sample types, especially in the main application fields of characterization of nuclear and radioactive waste material, environmental research and health controls.

UHPLC-MS/MS method for the quantitation of penicillin G and metabolites in citrus fruit using internal standards.

PubMed

Canzani, Daniele; Hsieh, Kevin; Standland, Matthew; Hammack, Walter; Aldeek, Fadi

2017-02-15

Penicillin G has been applied to citrus trees as a potential treatment in the fight against Huanglongbing (HLB). Here, we have developed and validated a method to identify and quantitate penicillin G and two of its metabolites, penillic acid and penilloic acid, in citrus fruit using ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). This method improves upon a previous method by incorporating isotopically labeled internal standards, namely, penillic acid-D 5 , and penilloic acid-D 5 . These standards greatly enhanced the accuracy and precision of our measurements by compensating for recovery losses, degradation, and matrix effects. When 2g of citrus fruit sample is extracted, the limits of detection (LOD) were determined to be 0.1ng/g for penicillin G and penilloic acid, and 0.25ng/g for penillic acid. At fortification levels of 0.1, 0.25, 1, and 10ng/g, absolute recoveries for penillic and penilloic acids were generally between 50-70%. Recoveries corrected with the isotopically labeled standards were approximately 90-110%. This method will be useful for the identification and quantitation of drug residues and their degradation products using isotopically labeled standards and UHPLC-MS/MS. Published by Elsevier B.V.

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.

Origin discrimination of defatted pork via trace elements profiling, stable isotope ratios analysis, and multivariate statistical techniques.

PubMed

Park, Yu Min; Lee, Cheong Mi; Hong, Joon Ho; Jamila, Nargis; Khan, Naeem; Jung, Jong-Hyun; Jung, Young-Chul; Kim, Kyong Su

2018-09-01

This study verified the origin of 346 defatted Korean and non-Korean pork samples via trace elements profiling, and C and N stable isotope ratios analysis. The analyzed elements were 6 Li, 7 Li, 10 B, 11 B, 51 V , 50 Cr, 52 Cr, 53 Cr, 55 Mn, 58 Ni, 60 Ni, 59 Co, 63 Cu, 65 Cu, 64 Zn, 66 Zn, 69 Ga, 71 Ga, 75 As, 82 Se, 84 Sr, 86 Sr, 87 Sr, 88 Sr, 85 Rb, 94 Mo, 95 Mo, 97 Mo, 107 Ag, 109 Ag, 110 Cd, 111 Cd, 113 Cd, 112 Cd, 114 Cd, 116 Cd, 133 Cs, 206 Pb, 207 Pb, and 208 Pb. Content (mg/kg) of 51 V (0.012), 50 Cr (0.882), 75 As (0.017), 85 Rb (57.7), and 87 Sr (46.3) were high in Korean pork samples whereas 6 Li, 7 Li, 59 Co, 55 Mn, 58 Ni, 84 Sr, 86 Sr, 88 Sr, 111 Cd, and 133 Cs were found higher in non-Korean samples. The results of discriminant analysis showed that the trace elements content and stable isotope ratios were significant for the discrimination of geographical origins with a perfect discrimination rate of 100%. Copyright © 2018 Elsevier Ltd. All rights reserved.

Boron and strontium isotope ratios and major/trace elements concentrations in tea leaves at four major tea growing gardens in Taiwan.

PubMed

Chang, Cheng-Ta; You, Chen-Feng; Aggarwal, Suresh Kumar; Chung, Chuan-Hsiung; Chao, Hung-Chun; Liu, Hou-Chun

2016-06-01

Isotopic compositions of B and Sr in rocks and sediments can be used as tracers for plant provincial sources. This study aims to test whether tea leaf origin can be discriminated using (10)B/(11)B and Sr isotopic composition data, along with concentrations of major/trace elements, in tea specimens collected from major plantation gardens in Taiwan. The tea leaves were digested by microwave and analyzed by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). The data showed significant variations in (87)Sr/(86)Sr ratios (from 0.70482 to 0.71462), which reflect changes in soil, groundwater or irrigation conditions. The most radiogenic tea leaves were found at the Taitung garden and the least radiogenic ones were from the Hualien garden. The δ (11)B was found to change appreciably (δ (11)B = 0.38-23.73 ‰) which could be due to fertilizers. The maximum δ (11)B was also observed in tea samples from the Hualien garden. Principal component analysis combining (87)Sr/(86)Sr, δ (11)B and major/trace elements results successfully discriminated different sources of major tea gardens in Taiwan, except the Hualien gardens, and this may be due to rather complicated local geological settings.

Isotopes as Tracers of the Hawaiian Coffee-Producing Regions

PubMed Central

2011-01-01

Green coffee bean isotopes have been used to trace the effects of different climatic and geological characteristics associated with the Hawaii islands. Isotope ratio mass spectrometry (IRMS) and inductively coupled plasma mass spectrometry ((MC)-ICP-SFMS and ICP-QMS) were applied to determine the isotopic composition of carbon (δ13C), nitrogen (δ15N), sulfur (δ34S), and oxygen (δ18O), the isotope abundance of strontium (87Sr/86Sr), and the concentrations of 30 different elements in 47 green coffees. The coffees were produced in five Hawaii regions: Hawaii, Kauai, Maui, Molokai, and Oahu. Results indicate that coffee plant seed isotopes reflect interactions between the coffee plant and the local environment. Accordingly, the obtained analytical fingerprinting could be used to discriminate between the different Hawaii regions studied. PMID:21838232

TRANSPORT AND FATE OF AMMONIUM AND ITS IMPACT ON URANIUM AND OTHER TRACE ELEMENTS AT A FORMER URANIUM MILL TAILING SITE

PubMed Central

Miao, Ziheng; Nihat, Hakan; McMillan, Andrew Lee; Brusseau, Mark L.

2013-01-01

The remediation of ammonium-containing groundwater discharged from uranium mill tailing sites is a difficult problem facing the mining industry. The Monument Valley site is a former uranium mining site in the southwest US with both ammonium and nitrate contamination of groundwater. In this study, samples collected from 14 selected wells were analyzed for major cations and anions, trace elements, and isotopic composition of ammonium and nitrate. In addition, geochemical data from the U.S. Department of Energy (DOE) database were analyzed. Results showing oxic redox conditions and correspondence of isotopic compositions of ammonium and nitrate confirmed the natural attenuation of ammonium via nitrification. Moreover, it was observed that ammonium concentration within the plume area is closely related to concentrations of uranium and a series of other trace elements including chromium, selenium, vanadium, iron, and manganese. It is hypothesized that ammonium-nitrate transformation processes influence the disposition of the trace elements through mediation of redox potential, pH, and possibly aqueous complexation and solid-phase sorption. Despite the generally relatively low concentrations of trace elements present in groundwater, their transport and fate may be influenced by remediation of ammonium or nitrate at the site. PMID:24357895

Trace element geochemistry of Archean volcanic rocks

NASA Technical Reports Server (NTRS)

Jahn, B.-M.; Shih, C.-Y.; Murthy, V. R.

1974-01-01

The K, Rb, Sr, Ba and rare-earth-element contents of some Archean volcanic rocks from the Vermilion greenstone belt, northeast Minnesota, were determined by the isotopic dilution method. The characteristics of trace element abundances, supported by the field occurrences and major element chemistry, suggest that these volcanic rocks were formed in an ancient island arc system.

Chasing Neoproterozoic Atmospheric Oxygen Ghosts

NASA Astrophysics Data System (ADS)

Bjerrum, C. J.; Canfield, D. E.; Dahl, T. W.

2016-12-01

Increasing atmospheric oxygen has been considered a necessary condition for the evolution of animal life for over half a century. While direct proxies for atmospheric oxygen are difficult to obtain, a number of indirect proxies have been giving us a ghost image of rising atmospheric oxygen at the close of the Precambrian. In this context, redox sensitive elements and isotopes represent the hallmark for a significant reduction in anoxic areas of the world ocean, implicating a significant rise of atmospheric oxygen during the Neoproterozoic. Here, we test to what degree redox sensitive elements in ancient marine sediments are proxies of atmospheric oxygen. We model the redox-chemical evolution of the shelf seas and ocean using a combination of 3D high resolution shelf sea models and a simpler global ocean biogeochemical model including climate weathering feedbacks, a free sea level and parameterized icecaps. We find that ecosystem evolution would have resulted in reorganization of the nutrient and redox balance of the shelf-ocean system causing a significant increase in oxygenated areas that permitted a boosting of trace metal concentrations in the remaining anoxic areas. While this reorganization takes place there is limited net change in the modelled atmospheric oxygen, warning us against interpreting changing trace metal concentrations and isotopes as reflecting a rise in atmospheric oxygen.

The production of ultra-high purity single isotopes or tailored isotope mixtures by ICP-MS

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

Liezers, Martin; Farmer, Orville T.; Dion, Michael P.

2015-01-01

We report the development and testing of a simple collector arrangement for a commercial quadrupole ICP-MS that for the first time has been used to produce small quantities of highly enriched (>99.99%) single isotopes, with deposition rates >10 ng/hour. The collector assembly replaces the standard instrument detector allowing for implantation with simultaneous monitoring of the incident ion current. Even under zero bias implant conditions, low energy (<10 eV), ion collection efficiency was observed to be very high ~99%. 151Eu ion currents of 0.1-0.5 nA were collected on a simple, planar foil without resorting to any type of cup configuration. Recoverymore » of the enriched isotope from such foils is much simpler than from a more complex cup configuration. High rejection of adjacent mass isotopes was demonstrated by selectively implanting 167Er without any discernible co-implantation of 166Er and 168Er. The important analytical possibilities of the new approach to isotope ratio measurement, tracer purification and radiation measurements are discussed.« less

Biological forcing controls the chemistry of reef-building coral skeleton

NASA Astrophysics Data System (ADS)

Meibom, Anders; Mostefaoui, Smail; Cuif, Jean-Pierre; Dauphin, Yannicke; Houlbreque, Fanny; Dunbar, Robert; Constantz, Brent

2007-01-01

We present analyses of major elements C and Ca and trace elements N, S, Mg and Sr in a Porites sp. exoskeleton with a spatial resolution better than ˜150 nm. Trace element variations are evaluated directly against the ultra-structure of the skeleton and are ascribed to dynamic biological forcing. Individual growth layers in the bulk fibrous aragonite skeleton form on sub-daily timescales. Magnesium concentration variations are dramatically correlated with the growth layers, but are uncorrelated with Sr concentration variations. Observed (sub)seasonal relationships between water temperature and skeletal trace-element chemistry are secondary, mediated by sensitive biological processes to which classical thermodynamic formalism does not apply.

Plutonium isotopes in the atmosphere of Central Europe: Isotopic composition and time evolution vs. circulation factors.

PubMed

Kierepko, Renata; Mietelski, Jerzy W; Ustrnul, Zbigniew; Anczkiewicz, Robert; Wershofen, Herbert; Holgye, Zoltan; Kapała, Jacek; Isajenko, Krzysztof

2016-11-01

This paper reports evidence of Pu isotopes in the lower part of the troposphere of Central Europe. The data were obtained based on atmospheric aerosol fraction samples collected from four places in three countries (participating in the informal European network known as the Ring of Five (Ro5)) forming a cell with a surface area of about 200,000km(2). We compared our original data sets from Krakow (Poland, 1990-2007) and Bialystok (Poland, 1991-2007) with the results from two other locations, Prague (Czech Republic; 1997-2004) and Braunschweig (Germany; 1990-2003) to find time evolution of the Pu isotopes. The levels of the activity concentration for (238)Pu and for ((239+240))Pu were estimated to be a few and some tens of nBqm(-3), respectively. However, we also noted some results were much higher (even about 70 times higher) than the average concentration of (238)Pu in the atmosphere. The achieved complex data sets were used to test a new approach to the problem of solving mixing isotopic traces from various sources (here up to three) in one sample. Results of our model, supported by mesoscale atmospheric circulation parameters, suggest that Pu from nuclear weapon accidents or tests and nuclear burnt-up fuel are present in the air. Copyright © 2016 Elsevier B.V. All rights reserved.

Geochemical and isotopic evidence for paleoredox conditions during deposition of the Devonian-Mississippian New Albany Shale, southern Indiana

NASA Technical Reports Server (NTRS)

Beier, J. A.; Hayes, J. M.

1989-01-01

The upper part of the New Albany Shale is divided into three members. In ascending order, these are (1) the Morgan Trail Member, a laminated brownish-black shale; (2) the Camp Run Member, an interbedded brownish-black and greenish-gray shale; and (3) the Clegg Creek Member, also a laminated brownish-black shale. The Morgan Trail and Camp Run Members contain 5% to 6% total organic carbon (TOC) and 2% sulfide sulfur. Isotopic composition of sulfide in these members ranges from -5.0% to -20.0%. C/S plots indicate linear relationships between abundances of these elements, with a zero intercept characteristic of sediments deposited in a non-euxinic marine environment. Formation of diagenetic pyrite was carbon limited in these members. The Clegg Creek Member contains 10% to 15% TOC and 2% to 6% sulfide sulfur. Isotopic compositions of sulfide range from -5.0% to -40%. The most negative values occur in the uppermost Clegg Creek Member and are characteristic of syngenetic pyrite, formed within an anoxic water column. Abundances of carbon and sulfur are greater and uncorrelated in this member, consistent with deposition in as euxinic environment. In addition, DOP (degree of pyritization) values suggest that formation of pyrite was generally iron limited throughout Clegg Creek deposition, but sulfur isotopes indicate that syngenetic (water-column) pyrite becomes an important component in the sediment only in the upper part of the member. At the top of the Clegg Creek Member, a zone of phosphate nodules and trace-metal enrichment coincides with maximal TOC values. During euxinic deposition, phosphate and trace metals accumulated below the chemocline because of limited vertical circulation in the water column. Increased productivity would have resulted in an increased flux of particulate organic matter to the sediment, providing an effective sink for trace metals in the water column. Phosphate and trace metals released from organic matter during early diagenesis resulted in precipitation of metal-rich phosphate nodules.

Sulfur isotope and trace element data from ore sulfides in the Noranda district (Abitibi, Canada): implications for volcanogenic massive sulfide deposit genesis

NASA Astrophysics Data System (ADS)

Sharman, Elizabeth R.; Taylor, Bruce E.; Minarik, William G.; Dubé, Benoît; Wing, Boswell A.

2015-06-01

We examine models for volcanogenic massive sulfide (VMS) mineralization in the ~2.7-Ga Noranda camp, Abitibi subprovince, Superior Province, Canada, using a combination of multiple sulfur isotope and trace element data from ore sulfide minerals. The Noranda camp is a well-preserved, VMS deposit-rich area that is thought to represent a collapsed volcanic caldera. Due to its economic value, the camp has been studied extensively, providing a robust geological framework within which to assess the new data presented in this study. We explore previously proposed controls on mineralization within the Noranda camp and, in particular, the exceptional Au-rich Horne and Quemont deposits. We present multiple sulfur isotope and trace element compositional data for sulfide separates representing 25 different VMS deposits and "showings" within the Noranda camp. Multiple sulfur isotope data for this study have δ34SV-CDT values of between -1.9 and +2.5 ‰, and Δ33SV-CDT values of between -0.59 and -0.03 ‰. We interpret the negative Δ33S values to be due to a contribution of sulfur that originated as seawater sulfate to form the ore sulfides of the Noranda camp VMS deposits. The contribution of seawater sulfate increased with the collapse and subsequent evolution of the Noranda caldera, an inference supported by select trace and major element analyses. In particular, higher concentrations of Se occur in samples with Δ33S values closer to 0 ‰, as well as lower Fe/Zn ratios in sphalerite, suggesting lower pressures and temperatures of formation. We also report a relationship between average Au grade and Δ33S values within Au-rich VMS deposits of the Noranda camp, whereby higher gold grades are associated with near-zero Δ33S values. From this, we infer a dominance of igneous sulfur in the gold-rich deposits, either leached from the volcanic pile and/or directly degassed from an associated intrusion.

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

NASA Technical Reports Server (NTRS)

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

2013-01-01

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

Do Melt Inclusions Answer Big Questions?

NASA Astrophysics Data System (ADS)

Hofmann, A. W.; Sobolev, A. V.

2009-12-01

In a pioneering paper, Sobolev and Shimizu (1993) demonstrated the existence of ultra-depleted melt inclusions in olivine phenocrysts in MORB. They interpreted these as evidence for the preservation of parental melts formed by progressive near-fractional melting. Subsequently many cases have been described where melt inclusions from single basalt samples display enormous chemical and isotopic heterogeneity. The interpretation of these observations hinges critically on whether such melt inclusions can faithfully preserve primary or parental melt composition. If they do, melt inclusion data can truly answer big questions from small-scale observations. If they do not, they answer rather small questions. Favoring the second possibility, Danyushevsky et al. (2004) have suggested that much of the observed variability of highly incompatible trace elements in melt inclusions “may not represent geologically significant melts, but instead reflect localized, grain-scale reaction processes within the magmatic plumbing system.” We disagree and show that this mechanism cannot, for example, explain isotopic heterogeneity measured in several suites of melt inclusions, nor does it not account for the presence of ultra-depleted melts and "ghost" plagioclase signatures in other inclusions. More recently, Spandler et al. (2007) have suggested on the basis of experimental evidence that diffusion rates for REE in olivine are so rapid that parental melt compositions in melt inclusions are rapidly falsified by diffusional exchange with (evolved) host lava. We show that the very fact that extreme chemical and isotopic heterogeneities are routinely preserved in melt inclusions demonstrates that this conclusion is unwarranted, either because residence times of the olivine phenocrysts are much shorter than assumed by Spandler et al. or because the high experimental diffusion rates are caused by an unknown experimental artifact. Although there is no obvious flaw in design and execution of their experiments, geologically relevant diffusion rates are notoriously difficult to determine and may depend on factors not incorporated in the laboratory experiments. More recent diffusion experiments by Remmert et al. (2008) and by Cherniak (2009) have yielded diffusion coefficients three order of magnitude lower than those measured by Spandler. The heavy REE represent a possible exception to the above conclusions. We present data from olivine melt inclusions from Iceland basalts, which show unusual HREE patterns possibly caused by diffusional exchange with the host lava. Sobolev, A.V. & Shimizu, N. (1993) Nature 363, 151-154. Danyushevskii, L.V. et al. (2004) J. Petrol. 45, 2531-2553. Spandler, G., O’Neill, H.St.C., Kamenetsky, V.S. (2007) Nature, 447, 303-306. Remmert, P. Dohmen, R., Chakraborty, S. (2008) EOS Trans. AGU abs. MR331-1844. Cherniak, D.J. (2009) Am. Mineral. Ms. subm.

Extraction of pesticides, dioxin-like PCBs and PAHs in water based commodities using liquid-liquid microextraction and analysis by gas chromatography-mass spectrometry.

PubMed

Dasgupta, Soma; Banerjee, Kaushik; Utture, Sagar; Kusari, Parijat; Wagh, Sameer; Dhumal, Kondiba; Kolekar, Sanjay; Adsule, Pandurang G

2011-09-23

Water based samples such as flavored drinks, juices and drinking water may contain contaminants at ultra trace level belonging to different chemical classes. A novel, simple, low-cost and fast method was developed and validated for trace residue extraction of pesticides, dioxin-like PCBs and PAHs from water and water based samples followed by analysis through gas chromatography (GC) coupled with time-of-flight mass spectrometry (ToFMS). The extraction solvent type, volume; sample volume and other extraction conditions were optimized. This was achieved by extracting 10 mL sample with 250 μL chloroform by vortexing (1 min, standing time of 2 min) followed by centrifugation (6000 rpm, 5 min). The bottom organic layer (200 μL) was pipetted out, evaporated to near dryness and reconstituted in 20 μL of ethyl acetate+cyclohexane (1:9) mixture resulting in an enrichment factor of 400. The recoveries of all compounds were within 76-120% (±10%) with the method detection limit (MDL) ranging from 1 to 250 ng/L depending on the analyte response. The MDLs were 400 times lower than the instrument quantification limits that ranged from 0.4 to 100 ng/mL. The method was further validated in water based drinks (e.g. apple, lemon, pineapple, orange, grape and pomegranate juice). For the juices with suspended pulp, the extraction was carried out with 400 μL chloroform. The extract was analyzed by GC-ToFMS at both 1D and GC×GC modes to chromatographically separate closely eluting interfering compounds the effect of which could not be minimized otherwise. The resulting peak table was filtered to identify a range of compounds belonging to specific classes viz. polycyclic aromatic hydrocarbons, chlorinated, brominated, and nitro compounds. User developed scripts were employed on the basis of identification of the molecular ion and isotope clusters or other spectral characteristics. The method performed satisfactorily in analyzing both incurred as well as market samples. Copyright © 2011 Elsevier B.V. All rights reserved.

Tracing the metabolism of HT-2 toxin and T-2 toxin in barley by isotope-assisted untargeted screening and quantitative LC-HRMS analysis

USDA-ARS?s Scientific Manuscript database

An extensive study of the metabolism of the type-A trichothecene mycotoxins HT-2 toxin and T-2 toxin in barley using liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) is reported. A recently developed untargeted approach based on stable isotopic labelling, LC-Orbitrap-MS a...

Stable isotope fingerprinting: a novel method for identifying plant, fungal, or bacterial origins of amino acids

Treesearch

Thomas Larsen; D. Lee Taylor; Mary Beth Leigh; Diane M. O' Brien

2009-01-01

Amino acids play an important role in ecology as essential nutrients for animals and as currencies in symbiotic associations. Here we present a new approach to tracing the origins of amino acids by identifying unique patterns of carbon isotope signatures generated by amino acid synthesis in plants, fungi, and bacteria ("13C fingerprints...

ChelomEx: Isotope-assisted discovery of metal chelates in complex media using high-resolution LC-MS.

PubMed

Baars, Oliver; Morel, François M M; Perlman, David H

2014-11-18

Chelating agents can control the speciation and reactivity of trace metals in biological, environmental, and laboratory-derived media. A large number of trace metals (including Fe, Cu, Zn, Hg, and others) show characteristic isotopic fingerprints that can be exploited for the discovery of known and unknown organic metal complexes and related chelating ligands in very complex sample matrices using high-resolution liquid chromatography mass spectrometry (LC-MS). However, there is currently no free open-source software available for this purpose. We present a novel software tool, ChelomEx, which identifies isotope pattern-matched chromatographic features associated with metal complexes along with free ligands and other related adducts in high-resolution LC-MS data. High sensitivity and exclusion of false positives are achieved by evaluation of the chromatographic coherence of the isotope pattern within chromatographic features, which we demonstrate through the analysis of bacterial culture media. A built-in graphical user interface and compound library aid in identification and efficient evaluation of results. ChelomEx is implemented in MatLab. The source code, binaries for MS Windows and MAC OS X as well as test LC-MS data are available for download at SourceForge ( http://sourceforge.net/projects/chelomex ).

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

PubMed

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

2015-04-01

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

Measurements of actinides in soil, sediments, water and vegetation in Northern New Mexico

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

Gallaher, B. M.; Efurd, D. W.

2002-01-01

This study was undertaken during 1991 - 1998 to identify the origin of plutonium uranium in northern New Mexico Rio Grande and tributary stream sediments. Isotopic fingerprinting techniques help distinguish radioactivity from Los Alamos National Laboratory (LANL) and from global fallout or natural sources. The geographic area covered by the study extended from the headwaters of the Rio Grande in southern Colorado to Elephant Butte Reservoir in southern New Mexico. Over 100 samples of stream channel and reservoir bottom sediments were analyzed for the atom ratios of plutonium and uranium isotopes using thermal ionization mass spectrometry (TIMS). Comparison of thesemore » ratios against those for fallout or natural sources allowed for quantification of the Laboratory impact. Of the seven major drainages crossing LANL, movement of LANL plutonium into the Rio Grande can only be traced via Los Alamos Canyon. The majority of sampled locations within and adjacent to LANL have little or no input of plutonium from the Laboratory. Samples collected upstream and distant to L A N show an average (+ s.d.) fallout 240Pu/239Pauto m ratio of 0.169 + 0.012, consistent with published worldwide global fallout values. These regional background ratios differ significantly from the 240Pu/239Pu atom ratio of 0.015 that is representative of LANL-derived plutonium entering the Rio Grande at Los Alamos Canyon. Mixing calculations of these sources indicate that the largest proportion (60% to 90%) of the plutonium in the Rio Grande sediments is from global atmospheric fallout, with an average of about 25% from the Laboratory. The LANL plutonium is identifiable intermittently along the 35-km reach of the Rio Grande to Cochiti Reservoir. The source of the LANL-derived plutonium in the Rio Grande was traced primarily to pre-1960 discharges of liquid effluents into a canyon bottom at a distance approximately 20 km upstream of the river. Plutonium levels decline exponentially with distance downstream after mixing with cleaner sediments, yet the LANL isotopic fingerprint remains distinct for at least 55 km from the effluent source. Plutonium isotopes in Rio Grande and Pajarito Plateau sediments are not at levels known to adversely affect public health. Activities of 239+240pwui thin this sample set ranged from 0.001- 0.046 pCUg in the Rio Grande to 3.7 pCi/g near the effluent discharge point. Levels in the Rio Grande are usually more than 1000 times. lower than prescribed cleanup standards. Uranium in stream and reservoir sediments is predominantly within natural concentration ranges and is of natural uranium isotopic composition. None of the sediments from the Rio Grande show identifiable Laboratory uranium, using the isotopic ratios. These results suggest that the mass of Laboratory-derived uranium entering the Rio Grande is small relative to the natural load carried with river sediments.« less

Applications of an NMHC isotope analysis system on trace gases from plant and CARIBIC samples

NASA Astrophysics Data System (ADS)

Zuiderweg, A.; Holzinger, R.; Röckmann, T.; Brenninkmeijer, C. A. M.

2009-04-01

Isotope analysis can be a useful tool in constraining the budgets (sources and sinks) of atmospheric trace species and is increasingly applied for organic constituents. We present initial results from an automated system for isotope ratio measurements on atmospheric hydrocarbons. The inlet system is flexible and allows analysis of trace gases from medium size to large ambient air samples (5-300L) as well as CO2-concentrates from samples that have been extracted offline. Long-term testing has shown this system to be stable to 1.5‰ vs. VPDB (or better) across all tested C2-C6 compounds, and methyl chloride. This system has now been utilized to analyze emissions rates and isotopic fractionation of 7 NMHCs from Sequoia leaf litter under conditions of UV exposure. These experiments indicate, for example, δ13C depletion in methyl chloride (CH3Cl) In the range of -90 to -113 v. VPDB with continuously increasing emission rates reaching to 3.26 ng/h/gdw after constant UV exposure of 7 hours, in a dynamic reactor. Other experiments with variation in UV exposure were also undertaken, indicating variation in emission rates and δ13C with UV intensity. In addition, first results from analysis of samples from concentrates taken during the CARIBIC II (http://www.caribic-atmospheric.com/) campaign, beginning with flight 26 (return flight, Male, Maldives, to Dusseldorf, Germany, August 2000), which features flight path air originating from over the Atlantic Ocean and the Indian subcontinent, is presented.

Volatile abundances and oxygen isotopes in basaltic to dacitic lavas on mid-ocean ridges: The role of assimilation at spreading centers

USGS Publications Warehouse

Wanless, V.D.; Perfit, M.R.; Ridley, W.I.; Wallace, P.J.; Grimes, Craig B.; Klein, E.M.

2011-01-01

Most geochemical variability in MOR basalts is consistent with low- to moderate-pressure fractional crystallization of various mantle-derived parental melts. However, our geochemical data from MOR high-silica glasses, including new volatile and oxygen isotope data, suggest that assimilation of altered crustal material plays a significant role in the petrogenesis of dacites and may be important in the formation of basaltic lavas at MOR in general. MOR high-silica andesites and dacites from diverse areas show remarkably similar major element trends, incompatible trace element enrichments, and isotopic signatures suggesting similar processes control their chemistry. In particular, very high Cl and elevated H2O concentrations and relatively light oxygen isotope ratios (~ 5.8‰ vs. expected values of ~ 6.8‰) in fresh dacite glasses can be explained by contamination of magmas from a component of ocean crust altered by hydrothermal fluids. Crystallization of silicate phases and Fe-oxides causes an increase in δ18O in residual magma, but assimilation of material initially altered at high temperatures results in lower δ18O values. The observed geochemical signatures can be explained by extreme fractional crystallization of a MOR basalt parent combined with partial melting and assimilation (AFC) of amphibole-bearing altered oceanic crust. The MOR dacitic lavas do not appear to be simply the extrusive equivalent of oceanic plagiogranites. The combination of partial melting and assimilation produces a distinct geochemical signature that includes higher incompatible trace element abundances and distinct trace element ratios relative to those observed in plagiogranites.

Genesis of the Permian karstic Pingguo bauxite deposit, western Guangxi, China

NASA Astrophysics Data System (ADS)

Liu, Xuefei; Wang, Qingfei; Zhang, Qizuan; Yang, Shujuan; Liang, Yayun; Zhang, Ying; Li, Yan; Guan, Tao

2017-10-01

More than 0.5 billion tons of late Permian bauxite overlies the karstic topography of the Maokou Formation of western Guangxi in China. Here, we provide new mineralogical, geochemical, Sr-Nd-Pb isotopic, and pyrite S isotope and trace element compositional data for the Pingguo bauxite deposit, aiming to further our understanding of the genesis of Permian bauxite. The Pingguo bauxite contains three distinct layers: a lower layer dominated by ferric clay or weathered iron ore, a middle layer of cryptocrystalline and oolitic bauxite ore, and an upper layer dominated by argillaceous bauxite. The bauxite ore is mainly diaspore, pyrite, chamosite, and anatase, whereas the argillaceous bauxite contains diaspore, kaolinite, pyrophyllite, pyrite, and anatase. Two types of pyrite have been identified within the bauxite: fine-grained and framboidal pyrite (Py1) occurring in aggregates and coarse-grained and euhedral pyrite (Py2). Py1 is enriched in trace elements and is thought to have a diagenetic origin, whereas Py2 is deficient in trace elements and is considered to have formed by later recrystallization. The S isotopic composition of pyrite (-34.11 to -18.91‰) and visible ovoid microorganisms within the bauxite provide evidences of microbial activity during bauxite formation. The Sr-Nd-Pb isotopic composition of the bauxite indicates that these ores were generated by the weathering of basalts belonging to the Emeishan Large Igneous Province (LIP) and limestones of the Maokou Formation. Microorganisms were likely to have enhanced the dissolution and weathering of the parent rock and facilitated the precipitation of diaspore under near-surface conditions.

A novel method for rapid in vitro radiobioassay

NASA Astrophysics Data System (ADS)

Crawford, Evan Bogert

Rapid and accurate analysis of internal human exposure to radionuclides is essential to the effective triage and treatment of citizens who have possibly been exposed to radioactive materials in the environment. The two most likely scenarios in which a large number of citizens would be exposed are the detonation of a radiation dispersal device (RDD, "dirty bomb") or the accidental release of an isotope from an industrial source such as a radioisotopic thermal generator (RTG). In the event of the release and dispersion of radioactive materials into the environment in a large city, the entire population of the city -- including all commuting workers and tourists -- would have to be rapidly tested, both to satisfy the psychological needs of the citizens who were exposed to the mental trauma of a possible radiation dose, and to satisfy the immediate medical needs of those who received the highest doses and greatest levels of internal contamination -- those who would best benefit from rapid, intensive medical care. In this research a prototype rapid screening method to screen urine samples for the presence of up to five isotopes, both individually and in a mixture, has been developed. The isotopes used to develop this method are Co-60, Sr-90, Cs-137, Pu-238, and Am-241. This method avoids time-intensive chemical separations via the preparation and counting of a single sample on multiple detectors, and analyzing the spectra for isotope-specific markers. A rapid liquid-liquid separation using an organic extractive scintillator can be used to help quantify the activity of the alpha-emitting isotopes. The method provides quantifiable results in less than five minutes for the activity of beta/gamma-emitting isotopes when present in the sample at the intervention level as defined by the Centers for Disease Control and Prevention (CDC), and quantifiable results for the activity levels of alpha-emitting isotopes present at their respective intervention levels in approximately 30 minutes of sample preparation and counting time. Radiation detector spectra -- e.g. those from high-purity germanium (HPGe) gamma detectors and liquid scintillation detectors -- which contain decay signals from multiple isotopes often have overlapping signals: the counts from one isotope's decay can appear in energy channels associated with another isotope's decay, complicating the calculation of each isotope's activity. The uncertainties associated with analyzing these spectra have been traced in order to determine the effects of one isotope's count rate on the sensitivity and uncertainty associated with each other isotope. The method that was developed takes advantage of activated carbon filtration to eliminate quenching effects and to make the liquid scintillation spectra from different urine samples comparable. The method uses pulse-shape analysis to reduce the interference from beta emitters in the liquid scintillation spectrum and improve the minimum detectable activity (MDA) and minimum quantifiable activity (MQA) for alpha emitters. The method uses an HPGe detector to quantify the activity of gamma emitters, and subtract their isotopes' contributions to the liquid scintillation spectra via a calibration factor, such that the pure beta and pure alpha emitters can be identified and quantified from the resulting liquid scintillation spectra. Finally, the method optionally uses extractive scintillators to rapidly separate the alpha emitters from the beta emitters when the activity from the beta emitters is too great to detect or quantify the activity from the alpha emitters without such a separation. The method is able to detect and quantify all five isotopes, with uncertainties and biases usually in the 10-40% range, depending upon the isotopic mixtures and the activity ratios between each of the isotopes.

Climate variations of Central Asia on orbital to millennial timescales.

PubMed

Cheng, Hai; Spötl, Christoph; Breitenbach, Sebastian F M; Sinha, Ashish; Wassenburg, Jasper A; Jochum, Klaus Peter; Scholz, Denis; Li, Xianglei; Yi, Liang; Peng, Youbing; Lv, Yanbin; Zhang, Pingzhong; Votintseva, Antonina; Loginov, Vadim; Ning, Youfeng; Kathayat, Gayatri; Edwards, R Lawrence

2016-11-11

The extent to which climate variability in Central Asia is causally linked to large-scale changes in the Asian monsoon on varying timescales remains a longstanding question. Here we present precisely dated high-resolution speleothem oxygen-carbon isotope and trace element records of Central Asia's hydroclimate variability from Tonnel'naya cave, Uzbekistan, and Kesang cave, western China. On orbital timescales, the supra-regional climate variance, inferred from our oxygen isotope records, exhibits a precessional rhythm, punctuated by millennial-scale abrupt climate events, suggesting a close coupling with the Asian monsoon. However, the local hydroclimatic variability at both cave sites, inferred from carbon isotope and trace element records, shows climate variations that are distinctly different from their supra-regional modes. Particularly, hydroclimatic changes in both Tonnel'naya and Kesang areas during the Holocene lag behind the supra-regional climate variability by several thousand years. These observations may reconcile the apparent out-of-phase hydroclimatic variability, inferred from the Holocene lake proxy records, between Westerly Central Asia and Monsoon Asia.

Climate variations of Central Asia on orbital to millennial timescales

PubMed Central

Cheng, Hai; Spötl, Christoph; Breitenbach, Sebastian F. M.; Sinha, Ashish; Wassenburg, Jasper A.; Jochum, Klaus Peter; Scholz, Denis; Li, Xianglei; Yi, Liang; Peng, Youbing; Lv, Yanbin; Zhang, Pingzhong; Votintseva, Antonina; Loginov, Vadim; Ning, Youfeng; Kathayat, Gayatri; Edwards, R. Lawrence

2016-01-01

The extent to which climate variability in Central Asia is causally linked to large-scale changes in the Asian monsoon on varying timescales remains a longstanding question. Here we present precisely dated high-resolution speleothem oxygen-carbon isotope and trace element records of Central Asia’s hydroclimate variability from Tonnel’naya cave, Uzbekistan, and Kesang cave, western China. On orbital timescales, the supra-regional climate variance, inferred from our oxygen isotope records, exhibits a precessional rhythm, punctuated by millennial-scale abrupt climate events, suggesting a close coupling with the Asian monsoon. However, the local hydroclimatic variability at both cave sites, inferred from carbon isotope and trace element records, shows climate variations that are distinctly different from their supra-regional modes. Particularly, hydroclimatic changes in both Tonnel’naya and Kesang areas during the Holocene lag behind the supra-regional climate variability by several thousand years. These observations may reconcile the apparent out-of-phase hydroclimatic variability, inferred from the Holocene lake proxy records, between Westerly Central Asia and Monsoon Asia. PMID:27833133

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.

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

PubMed Central

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

2016-01-01

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

The nitrogen isotopic ratio of HC3N towards the L1544 prestellar core

NASA Astrophysics Data System (ADS)

Hily-Blant, P.; Faure, A.; Vastel, C.; Magalhaes, V.; Lefloch, B.; Bachiller, R.

2018-06-01

The origin of the heavily fractionated reservoir of nitrogen in comets remains an issue in the theory of their formation and hence of the solar system. Whether the fractionated reservoir traced by comets is inherited from the interstellar cloud or is the product of processes taking place in the protostar, or in the protoplanetary disk, remains unclear. So far, observations of nitrogen isotopic ratios in protostars or prestellar cores have not securely identified such a fractionated reservoir owing to the intrinsic difficulty of direct isotopic ratios measurements. In this article, we report the detection of 5 rotational lines of HC3N, including the weaker components of the hyperfine multiplets, and two rotational lines of its 15N isotopologue, towards the L1544 prestellar core. Based on a MCMC/non-LTE multi-line analysis at the hyperfine level, we derive the column densities of HC3N (8.0 ± 0.4 × 1013cm-2) and HC_3^{15}N (2.0 ± 0.4 × 1011cm-2) and derive an isotopic ratio of 400±20(1σ). This value suggests that HC3N is slightly depleted in 15N in L1544 with respect to the elemental 14N/15N ratio of ≈330 in the present-day local interstellar medium. Our study also stresses the need for radiative calculations at the hyperfine level. Finally, the comparison of the derived ratio with those obtained in CN and HCN in the same core seems to favor CN+C2H2 as the dominant formation route to HC3N. However, uncertainties in the isotopic ratios preclude definitive conclusions.

Sufficient oxygen for animal respiration 1,400 million years ago

PubMed Central

Zhang, Shuichang; Wang, Xiaomei; Wang, Huajian; Bjerrum, Christian J.; Hammarlund, Emma U.; Costa, M. Mafalda; Connelly, James N.; Zhang, Baomin; Su, Jin; Canfield, Donald E.

2016-01-01

The Mesoproterozoic Eon [1,600–1,000 million years ago (Ma)] is emerging as a key interval in Earth history, with a unique geochemical history that might have influenced the course of biological evolution on Earth. Indeed, although this time interval is rather poorly understood, recent chromium isotope results suggest that atmospheric oxygen levels were <0.1% of present levels, sufficiently low to have inhibited the evolution of animal life. In contrast, using a different approach, we explore the distribution and enrichments of redox-sensitive trace metals in the 1,400 Ma sediments of Unit 3 of the Xiamaling Formation, North China Block. Patterns of trace metal enrichments reveal oxygenated bottom waters during deposition of the sediments, and biomarker results demonstrate the presence of green sulfur bacteria in the water column. Thus, we document an ancient oxygen minimum zone. We develop a simple, yet comprehensive, model of marine carbon−oxygen cycle dynamics to show that our geochemical results are consistent with atmospheric oxygen levels >4% of present-day levels. Therefore, in contrast to previous suggestions, we show that there was sufficient oxygen to fuel animal respiration long before the evolution of animals themselves. PMID:26729865

Iron isotope biogeochemistry of Neoproterozoic marine shales

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Experiment to Characterize Aircraft Volatile Aerosol and Trace-Species Emissions (EXCAVATE)

NASA Technical Reports Server (NTRS)

Anderson, B. E.; Branham, H.-S.; Hudgins, C. H.; Plant, J. V.; Ballenthin, J. O.; Miller, T. M.; Viggiano, A. A.; Blake, D. R.; Boudries, H.; Canagaratna, M.

2005-01-01

The Experiment to Characterize Aircraft Volatile and Trace Species Emissions (EXCAVATE) was conducted at Langley Research Center (LaRC) in January 2002 and focused upon assaying the production of aerosols and aerosol precursors by a modern commercial aircraft, the Langley B757, during ground-based operation. Remaining uncertainty in the postcombustion fate of jet fuel sulfur contaminants, the need for data to test new theories of particle formation and growth within engine exhaust plumes, and the need for observations to develop air quality models for predicting pollution levels in airport terminal areas were the primary factors motivating the experiment. NASA's Atmospheric Effects of Aviation Project (AEAP) and the Ultra Effect Engine Technology (UEET) Program sponsored the experiment which had the specific objectives of determining ion densities; the fraction of fuel S converted from S(IV) to S(VI); the concentration and speciation of volatile aerosols and black carbon; and gas-phase concentrations of long-chain hydrocarbon and PAH species, all as functions of engine power, fuel composition, and plume age.

Distribution of siderophile and other trace elements in melt rock at the Chicxulub impact structure

NASA Technical Reports Server (NTRS)

Schuraytz, B. C.; Lindstrom, D. J.; Martinez, R. R.; Sharpton, V. L.; Marin, L. E.

1994-01-01

Recent isotopic and mineralogical studies have demonstrated a temporal and chemical link between the Chicxulub multiring impact basin and ejecta at the Cretaceous-Tertiary boundary. A fundamental problem yet to be resolved, however, is identification of the projectile responsible for this cataclysmic event. Drill core samples of impact melt rock from the Chichxulub structure contain Ir and Os abundances and Re-Os isotopic ratios indicating the presence of up to approx. 3 percent meteoritic material. We have used a technique involving microdrilling and high sensitivity instrumental neutron activation analysis (INAA) in conjunction with electron microprobe analysis to characterize further the distribution of siderophile and other trace elements among phases within the C1-N10 melt rock.

Pb, Sr and Nd isotopic composition and trace element characteristics of coarse airborne particles collected with passive samplers

NASA Astrophysics Data System (ADS)

Hoàng-Hòa, Thi Bich; Stille, Peter; Dietze, Volker; Guéguen, Florence; Perrone, Thierry; Gieré, Reto

2015-09-01

Passive samplers for collection of coarse airborne particulate matter have been installed in and around the coal-mining town of Cam Pha, Quang Ninh Province (Vietnam). Analysis of Pb, Sr, and Nd isotope ratios and of major and trace element distribution patterns in atmospheric particulates collected at three stations allowed for the identification of four important dust components: (1) coal dust from an open-pit mine and fly ash particles from a coal-fired power station, (2) diesel soot, (3) traffic dust from metal, tire and pavement abrasion, and (4) limestone-derived dust. Outside of the coal-mining area, traffic-derived dust defines the atmospheric baseline composition of the studied environment.

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Anthropogenic plutonium-244 in the environment: Insights into plutonium’s longest-lived isotope

DOE PAGES

Armstrong, Christopher R.; Brant, Heather A.; Nuessle, Patterson R.; ...

2016-02-22

Owing to the rich history of heavy element production in the unique high flux reactors that operated at the Savannah River Site, USA (SRS) decades ago, trace quantities of plutonium with highly unique isotopic characteristics still persist today in the SRS terrestrial environment. Development of an effective sampling, processing, and analysis strategy enables detailed monitoring of the SRS environment, revealing plutonium isotopic compositions, e.g., 244Pu, that reflect the unique legacy of plutonium production at SRS. This work describes the first long-term investigation of anthropogenic 244Pu occurrence in the environment. Environmental samples, consisting of collected foot borne debris, were taken atmore » SRS over an eleven year period, from 2003 to 2014. Separation and purification of trace plutonium was carried out followed by three stage thermal ionization mass spectrometry (3STIMS) measurements for plutonium isotopic content and isotopic ratios. Furthermore, significant 244Pu was measured in all of the years sampled with the highest amount observed in 2003. The 244Pu content, in femtograms (fg = 10 –15 g) per gram, ranged from 0.31 fg/g to 44 fg/g in years 2006 and 2003 respectively. In all years, the 244Pu/ 239Pu atom ratios were significantly higher than global fallout, ranging from 0.003 to 0.698 in years 2014 and 2003 respectively.« less

Potential use of stable isotope and fatty acid analyses for traceability of geographic origins of jumbo squid (Dosidicus gigas).

PubMed

Gong, Yi; Li, Yunkai; Chen, Xinjun; Chen, Ling

2018-04-15

Squid is an important seafood resource for Asian and European countries. With the continuous development of processed squid products, an effective traceability system has become increasingly prominent. Here, we attempt to trace the fishery products of the main target species, jumbo squid (Dosidicus gigas), by using biochemical tracers. Carbon and nitrogen isotope ratios (δ 13 C and δ 15 N values) and fatty acid profiles were identified in squid from three harvest locations in the eastern Pacific Ocean by isotope ratio mass spectrometry and gas chromatography/mass spectrometry, respectively. Comparative analysis was used to evaluate the geographic variations in tracers and to identify the suitable discriminatory variables among origins. Significant spatial variations were found in isotopic values and fatty acid profiles in squid muscle tissues, possibly because of different food availability and/or oceanographic conditions that each group experiences at a given location. The stepwise discriminant analysis indicated that δ 15 N, C16:1n7, C17:1n7, C18:2n6, C20:1 and C20:4n6 were effective variables at differentiating origin. Combined use of stable isotope ratios and fatty acid analyses could trace geographic origins of jumbo squid. This study provides an alternative approach for improving authenticity evaluation of commercial squid products. Copyright © 2018 John Wiley & Sons, Ltd.

Anthropogenic plutonium-244 in the environment: Insights into plutonium’s longest-lived isotope

PubMed Central

Armstrong, Christopher R.; Brant, Heather A.; Nuessle, Patterson R.; Hall, Gregory; Cadieux, James R.

2016-01-01

Owing to the rich history of heavy element production in the unique high flux reactors that operated at the Savannah River Site, USA (SRS) decades ago, trace quantities of plutonium with highly unique isotopic characteristics still persist today in the SRS terrestrial environment. Development of an effective sampling, processing, and analysis strategy enables detailed monitoring of the SRS environment, revealing plutonium isotopic compositions, e.g., 244Pu, that reflect the unique legacy of plutonium production at SRS. This work describes the first long-term investigation of anthropogenic 244Pu occurrence in the environment. Environmental samples, consisting of collected foot borne debris, were taken at SRS over an eleven year period, from 2003 to 2014. Separation and purification of trace plutonium was carried out followed by three stage thermal ionization mass spectrometry (3STIMS) measurements for plutonium isotopic content and isotopic ratios. Significant 244Pu was measured in all of the years sampled with the highest amount observed in 2003. The 244Pu content, in femtograms (fg = 10−15 g) per gram, ranged from 0.31 fg/g to 44 fg/g in years 2006 and 2003 respectively. In all years, the 244Pu/239Pu atom ratios were significantly higher than global fallout, ranging from 0.003 to 0.698 in years 2014 and 2003 respectively. PMID:26898531

Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

USGS Publications Warehouse

Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

2017-01-01

Conclusions: The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and is universally applicable for both heteroelement-bearing and heteroelement-free organic-compound classes. The sensitivity and simplicity of the on-line EA-Cr/HTC-IRMS technique provide a much needed tool for routine hydrogen-isotope source tracing of organic contaminants in the environment. Copyright © 2016 John Wiley & Sons, Ltd.

Paragneiss zircon geochronology and trace element geochemistry, North Qaidam HP/UHP terrane, western China

USGS Publications Warehouse

Mattinson, C.G.; Wooden, J.L.; Zhang, J.X.; Bird, D.K.

2009-01-01

In the southeastern part of the North Qaidam terrane, near Dulan, paragneiss hosts minor peridotite and UHP eclogite. Zircon geochronology and trace element geochemistry of three paragneiss samples (located within a ???3 km transect) indicates that eclogite-facies metamorphism resulted in variable degrees of zircon growth and recrystallization in the three samples. Inherited zircon core age groups at 1.8 and 2.5 Ga suggest that the protoliths of these rocks may have received sediments from the Yangtze or North China cratons. Mineral inclusions, depletion in HREE, and absence of negative Eu anomalies indicate that zircon U-Pb ages of 431 ?? 5 Ma and 426 ?? 4 Ma reflect eclogite-facies zircon growth in two of the samples. Ti-in-zircon thermometry results are tightly grouped at ???660 and ???600 ??C, respectively. Inclusions of metamorphic minerals, scarcity of inherited cores, and lack of isotopic or trace element inheritance demonstrate that significant new metamorphic zircon growth must have occurred. In contrast, zircon in the third sample is dominated by inherited grains, and rims show isotopic and trace element inheritance, suggesting solid-state recrystallization of detrital zircon with only minor new growth. ?? 2009 Elsevier Ltd.

The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

NASA Technical Reports Server (NTRS)

Lauretta, D. S.

2004-01-01

During the past three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. As part of my startup package I received funds to construct a state-of-the-art experimental facility to study gas-solid reaction kinetics. Much of our effort was spent developing the methodology to measure the abundance and isotopic composition of Hg at ultratrace levels in solid materials. In our first study, the abundance and isotopic composition of Hg was determined in bulk samples of the Murchison (CM) and Allende (CV) carbonaceous chondrites. We have continued our study of mercury in primitive meteorites and expanded the suite of meteorites to include other members of the CM and CV chondrite group as well as CI and CO chondrites. Samples of the CI chondrite Orgueil, the CM chondrites Murray, Nogoya, and Cold Bokkeveld, the CO chondrites Kainsaz, Omans, and Isna, and the CV chondrites Vigarano, Mokoia, and Grosnaja were tested. We have developed a thermal analysis ICP-MS technique and applied it to the study of a suite of thermally labile elements (Zn, As, Se, Cd, In, Sn, Sb, Te, Hg, Au, Tl, Pb, and Bi) in geologic materials as well.

Origin Of Extreme 3He/4He Signatures In Icelandic Lavas: Insights From Melt Inclusion Studies

NASA Astrophysics Data System (ADS)

Harlou, R.; Kent, A. J.; Breddam, K.; Davidson, J. P.; Pearson, D. G.

2003-12-01

Helium isotopes are considered a powerful tool for tracking different mantle domains. Yet, the origin of He isotope variations in many basaltic suites remains enigmatic and often difficult to link with more lithophile chemical and isotopic tracers. One problem is that He isotope ratios are measured from crushed olivines and thus reflect prior fluid and melt fluxes trapped in inclusions within the olivine grains, whereas the lithophile elements mainly reflect the host lava. In an attempt to link He and lithophile element variations, we have characterized the major and trace element composition including volatile elements, of olivine-hosted melt inclusions from three ankaramitic lavas from Vestfirdir, NW-Iceland. Previous studies have reported extreme 3He/4He ratios from NW-Iceland and one ankaramite (SEL97) has been suggested to provide the most precise estimate of the radiogenic (Sr-Nd-Pb) isotopic composition of a relatively undegassed (high 3He/4He) mantle component (C or FOZO) common to several ocean islands (Hilton et al. 1999, EPSL 173, 53-60). The samples investigated here exhibit amongst the highest 3He/4He ratios observed in terrestrial rocks (42.9 and 34.8 R/Ra). A detailed account of the trace element signature of melt inclusions in these samples may thus help explain the origin of FOZO. One sample of similar composition to these, has a lower He content and a relatively poorly defined He isotope composition of 8.15 +/- 5.1 R/Ra (Breddam & Kurz, 2001, EOS, 82, F1315). In terms of major elements, the whole rock data reflect olivine accumulation, whereas the melt inclusion data reflect ol + cpx fractionation. The melt inclusions are generally basaltic (Mg#: 52-62), with primitive mantle normalised trace element concentrations that are broadly parallel the host lavas. There is little compositional difference between melt inclusion populations from high and low 3He/4He lavas, although inclusions of the low 3He/4He lava have lower S and moderately lower Cl. The observed range of trace element ratios: [La/Sm]N 1-4, [La/Yb]N 1-5, Sr/Nd 14-24, Ba/Rb 9-23, and Ce/Pb 5-46, covers much of the range observed in Icelandic alkali basalts. The compositional similarities between inclusions and host lavas suggests that bulk rock compositions are petrogenetically related to the melts sampled by melt inclusions. If He predominantly resides in these inclusions, it suggests that the whole rock composition is an aggregate derived from the same melts that contain the measured He.

Tracing Life in the Earliest Terrestrial Rock Record

NASA Astrophysics Data System (ADS)

Lepland, A.; van Zuilen, M.; Arrhenius, G.

2001-12-01

The principal method for studying the earliest traces of life in the metamorphosed, oldest (> 3.5 Ga) terrestrial rocks involves determination of isotopic composition of carbon, mainly prevailing as graphite. It is generally believed that this measure can distinguish biogenic graphite from abiogenic varieties. However, the interpretation of life from carbon isotope ratios has to be assessed within the context of specific geologic circumstances requiring (i) reliable protolith interpretation (ii) control of secondary, metasomatic processes, and (iii) understanding of different graphite producing mechanisms and related carbon isotopic systematics. We have carried out a systematic study of abundance, isotopic composition and petrographic associations of graphite in rocks from the ca. 3.8 Ga Isua Supracrustal Belt (ISB) in southern West Greenland. Our study indicates that most of the graphite in ISB occurs in carbonate-rich metasomatic rocks (metacarbonates) while sedimentary units, including banded iron formations (BIFs) and metacherts, have exceedingly low graphite concentrations. Regardless of isotopic composition of graphite in metacarbonate rocks, their secondary origin disqualifies them from providing evidence for traces of life stemming from 3.8 Ga. Recognition of the secondary origin of Isua metacarbonates thus calls for reevaluation of biologic interpretations by Schidlowski et al. (1979) and Mojzsis et al. (1996) that suggested the occurrence of 3.8 Ga biogenic graphite in these rocks. The origin of minute quantities of reduced carbon, released from sedimentary BIFs and metacherts at combustion steps > 700 C remains to be clarified. Its isotopic composition (d13C from -18 to -25%) may hint at a biogenic origin. However, such isotopically light carbon was also found in Proterozoic mafic dykes cross-cutting the metasedimentary units in the ISB. The occurrence of isotopically light, reduced carbon in biologically irrelevant dykes may indicate secondary graphite crystallization from CO2 or CH4- containing fluids that in turn may derive from bioorganic sources. If this were the case, trace amounts of isotopically light secondary graphite can also be expected in metasediments, complicating the usage of light graphite as primary biomarker. The possibility of recent organic contamination, particularly important in low graphite samples, needs also to be considered; it appears as a ubiquitous component released at combustion in the 400 to 500 deg range. - A potential use of the apatite-graphite association as a biomarker has been proposed in the study by Mojzsis et al. (1996). Close inspection of several hundred apatite crystals from Isua BIFs and metacherts did, however, not show an association between these two minerals, moreover graphite is practically absent in these metasediments. In contrast, apatite crystals in the non-sedimentary metacarbonate rocks were found commonly to have invaginations, coatings and inclusions of abundant graphite. Considering that such graphite inclusions in apatite are restricted to the secondary metasomatic carbonate rocks in the ISB this association can not be considered as a primary biomarker in the Isua Supracrustal Belt References: Mojzsis,S.J, .Arrhenius,G., McKeegan, K.D.,.Harrison, T.M.,.Nutman, A.P & C.R.L.Friend.,1996. Nature 384: 55 Schidlowski, M., Appel, P.W.U., Eichmann, R. & Junge, C.E., 1979. Geochim. Cosmochim. Acta 43: 189-190.

Estimation of Plutonium-240 Mass in Waste Tanks Using Ultra-Sensitive Detection of Radioactive Xenon Isotopes from Spontaneous Fission

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

Bowyer, Theodore W.; Gesh, Christopher J.; Haas, Daniel A.

This report details efforts to develop a technique which is able to detect and quantify the mass of 240Pu in waste storage tanks and other enclosed spaces. If the isotopic ratios of the plutonium contained in the enclosed space is also known, then this technique is capable of estimating the total mass of the plutonium without physical sample retrieval and radiochemical analysis of hazardous material. Results utilizing this technique are reported for a Hanford Site waste tank (TX-118) and a well-characterized plutonium sample in a laboratory environment.

Understanding the Marine Chromium Isotope Record from Modern and Ancient Carbonates

NASA Astrophysics Data System (ADS)

Parkinson, I. J.; Bonnand, P.; James, R. H.; Fairchild, I. J.; Dixon, S.

2011-12-01

Chromium isotopes may provide a powerful tool for reconstructing the redox state of ancient seawater because Cr isotope fractionation is large (up to 7% in δ53Cr) during the reduction of Cr(VI) to Cr(III) in natural waters [1]. Recent studies have demonstrated that although Cr(VI) is predicted to be the thermodynamically stable form in seawater (as CrO42-), significant amounts (5-20%) of Cr(III) may also be present in surface waters [2]. Therefore the δ53Cr of seawater could vary by up to 2%. Marine carbonates potentially provide a means to extracting information about the Cr isotopic composition of seawater in the geological past and we have developed a high-precision double-spike technique for analysing Cr isotopes in carbonates [3]. The δ53Cr of modern Bahamas Bank carbonates (+0.76%) is broadly consistent with these carbonates recording a seawater Cr signature. Moreover, these pure carbonates contain significant amounts of Cr (1-4 ppm), which indicates that Cr is strongly partitioned into calcium carbonate. Therefore carbonates are likely to provide a faithful record of the δ53Cr composition of seawater. Shallow marine carbonates from the Phanerozoic range in δ53Cr from +0.76 to +1.8%, and some Neoproterozoic carbonates also have heavy Cr isotopic compositions of +0.5 to +1.0 %. Such compositions may reflect changes in the inputs of Cr to the oceans and/or changes in the redox state of the oceans. However, to interpret Cr isotopic compositions in ancient carbonates additionally requires a careful assessment of their trace element contents. This study aims to demonstrate how a combination of redox sensitive trace elements, such as Ce, and Cr isotopes allow an assessment of the marine chromium isotope record. [1] Ellis et al., 2002, Science, 295, 2060-2062. [2] Connolly et al., 2006, Deep Sea Res. Part I, 2006 53, 1975-1988. [3] P. Bonnand, et al., 2011, J. Anal. At. Spectr., 26, 528-535.

Hf-Nd isotope decoupling in the oceanic lithosphere: constraints from spinel peridotites from Oahu, Hawaii

NASA Astrophysics Data System (ADS)

Bizimis, Michael; Sen, Gautam; Salters, Vincent J. M.

2004-01-01

We present a detailed geochemical investigation on the Hf, Nd and Sr isotope compositions and trace and major element contents of clinopyroxene mineral separates from spinel lherzolite xenoliths from the island of Oahu, Hawaii. These peridotites are believed to represent the depleted oceanic lithosphere beneath Oahu, which is a residue of a MORB-related melting event some 80-100 Ma ago at a mid-ocean ridge. Clinopyroxenes from peridotites from the Salt Lake Crater (SLC) show a large range of Hf isotopic compositions, from ɛHf=12.2 (similar to the Honolulu volcanics series) to extremely radiogenic, ɛHf=65, at nearly constant 143Nd/ 144Nd ratios ( ɛNd=7-8). None of these samples show any isotopic evidence for interaction with Koolau-type melts. A single xenolith from the Pali vent is the only sample with Hf and Nd isotopic compositions that falls within the MORB field. The Hf isotopes correlate positively with the degree of depletion in the clinopyroxene (e.g. increasing Mg#, Cr#, decreasing Ti and heavy REE contents), but also with increasing Zr and Hf depletions relative to the adjacent REE in a compatibility diagram. The Lu/Hf isotope systematics of the SLC clinopyroxenes define apparent ages of 500 Ma or older and these compositions cannot be explained by mixing between any type of Hawaiian melts and the depleted Pacific lithosphere. Metasomatism of an ancient (e.g. 1 Ga or older) depleted peridotite protolith can, in principle, explain these apparent ages and the Nd-Hf isotope decoupling, but requires that the most depleted samples were subject to the least amount of metasomatism. Alternatively, the combined isotope, trace and major element compositions of these clinopyroxenes are best described by metasomatism of the 80-100 Ma depleted oceanic lithosphere by melts products of extensive mantle-melt interaction between Honolulu Volcanics-type melts and the depleted lithosphere.

The Canadian Geo-location Endeavour Using Isotopes and Trace Elements in Hair

NASA Astrophysics Data System (ADS)

Chartrand, Michelle M. G.; St-Jean, Gilles; Dalpe, Claude; Wojtyk, James

2010-05-01

The Canadian human hair provenance project has two main objectives: 1) to build a Canadian database of isotopes and trace elements from tap water and hair samples, and 2) to assess the extent of temporal effects on these samples. To address objective 1, a cross-Canada sampling campaign has been started to collect hair and tap water samples. In the past two years, our group has collected samples from the eastern part of Canada (Newfoundland, Nova Scotia, New Brunswick, Prince Edward Island, Quebec and Ontario). Water samples are divided into three groups - groundwater, surface water and bottled water. The GIS maps show the isotopic distribution of the tap water sources varies with latitude. Hair is analyzed for carbon (C), nitrogen (N) and hydrogen (H) isotopes. The C and N results show that in general, Canadians eat a typical diet showing a small isotopic variation. However, some cases will be presented which may explain why some people have C and N values outlying the collected sample average. In terms of H isotopes in human hair, GIS maps illustrate the distribution of this isotope in the eastern provinces of Canada. In some cases, a large variation in H was observed for the same locality with no significant difference in human activities and/or consumption. However, based on hair collected from across Canada from previous years, H isotopes in hair show a correlation to water collected from the same locality. To address objective 2, hair and tap water samples were collected at 4 month intervals (to represent different seasons in Canada) from several volunteers residing in two cities located in the province of Ontario (i.e. Sudbury and Ottawa) and one city from the province of Quebec (i.e. Montreal). For all isotopes measured, there was little variation observed over the course of the year in any individual from those small to medium-size cities. On-going sampling efforts will address if any variation may occur on a yearly basis.

Magma mixing and the generation of isotopically juvenile silicic magma at Yellowstone caldera inferred from coupling 238U–230Th ages with trace elements and Hf and O isotopes in zircon and Pb isotopes in sanidine

USGS Publications Warehouse

Stelten, Mark E.; Cooper, Kari M.; Vazquez, Jorge A.; Reid, Mary R.; Barfod, Gry H.; Wimpenny, Josh; Yin, Qing-Zhu

2013-01-01

The nature of compositional heterogeneity within large silicic magma bodies has important implications for how silicic reservoirs are assembled and evolve through time. We examine compositional heterogeneity in the youngest (~170 to 70 ka) post-caldera volcanism at Yellowstone caldera, the Central Plateau Member (CPM) rhyolites, as a case study. We compare 238U–230Th age, trace-element, and Hf isotopic data from zircons, and major-element, Ba, and Pb isotopic data from sanidines hosted in two CPM rhyolites (Hayden Valley and Solfatara Plateau flows) and one extracaldera rhyolite (Gibbon River flow), all of which erupted near the caldera margin ca. 100 ka. The Hayden Valley flow hosts two zircon populations and one sanidine population that are consistent with residence in the CPM reservoir. The Gibbon River flow hosts one zircon population that is compositionally distinct from Hayden Valley flow zircons. The Solfatara Plateau flow contains multiple sanidine populations and all three zircon populations found in the Hayden Valley and Gibbon River flows, demonstrating that the Solfatara Plateau flow formed by mixing extracaldera magma with the margin of the CPM reservoir. This process highlights the dynamic nature of magmatic interactions at the margins of large silicic reservoirs. More generally, Hf isotopic data from the CPM zircons provide the first direct evidence for isotopically juvenile magmas contributing mass to the youngest post-caldera magmatic system and demonstrate that the sources contributing magma to the CPM reservoir were heterogeneous in 176Hf/177Hf at ca. 100 ka. Thus, the limited compositional variability of CPM glasses reflects homogenization occurring within the CPM reservoir, not a homogeneous source.

Temporal geochemical evolution of Kilauea Volcano: Comparison of Hilina and Puna Basalt

NASA Astrophysics Data System (ADS)

Chen, C.-Y.; Frey, F. A.; Rhodes, J. M.; Eastern, R. M.

Temporal geochcmical variations in Hawaiian shield-building lavas provide important constraints on the origin and evolution of these lavas. We determined the major and trace element content, and Sr, Nd and Pb isotopic ratios of the oldest subaerially exposed lavas on Kilauea Volcano, i.e., the >25 Ka to perhaps 100 Ka, Hilina Basalt. Except for lower K2O and Rb abundances in Hilina lavas, the compositions of these prehistoric lavas overlap with historical Kilauea lavas. Although the studied Hilina lavas are not highly altered, the lower abundances of K2O and Rb may reflect post-eruptive alteration. Compared with historical Kilauea lavas, Hilina lavas have a similar range in Sr and Nd isotopic ratios, but they range to more radiogenic Pb isotopic ratios. The mantle source of Kilauea lavas is heterogeneous in isotopic ratios and perhaps in abundance ratios of some incompatible elements, but there is no evidence for systematic long-term geochemical variations in the source of Kilauea lavas. None of the prehistoric Kilauea lavas have isotopic characteristics similar to those of subaerial Mauna Loa lavas. Apparently, the sources and ascent paths of lavas forming the adjacent Kilauea and Mauna Loa shields have largely remained distinct during subaerial growth of the Kilauea shield. Compared to lavas from other Hawaiian shields, Kilauea lavas range to relatively high 206Pb/204Pb and low 87Sr/86Sr. These isotopic ratios are correlated with trace element abundance ratios that involve Nb, e.g., Zr/Nb; some Hilina lavas define the upper range in 206Pb/204Pb (˜18.82), and they have low Zr/Nb (˜8). This "Kilauea component" which has isotopic characteristics similar to the FOZO component (e.g., Hauri et al., 1994a] is an intrinsic part of the Hawaiian plume.

Ultra-Sensitive Elemental Analysis Using Plasmas 4.Application of Inductively Coupled Plasma Mass Spectrometry to the Study of Environmental Radioactivity

NASA Astrophysics Data System (ADS)

Yoshida, Satoshi

Applications of inductively coupled plasma mass spectrometry (ICP-MS) to the determination of long-lived radionuclides in environmental samples were summarized. In order to predict the long-term behavior of the radionuclides, related stable elements were also determined. Compared with radioactivity measurements, the ICP-MS method has advantages in terms of its simple analytical procedures, prompt measurement time, and capability of determining the isotope ratio such as240Pu/239Pu, which can not be separated by radiation. Concentration of U and Th in Japanese surface soils were determined in order to determine the background level of the natural radionuclides. The 235U/238U ratio was successfully used to detect the release of enriched U from reconversion facilities to the environment and to understand the source term. The 240Pu/239Pu ratios in environmental samples varied widely depending on the Pu sources. Applications of ICP-MS to the measurement of I and Tc isotopes were also described. The ratio between radiocesium and stable Cs is useful for judging the equilibrium of deposited radiocesium in a forest ecosystem.

What's New in the Site Characterization Tool Box: Molecular Biological Tools to Identify Microorganisms that Degrade Contaminants and Contaminant-Specific Isotope Analysis to Identify Sources and Document Degradation

EPA Science Inventory

In the past, it was necessary to conduct intensive sampling and monitoring of concentrations of contaminants in ground water to trace plumes back to their true source. Now it is possible to determine the ratio of stable isotopes of carbon, hydrogen or chlorine in the contaminan...

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

ERIC Educational Resources Information Center

Mead, Chris

2014-01-01

This dissertation is presented in two sections. First, I explore two methods of using stable isotope analysis to trace environmental and biogeochemical processes. Second, I present two related studies investigating student understanding of the biogeochemical concepts that underlie part one. Fe and Hg are each biogeochemically important elements in…

Stable isotope tracing of Ni and Cu pollution in North-East Norway: Potentials and drawbacks.

PubMed

Šillerová, Hana; Chrastný, Vladislav; Vítková, Martina; Francová, Anna; Jehlička, Jan; Gutsch, Marissa R; Kocourková, Jana; Aspholm, Paul E; Nilsson, Lars O; Berglen, Tore F; Jensen, Henning K B; Komárek, Michael

2017-09-01

The use of Ni and Cu isotopes for tracing contamination sources in the environment remains a challenging task due to the limited information about the influence of various biogeochemical processes influencing stable isotope fractionation. This work focuses on a relatively simple system in north-east Norway with two possible endmembers (smelter-bedrock) and various environmental samples (snow, soil, lichens, PM 10 ). In general, the whole area is enriched in heavy Ni and Cu isotopes highlighting the impact of the smelting activity. However, the environmental samples exhibit a large range of δ 60 Ni (-0.01 ± 0.03‰ to 1.71 ± 0.02‰) and δ 65 Cu (-0.06 ± 0.06‰ to -3.94 ± 0.3‰) values which exceeds the range of δ 60 Ni and δ 65 Cu values determined in the smelter, i.e. in feeding material and slag (δ 60 Ni from 0.56 ± 0.06‰ to 1.00 ± 0.06‰ and δ 65 Cu from -1.67 ± 0.04‰ to -1.68 ± 0.15‰). The shift toward heavier Ni and Cu δ values was the most significant in organic rich topsoil samples in the case of Ni (δ 60 Ni up to 1.71 ± 0.02‰) and in lichens and snow in the case of Cu (δ 65 Cu up to -0.06 ± 0.06‰ and -0.24 ± 0.04‰, respectively). These data suggest an important biological and biochemical fractionation (microorganisms and/or metal uptake by higher plants, organo-complexation etc.) of Ni and Cu isotopes, which should be quantified separately for each process and taken into account when using the stable isotopes for tracing contamination in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Atmospheric Trace Gas Abundances and Stable Isotope Ratios via IR-LIF

NASA Technical Reports Server (NTRS)

Blake, Geoffrey A.

2004-01-01

We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These studies form the necessary precursors to the development of compact, lightweight stable isotope/trace gas sensors for future planetary missions.

Detection and Monitoring of Toxic Chemical at Ultra Trace Level by Utilizing Doped Nanomaterial

PubMed Central

Khan, Sher Bahadar; Rahman, Mohammed M.; Akhtar, Kalsoom; Asiri, Abdullah M.

2014-01-01

Composite nanoparticles were synthesized by eco-friendly hydrothermal process and characterized by different spectroscopic techniques. All the spectroscopic techniques suggested the synthesis of well crystalline optically active composite nanoparticles with average diameter of ∼30 nm. The synthesized nanoparticles were applied for the development of chemical sensor which was fabricated by coating the nanoparticles on silver electrode for the recognition of phthalimide using simple I–V technique. The developed sensor exhibited high sensitivity (1.7361 µA.mM−1.cm−2), lower detection limit (8.0 µM) and long range of detection (77.0 µM to 0.38 M). Further the resistances of composite nanoparticles based sensor was found to be 2.7 MΩ which change from 2.7 to 1.7 with change in phthalimide concentration. The major advantages of the designed sensor over existing sensors are its simple technique, low cost, lower detection limit, high sensitivity and long range of detection. It can detect phthalimide even at trace level and sense over wide range of concentrations. Therefore the composite nanoparticals would be a better choice for the fabrication of phthalimide chemical sensor and would be time and cost substituted implement for environmental safety. PMID:25329666

MONITORING OF WATERWAYS FOR EMERGING ...

EPA Pesticide Factsheets

Assessing the potential impact to the aquatic environment from emerging contaminants, entails monitoring a complex mixture (pharmaceuticals, polar pesticides, industrial by- products and degradation products) in natural waters. The presence of these chemicals, often at ultra-trace levels, may be responsible for development of sub-lethal toxic effects in aquatic organisms (i.e., reproductive dysfunction, immune dysfunction, neurological disorders). Conventional sampling techniques (i.e., grab sampling) often are insufficient for detecting these trace levels. An integrative sampler, the Polar Organic Chemical Integrative Sampler (POCIS), developed by the USGS Columbia Environmental Research Center, provided a way to measure the time-weighted average concentrations of these complex mixtures of contaminants. When POCIS was combined with liquid chromatography/mass spectrometry (LC/MS), it proved to be a powerful tool in identification and quantification of polar anthropogenic contaminants. Data from a pilot study showed the antibiotic azithromycin, illicit drugs [methamphetamine and MDMA (Ecstasy)], polyfluorinated organic acids (PFOA and PFOS) (essential ingredients in the manufacture of fluoropolymers), and surfactants [i.e., diethanolamine polyethylene glycols (DAPGs), polyethylene glycols (PEGs), and nonylphenol ethoxylates (NPEOs)] were all present in the extracts from the effluents of three wastewater treatment plants and other bodies of natural waters. Althoug

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

USGS Publications Warehouse

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

1981-01-01

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

Trace Element Study of MORB Glasses from 14¡ã-16¡ãN along Mid-Atlantic Ridge by LA-ICP- MS

NASA Astrophysics Data System (ADS)

Barzoi, C. A.; Casey, J. F.; Gao, Y.; Lapen, T.

2007-12-01

A comparison of 20 MORB glasses from 14°-16° N along the Mid-Atlantic Ridge using both solution-based and in situ laser ablation-based ICP-MS trace element analyses on the same samples was conducted. Li, Be, Sc, Ti, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Tb, Gd, Dy, Ho, Er, Tm, Yb,Lu, Hf, Ta, Pb, Th, and U were analyzed using the Varian 810 quadrupole ICP-MS. The instrument features a 90 degree ion mirror and low noise double-off-axis quadrupole that allows high sensitivity and low backgrounds. Precision in term of relative standard deviation (RSD) of the measurements for both methods based on repeated analyses of USGS BIR-1G and BHVO-2G glass standards and Max Planck KL-2G glass standard is within 5 % for all trace elements with the exception of Pb, which averaged 12 %. Measured trace element abundances are within 2% of recommended standard values using both solution and laser ablation methods. Comparison between the analyte concentrations obtained by solution-based ICP-MS and in situ microanalysis by laser ablation reveals little systematic differences in abundances(<5% for all elements). The two-method correlation and strong repeatability of the results indicate that rapid in situ trace element analysis by laser ablation ICP-MS is likely to become a preferred method of trace element analysis for MORB glasses. Our geochemical results and previous studies of MORB glasses in the region of the MAR between 14°-16°N show that basalts are characterized isotopic and incompatible element enrichment.The nature of the enrichment has been the topic of significant discussion and speculation because a specific mantle plume is not well defined in the region. Likewise the magma supply is probably small in the region as the magmatic crust is interpreted to be very thin in most of the area studied. Integrated studies of major element, trace element, and isotopic variations among basalts, gabbroic rocks and igneous and residual ultramafic rocks in the region indicate that 1) the enriched basalts have positive Ta-Nb anomalies, enriched relative to U, Th, and La 2) basalts have relatively high SiO2 abundances compared to the global average, 3) basalts show a HIMU isotopic signature, and 4) bulk major element abundances and mineral chemistry in mantle rocks indicate that they are among the most depleted,although variably refertilized, residual mantle assemblages sampled to date along MORs.We suggest that much of the regional variation in major and trace element data, as well as isotopic data and the unusual regional geology (multiple core complexes) can be explained by melting of a sub-axial mantle that contains two end members, one highly depleted and the other enriched. These components appear to involve ancient recycled ocean crust and lithospheric mantle.

Quantitative Determination of Isotope Ratios from Experimental Isotopic Distributions

PubMed Central

Kaur, Parminder; O’Connor, Peter B.

2008-01-01

Isotope variability due to natural processes provides important information for studying a variety of complex natural phenomena from the origins of a particular sample to the traces of biochemical reaction mechanisms. These measurements require high-precision determination of isotope ratios of a particular element involved. Isotope Ratio Mass Spectrometers (IRMS) are widely employed tools for such a high-precision analysis, which have some limitations. This work aims at overcoming the limitations inherent to IRMS by estimating the elemental isotopic abundance from the experimental isotopic distribution. In particular, a computational method has been derived which allows the calculation of 13C/12C ratios from the whole isotopic distributions, given certain caveats, and these calculations are applied to several cases to demonstrate their utility. The limitations of the method in terms of the required number of ions and S/N ratio are discussed. For high-precision estimates of the isotope ratios, this method requires very precise measurement of the experimental isotopic distribution abundances, free from any artifacts introduced by noise, sample heterogeneity, or other experimental sources. PMID:17263354

Integration of ultra-high field MRI and histology for connectome based research of brain disorders

PubMed Central

Yang, Shan; Yang, Zhengyi; Fischer, Karin; Zhong, Kai; Stadler, Jörg; Godenschweger, Frank; Steiner, Johann; Heinze, Hans-Jochen; Bernstein, Hans-Gert; Bogerts, Bernhard; Mawrin, Christian; Reutens, David C.; Speck, Oliver; Walter, Martin

2013-01-01

Ultra-high field magnetic resonance imaging (MRI) became increasingly relevant for in vivo neuroscientific research because of improved spatial resolutions. However, this is still the unchallenged domain of histological studies, which long played an important role in the investigation of neuropsychiatric disorders. While the field of biological psychiatry strongly advanced on macroscopic levels, current developments are rediscovering the richness of immunohistological information when attempting a multi-level systematic approach to brain function and dysfunction. For most studies, histology sections lost information on three-dimensional reconstructions. Translating histological sections to 3D-volumes would thus not only allow for multi-stain and multi-subject alignment in post mortem data, but also provide a crucial step in big data initiatives involving the network analyses currently performed with in vivo MRI. We therefore investigated potential pitfalls during integration of MR and histological information where no additional blockface information is available. We demonstrated that strengths and requirements from both methods can be effectively combined at a spatial resolution of 200 μm. However, the success of this approach is heavily dependent on choices of hardware, sequence and reconstruction. We provide a fully automated pipeline that optimizes histological 3D reconstructions, providing a potentially powerful solution not only for primary human post mortem research institutions in neuropsychiatric research, but also to help alleviate the massive workloads in neuroanatomical atlas initiatives. We further demonstrate (for the first time) the feasibility and quality of ultra-high spatial resolution (150 μm isotopic) imaging of the entire human brain MRI at 7T, offering new opportunities for analyses on MR-derived information. PMID:24098272

Time constraints on the origin of large volume basalts derived from O-isotope and trace element mineral zoning and U-series disequilibria in the Laki and Grímsvötn volcanic system

NASA Astrophysics Data System (ADS)

Bindeman, Ilya N.; Sigmarsson, Olgeir; Eiler, John

2006-05-01

The 1783-1784 AD fissure eruption of Laki (Iceland) produced 15 km 3 of homogeneous basaltic lavas and tephra that are characterized by extreme (3‰) 18O-depletion relative to normal mantle. Basaltic tephra erupted over the last 8 centuries and as late as in November 2004 from the Grímsvötn central volcano, which together with Laki are a part of a single volcanic system, is indistinguishable in δ18O from Laki glass. This suggests that all tap a homogeneous and long-lived low- δ18O magma reservoir. In contrast, we observe extreme oxygen isotope heterogeneity (2.2-5.2‰) in olivine and plagioclase contained within these lavas and tephra, and disequilibrium mineral-glass oxygen-isotope fractionations. Such low- δ18O glass values, and extreme 3‰ range in δ18O olivine have not been described in any other unaltered basalt. The energy constrained mass balance calculation involving oxygen isotopes and major element composition calls for an origin of the Laki-Grímsvötn quartz tholeiitic basaltic melts with δ18O = 3.1‰ by bulk digestion of low- δ18O hydrated basaltic crust with δ18O = - 4‰ to + 1‰, rather than magma mixing with ultra-low- δ18O silicic melt. The abundant Pleistocene hyaloclastites, which were altered by synglacial meltwaters, can serve as a likely assimilant material for the Grímsvötn magmas. The ( 226Ra / 230Th) activity ratio in Laki lavas and 20th century Grímsvötn tephras is 13% in-excess of secular equilibrium, but products of the 20th century Grímsvötn eruptions have equilibrium ( 210Pb / 226Ra). Modeling of oxygen isotope exchange between disequilibrium phenocrysts and magmas, and these short-lived U-series nuclides yields a coherent age for the Laki-Grímsvötn magma reservoir between 100 and 1000 yrs. We propose the existence of uniquely fingerprinted, low- δ18O, homogeneous, large volume, and long-lived basaltic reservoir beneath the Laki-Grímsvötn volcanic system that has been kept alive in its position above the center of the Icelandic mantle plume. Melt generation, crustal assimilation, magma storage and homogenization all took place in only a few thousands of years at most.

Flotation-separation and ICP-AES determination of ultra trace amounts of copper, cadmium, nickel and cobalt using 2-aminocyclopentene-1-dithiocarboxylic acid.

PubMed

Shamsipur, Mojtaba; Hashemi, Omid Reza; Safavi, Afsaneh

2005-09-01

A rapid flotation method for separation and enrichment of ultra trace amounts of copper(II), cadmium(II), nickel(II) and cobalt(II) ions from water samples is established. At pH 6.5 and with sodium dodecylsulfate used as a foaming reagent, Cu2+, Cd2+, Ni2+ and Co2+ were separated simultaneously with 2-aminocyclopentene-1-dithiocarboxylic acid (ACDA) added to 1 l of aqueous solution. The proposed procedure of preconcentration is applied prior to the determination of these four analytes using inductivity coupled plasma-atomic emission spectrometry (ICP-AES). The effects of pH, concentration of ACDA, applicability of different surfactants and foreign ions on the separation efficiency were investigated. The preconcentration factor of the method is 1000 and the detection limits of copper(II), cadmium(II), nickel(II) and cobalt(II) ions are 0.078, 0.075, 0.072 and 0.080 ng ml(-1), respectively.

Major, Trace, and Volatile (CO2, H2O, S, F, and Cl) Elements from 1000+ Hawaiian Olivine-hosted Melt Inclusions Reveal the Dynamics of Crustal Recycling

NASA Astrophysics Data System (ADS)

Marske, J. P.; Hauri, E. H.; Trusdell, F.; Garcia, M. O.; Pietruszka, A. J.

2015-12-01

Global cycling of volatile elements (H2O, CO2, F, S, Cl) via subduction to deep mantle followed by entrainment and melting within ascending mantle plumes is an enigmatic process that controls key aspects of hot spot volcanism (i.e. melting rate, magma supply, degassing, eruptive style). Variations in radiogenic isotope ratios (e.g.187Os/188Os) at hot spots such as Hawaii reveal magmatic processes within deep-seated mantle plumes (e.g. mantle heterogeneity, lithology, and melt transport). Shield-stage lavas from Hawaii likely originate from a mixed plume source containing peridotite and recycled oceanic crust (pyroxenite) based on variations of radiogenic isotopes. Hawaiian lavas display correlations among isotopes, major and trace elements [1] that might be expected to have an expression in the volatile elements. To investigate this link, we present Os isotopic ratios (n=51), and major, trace, and volatile elements from 1003 olivine-hosted melt inclusions (MI) and their host minerals from tephra from Koolau, Mauna Loa, Hualalai, Kilauea, and Loihi volcanoes. The data show a strong correlation between MI volatile contents and incompatible trace element ratios (La/Yb) with Os isotopes of the same host olivines and reveal large-scale volatile heterogeneity and zonation exists within the Hawaiian plume. 'Loa' chain lavas, which are thought to originate from greater proportions of recycled oceanic crust/pyroxenite, have MIs with lower H2O, S, F, and Cl contents compared to 'Kea' chain lavas that were derived from more peridotite-rich sources. The depletion of volatile elements in the 'Loa' volcano MIs can be explained if they tapped an ancient dehydrated oceanic crust component within the Hawaiian plume. Higher extents of melting beneath 'Loa' volcanoes can also explain these depletions. The presence of dehydrated recycled mafic material in the plume source suggests that subduction effectively devolatilizes part of the oceanic crust. These results are similar to the observed shifts in H2O/Ce ratios near the Easter and Samoan hotspots [2,3]. Thus, it appears that multiple hotspots may record relative H2O depletions and possibly other volatiles. [1] Hauri et al. 1996, Nature 382, 415-419. [2] Dixon et al. 2002, Nature 420:385-89 [3] Workman et al. 2006, EPSL 241:932-51.

Understanding the Calcium Isotope and Trace Metal Composition of Elasmobranch Teeth: Implications for Recreating the δ44/40Ca of Seawater

NASA Astrophysics Data System (ADS)

Akhtar, A.; Higgins, J. A.

2017-12-01

Non-traditional stable isotopes in marine fossils have the potential to act as archives of paleo-seawater chemistry, biological evolution, and ancient ecosystems. In particular, bioapatite in elasmobranch enamel has been shown to be a robust proxy for environmental, geochemical and ecological reconstructions through Earth history due to its temporal range (from Devonian to present day) and resistance to diagenetic alteration. Moreover, frequent replacement rates of teeth in individuals, and high species level diversity and global distribution ensure a sample suite that encompasses a wide range of geographies and ecosystems. Here we present δ44/40Ca, δ87/86Sr and trace element (e.g. Sr/Ca, Mg/Ca) data from a suite of 300 teeth spanning the Cretaceous to present day and representing primary, secondary and tertiary piscivores. Modern teeth analyzed as part of this study have an average δ44/40Ca value of -2.07±0.48‰ (2s, n = 80) and Sr/Ca ratio of 2.30±0.24 mmol/mol (2s, n = 40), both offset from present day seawater (0 permil and 8.6 mmol/mol, respectively) due to a combination of inorganic (e.g. mineral precipitation) and biological (e.g. ionic regulation) effects. The total range in δ44/40Ca values in modern teeth is 1.19‰, the same order as that expected for variations in the δ44/40Ca value of ancient seawater. Using results from synthetic apatite synthesis experiments, mathematical modeling, and measurements of shark soft-tissue (e.g. blood and flesh), we explore sources of Ca isotope variability in shark teeth and evaluate their potential as archives of ancient seawater chemistry.

Isotopic and elemental analysis of fish tissues for provenance determination

NASA Astrophysics Data System (ADS)

Zannella, Carmela; Adamo, Paola; Opper, Christine; Schwendinger, Susanne; Knezevic, Sara; Van den Oever, Sabrina; Tchaikovsky, Anastassiya; Zitek, Andreas; Prohaska, Thomas

2017-04-01

The reliable tracing of the productions flows of food products through the entire supply chain is an essential requirement for all types of food commodities qualified by origin, composition and quality. This is a minimum requirement to implement safety for the consumer, enhance consumer confidence and countervail fraudulent practices. One important food commodity is fish and fish products. Reliable methods to trace the origin of fish have become of high importance. The investigation focused on the identification of adequate geochemical marker in fish meat and the corresponding linkage to the ambient water. The Sr/Ca ratio along with the 87Sr/86Sr isotope ratio analyzed by (multi collector) inductively coupled plasma mass spectrometry (MC ICP-MS) proved to be the most potential tools in this respect. For the first time, a direct link of fish meat to water could be accomplished.In addition, fish hard parts (otoliths, fin rays, fish bones) were under investigation to reconstruct the habitat changes during the lifespan of a fishes life. Fish hard parts have the potential to serve as "life time recorder". Thus the spatial investigation of the elemental and isotopic composition can be used to monitor habitat changes with time. The spatially resolved data of hard tissues was collected by means of Laser Ablation Split Stream ICP-MS/MC ICP-MS. This work is accomplished within the scope of the project "CSI: TRACE YOUR FOOD".

Characterization of Surface Water and Groundwater Quality in the Lower Tano River Basin Using Statistical and Isotopic Approach.

NASA Astrophysics Data System (ADS)

Edjah, Adwoba; Stenni, Barbara; Cozzi, Giulio; Turetta, Clara; Dreossi, Giuliano; Tetteh Akiti, Thomas; Yidana, Sandow

2017-04-01

Adwoba Kua- Manza Edjaha, Barbara Stennib,c,Giuliano Dreossib, Giulio Cozzic, Clara Turetta c,T.T Akitid ,Sandow Yidanae a,eDepartment of Earth Science, University of Ghana Legon, Ghana West Africa bDepartment of Enviromental Sciences, Informatics and Statistics, Ca Foscari University of Venice, Italy cInstitute for the Dynamics of Environmental Processes, CNR, Venice, Italy dDepartment of Nuclear Application and Techniques, Graduate School of Nuclear and Allied Sciences University of Ghana Legon This research is part of a PhD research work "Hydrogeological Assessment of the Lower Tano river basin for sustainable economic usage, Ghana, West - Africa". In this study, the researcher investigated surface water and groundwater quality in the Lower Tano river basin. This assessment was based on some selected sampling sites associated with mining activities, and the development of oil and gas. Statistical approach was applied to characterize the quality of surface water and groundwater. Also, water stable isotopes, which is a natural tracer of the hydrological cycle was used to investigate the origin of groundwater recharge in the basin. The study revealed that Pb and Ni values of the surface water and groundwater samples exceeded the WHO standards for drinking water. In addition, water quality index (WQI), based on physicochemical parameters(EC, TDS, pH) and major ions(Ca2+, Na+, Mg2+, HCO3-,NO3-, CL-, SO42-, K+) exhibited good quality water for 60% of the sampled surface water and groundwater. Other statistical techniques, such as Heavy metal pollution index (HPI), degree of contamination (Cd), and heavy metal evaluation index (HEI), based on trace element parameters in the water samples, reveal that 90% of the surface water and groundwater samples belong to high level of pollution. Principal component analysis (PCA) also suggests that the water quality in the basin is likely affected by rock - water interaction and anthropogenic activities (sea water intrusion). This was confirm by further statistical analysis (cluster analysis and correlation matrix) of the water quality parameters. Spatial distribution of water quality parameters, trace elements and the results obtained from the statistical analysis was determined by geographical information system (GIS). In addition, the isotopic analysis of the sampled surface water and groundwater revealed that most of the surface water and groundwater were of meteoric origin with little or no isotopic variations. It is expected that outcomes of this research will form a baseline for making appropriate decision on water quality management by decision makers in the Lower Tano river Basin. Keywords: Water stable isotopes, Trace elements, Multivariate statistics, Evaluation indices, Lower Tano river basin.

Lu-Hf isotopic memory of plume-lithosphere interaction in the source of layered mafic intrusions, Windimurra Igneous Complex, Yilgarn Craton, Australia

NASA Astrophysics Data System (ADS)

Nebel, O.; Arculus, R. J.; Ivanic, T. J.; Nebel-Jacobsen, Y. J.

2013-10-01

Most layered mafic intrusions (LMI) are formed via multiple magma injections into crustal magma chambers. These magmas are originally sourced from the mantle, likely via plume activity, but may interact with the overriding lithosphere during ascent and emplacement in the crust. The magma injections lead to the establishment of different layers and zones with complex macroscopic, microscopic and cryptic compositional layering through magmatic differentiation and associated cumulate formation, sometimes accompanied by crustal assimilation. These complex mineralogical and petrological processes obscure the nature of the mantle sources of LMI, and typically have limited the degree to which parental liquids can be fully characterised. Here, we present Lu-Hf isotope data for samples from distinct layers of the Upper Zone of the Windimurra Igneous Complex (WIC), an immense late-Archean LMI in the West Australian Yilgarn Craton. Lu-Hf isotope systematics of whole rocks are well correlated (MSWD=5.6, n=17) with an age of ˜3.05±0.05 Ga and initial ɛHf˜+8. This age, however, is older than whole rock Sm-Nd and zircon U-Pb ages of the intrusion, both of which are ca. 2.8 Ga. Stratigraphically-controlled initial Hf isotope variations (associated with multiple episodes of emplacement at ca. 2.8 Ga) indicate isotope mixing between a near-chondritic and an ultra-radiogenic component, the latter with ɛHf[2.8 Ga]>+15. This Hf isotope mixing creates a pseudochron-relationship at the time of intrusion of ˜250 Myr that is superimposed on subsequent radiogenic ingrowth after crystallisation, generating an age that predates the actual emplacement event. Mixing between late-stage crystallisation products (melt + crystals) from the Middle Zone and replenishing, plume-derived liquids was followed by crystal accumulation in a chemically evolving magma chamber. The ultra-radiogenic Hf isotope endmember in the WIC mantle source requires parent-daughter ratios consistent with very early formation in Earth history, akin to early Archean komatiitic plume sources. We propose that plume-derived melts that formed the Windimurra LMI reacted with ancient refractory lithospheric keels already underpinning ancient cratons, creating a melt with extremely high ɛHf[t]. Melting a refractory component with super-chondritic, time-integrated high Lu/Hf, in this case by plume-lithosphere interaction, simultaneously accounts for the extreme Hf isotope signals, Hf-Nd isotope decoupling, and difference in radiometric Lu-Hf and Sm-Nd ages.

Determination of trace levels of benzophenone-type ultra-violet filters in real matrices by bar adsorptive micro-extraction using selective sorbent phases.

PubMed

Almeida, C; Stępkowska, A; Alegre, A; Nogueira, J M F

2013-10-11

Bar adsorptive micro-extraction (BAμE), using selective sorbent phases, followed by liquid desorption in combination with high performance liquid chromatography-diode array detection (BAμE-LD/HPLC-DAD), is proposed for the determination of trace levels of four benzophenone-type UV filters (benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2,4-hydroxybenzophenone and 4-hydroxybenzophenone) in real matrices. By comparing three polymers (P1, P2 and P3) and five activated carbons (AC1, AC2, AC3, AC4 and AC5) phases, P2 (a modified pyrrolidone polymer) and AC4 coatings showed much higher selectivity and capacity through BAμE, where the former offers multiple mechanisms of interaction and faster equilibrium kinetics. Assays performed on 25mL of ultra-pure water samples spiked at the 8.0μg/L level, yielded recoveries ranging from 76.6±8.3% to 103.5±6.4% depending on the sorbent phase used (P2 or AC4), under optimized experimental conditions. The analytical performance showed convenient detection limits (0.3-0.5μg/L) and good linear dynamic ranges (1.0-24.0μg/L) with remarkable determination coefficients (r(2)>0.9969). Excellent repeatability was also achieved through intraday (RSD<13.0%) and interday (RSD<8.9%) experiments. By using the standard addition methodology, the application of the present analytical approach on sea water, wastewater, commercial cosmetic products and urine samples revealed good sensitivity, absence of matrix effects and the occurrence of levels of some benzophenones. The proposed methodology that uses nanostructured particles and operates under the floating sampling technology proved to be a sorption-based static micro-extraction alternative to monitor benzophenone-type UV filters in real matrices. Moreover, is easy to implement, reliable, sensitive, requiring low sample volume and the possibility to choose the most selective sorbent coating according to the target compounds involved. Copyright © 2013. Published by Elsevier B.V.

Origins of strandline duricrusts around the Makgadikgadi Pans (Botswana Kalahari) as deduced from their chemical and isotope composition

NASA Astrophysics Data System (ADS)

Ringrose, S.; Harris, C.; Huntsman-Mapila, P.; Vink, B. W.; Diskins, S.; Vanderpost, C.; Matheson, W.

2009-07-01

Trace elements together with some O and C isotope analysis were undertaken on duricrust strandline deposits in the palaeo-Makgadikgadi sub-basin (PMSB) to provide insight into palaeo-climatic conditions through the interpretation of calcrete, silcrete-calcrete intergrade and silcrete deposits. Trace element content and relative abundance suggest that the duricrust origins are associated with the long-term weathering of the Karoo Large Igneous Province which underlies the PMSB. This work shows that duricrust origins are related to Ca 2+ and Si (and associated trace elements) being transported mainly through the groundwater and then subsequently precipitated at different strandline elevations over time. Local groundwater feeding in towards the pan margin and accumulating in near-neutral pan-marginal pools, appears to facilitate Si concentration and permeation of pre-existing calcretes. The silica precipitates as the pH drops when renewed freshwater enters the pools. Hence the inferred palaeo-climatic regime for silcretisation may be similar to that occurring in Botswana at present being dry semi-arid with low seasonal rainfall. In contrast the extensive calcrete precipitation in the strandlines results from abundant Ca 2+ in adjacent waters which appear to be derived from both local and regional sources. The arrival of Ca 2+ from regional sources (shown by trace element evidence) infers heavy rainfall in the upper catchment suggesting a major humid event followed by regional drying. Palaeo-climatic inferences suggest the juxtaposition of major humid events interspersed with more normal semi-arid palaeo-climates with an exception obtained from isotope data, of drier and cooler conditions than usual for the region around 80-90 000 years ago. Whereas trace element data can greatly assist in the interpretation of complex deposits such as duricrusts, care should be taken over the use of particular ratios (such as Yb/Gd ratio) which may produce spurious results.

Multi-isotope (C - O - S - H - B - Mg - Ca - Ba) and trace element variations along a vertical pore water profile across a brackish-fresh water transition, Baltic Sea

NASA Astrophysics Data System (ADS)

Böttcher, Michael E.; Lapham, Laura; Gussone, Nikolaus; Struck, Ulrich; Buhl, Dieter; Immenhauser, Adrian; Moeller, Kirsten; Pretet, Chloé; Nägler, Thomas F.; Dellwig, Olaf; Schnetger, Bernhard; Huckriede, Hermann; Halas, Stan; Samankassou, Elias

2013-04-01

The Holocene Baltic Sea has been switched several times between fresh water and brackish water modes. Modern linear sedimentation rates, based on 210-Pb, 137-Cs, and Hg dating of surface sediments, are between 0.1 and 0.2 mm per year. The change in paleo-environmental conditions caused downcore gradients in the concentrations of dissolved species from modern brackish waters towards fresh paleo-pore waters, interrupted by the brief brackish Yoldia stage. These strong physico-chemical changes had consequences for e.g., microbial activity and further physical and chemical water-solid interactions associated with multiple stable isotope fractionation processes, and, in turn, have strong implications for isotope and trace element partitioning upon early diagenetic mineral (trans)formations. In this communication, we present the results from the first integrated multi-isotope and trace element investigation conducted in this type of salinity-gradient system. It is found that concentrations of conservative elements (e.g., Na, Cl) decrease with depth due to diffusion of ions from brackish waters into underlying fresh waters. This is associated with pronounced depletions in H-2 and O-18 of pore water with depth. Covariations of both isotope systems are close to the meteoric water line as defined by modern Baltic Sea surface waters. A downward increase and decrease of Ca and Mg concentrations, respectively, is associated with decreasing Ca-44 and Mg-26 isotope values. B-11 isotope values decrease in the limnic part of the sediments, too. On the other hand, an increase in Ba concentrations with depth is associated with an increase in Ba-137/134 isotope values. Microbial sulfate reduction and organic matter oxidation lead to an increase in DIC, but a decrease in sulfate concentrations and in C-13 contents of DIC with depth. Suess (1981) was probably the first to propose, that desorption of Ca and Ba from glacial sediments due to downward diffusing ions may be responsible for a downcore increase in pore water concentrations of earth alkaline ions and the formation of authigenic barites. Coupled S-34 and O-18 isotope signals in authigenic barites suggest that they were formed in pre-Yoldia sediments from pore waters strongly depleted in O-18 (as low as -20 per mil vs. VSMOW). In the present communication, we will discuss possible impacts of diagenetic processes on multi-isotope signals in pore waters and authigenic phases. A combination of mixing between brackish and fresh water, ion exchange, precipitation/dissolution, and transport reactions is considered to explain most of the observed isotope variations along the vertical pore water profile. This work was supported by the Leibniz IOW, BONUS+ program, the Universities of Bern, Geneva, Bochum, Münster, and Oldenburg, and the Natural Museum of History, Berlin.

Position-specific isotope modeling of organic micropollutants transformations through different reaction pathways

NASA Astrophysics Data System (ADS)

Jin, Biao; Rolle, Massimo

2016-04-01

Organic compounds are produced in vast quantities for industrial and agricultural use, as well as for human and animal healthcare [1]. These chemicals and their metabolites are frequently detected at trace levels in fresh water environments where they undergo degradation via different reaction pathways. Compound specific stable isotope analysis (CSIA) is a valuable tool to identify such degradation pathways in different environmental systems. Recent advances in analytical techniques have promoted the fast development and implementation of multi-element CSIA. However, quantitative frameworks to evaluate multi-element stable isotope data and incorporating mechanistic information on the degradation processes [2,3] are still lacking. In this study we propose a mechanism-based modeling approach to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. We validate the proposed approach with the concentration and multi-element isotope data of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model precisely captures the dual element isotope trends characteristic of different reaction pathways and their range of variation consistent with observed multi-element (C, N) bulk isotope fractionation. The proposed approach can also be used as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. [1] Schwarzenbach, R.P., Egli, T., Hofstetter, T.B., von Gunten, U., Wehrli, B., 2010. Global Water Pollution and Human Health. Annu. Rev. Environ. Resour. doi:10.1146/annurev-environ-100809-125342. [2] Jin, B., Haderlein, S.B., Rolle, M., 2013. Integrated carbon and chlorine isotope modeling: Applications to chlorinated aliphatic hydrocarbons dechlorination. Environ. Sci. Technol. 47, 1443-1451. doi:10.1021/es304053h. [3] Jin, B., Rolle, M., 2014. Mechanistic approach to multi-element isotope modeling of organic contaminant degradation. Chemosphere 95, 131-139. doi:10.1016/j.chemosphere.2013.08.050.

Rich man's salt: the diamonds in the soup

NASA Astrophysics Data System (ADS)

Ott, Ulrich

Diamond nominally constitutes the most abundant of the presolar phases identified in primitive meteorites so far. An overview is given of known properties including isotopic abundances of trace elements that point to a supernova connection for at least part of the diamond grains. Scenarios for nucleosynthetic production of these trace elements and their introduction into the nanodiamonds are discussed as well as their observability.

Geochemistry of the Serifos calc-alkaline granodiorite pluton, Greece: constraining the crust and mantle contributions to I-type granitoids

NASA Astrophysics Data System (ADS)

Stouraiti, C.; Baziotis, I.; Asimow, P. D.; Downes, H.

2017-11-01

The Late Miocene (11.6-9.5 Ma) granitoid intrusion on the island of Serifos (Western Cyclades, Aegean Sea) is composed of syn- to post-tectonic granodiorite with quartz monzodiorite enclaves, cut by dacitic and aplitic dikes. The granitoid, a typical I-type metaluminous calcic amphibole-bearing calc-alkaline pluton, intruded the Cycladic Blueschists during thinning of the Aegean plate. Combining field, textural, geochemical and new Sr-Nd-O isotope data presented in this paper, we postulate that the Serifos intrusion is a single-zoned pluton. The central facies has initial 87Sr/86Sr = 0.70906 to 0.7106, ɛNd(t) = - 5.9 to - 7.5 and δ18Οqtz = + 10 to + 10.6‰, whereas the marginal zone (or border facies) has higher initial 87Sr/86Sr = 0.711 to 0.7112, lower ɛ Nd(t) = - 7.3 to - 8.3, and higher δ18Οqtz = + 10.6 to + 11.9‰. The small range in initial Sr and Nd isotopic values throughout the pluton is paired with a remarkable uniformity in trace element patterns, despite a large range in silica contents (58.8 to 72 wt% SiO2). Assimilation of a crustally derived partial melt into the mafic parental magma would progressively add incompatible trace elements and SiO2 to the evolving mafic starting liquid, but the opposite trend, of trace element depletion during magma evolution, is observed in the Serifos granodiorites. Thermodynamic modeling of whole-rock compositions during simple fractional crystallization (FC) or assimilation-fractional crystallization (AFC) processes of major rock-forming minerals—at a variety of pressure, oxidation state, and water activity conditions—fails to reproduce simultaneously the major element and trace element variations among the Serifos granitoids, implying a critical role for minor phases in controlling trace element fractionation. Both saturation of accessory phases such as allanite and titanite (at SiO2 ≥ 71 wt%)(to satisfy trace element constraints) and assimilation of partial melts from a metasedimentary component (to match isotopic data) must have accompanied fractional crystallization of the major phases.

Geochemistry and origin of regional dolomites. Final report

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

Hanson, G.N.; Meyers, W.J.

1995-05-01

The main goal of our research on dolomites has been to better understand the composition of the fluids and processes of the fluid-rock interaction responsible for the formation of massive dolostones occurring over regional scales within sedimentary sequences. Understanding the timing of dolomitization, the fluids responsible for the dolomitization and the timing of the development of porosity has major economic ramifications in that dolomites are major oil reservoirs often having better reservoir properties than associated limestones. Our approach has been to apply trace element, major element, petrographic, crystallographic, stable isotope and radiogenic isotope systems to test models for the originsmore » of dolomites and to give information that may allow us to develop new models. Fluid compositions and processes are evaluated through the use of numerical models which we have developed showing the simultaneous evolution of the trace element and isotope systems during dolomitization. Our research has included the application of B, O, C, Sr, Nd and Pb isotope systematics and the trace elements Mn, Fe St, rare earth elements, Rb, Ba, U, Th, Pb, Zn, Na, Cl, F and SO{sub 4}{sup 2-}. Analyses are possible on individual cements or dolomite types using micro-sampling or microprobe techniques. The microprobe techniques used include synchrotron X-ray microprobe analysis at Brookhaven National Laboratory or electron microprobe at Stony Brook. Lack of a modern analogue for ancient massive dolostones has limited the application of the uniformitarian concept to developing models for the ancient regional dolostones. In addition it has not been possible to synthesize dolomite in the laboratory under conditions similar to the sedimentary or diagenetic possible environments in which the dolomites must have formed.« less

Evolution of Early Paleoproterozoic Ocean Chemistry as Recorded by Black Shales

NASA Astrophysics Data System (ADS)

Scott, C.; Bekker, A.; Lyons, T. W.; Planavsky, N. J.; Wing, B. A.

2010-12-01

In recent years, Precambrian biogeochemists have focused largely on the abundance, speciation and isotopic composition of major and trace elements preserved in organic carbon-rich black shales in order to track the co-evolution of ocean chemistry and life on Earth. Despite the fact that the period from 2.5 to 2.0 Ga hosted major events in Earth’s history, such as the Great Oxidation Event (GOE), an era of global glaciations, a massive and long-lived carbon isotope excursion and the end to banded iron formation (BIF) deposition, each with the potential to directly alter global biogeochemical cycles, it is perhaps best known for its unknowns. In order to help close this gap in our understanding of the evolution of Precambrian ocean chemistry we present a detailed biogeochemical study of Paleoproterozoic black shales deposited between 2.5 and 2.0 Ga. Our study integrates Fe speciation, trace metal chemistry and C, S and N isotope analyses to provide a thorough characterization of marine biogeochemical cycles as they responded to the GOE and set the stage for the demise of BIFs at ca. 1.8 Ga. Our data reveal an ocean that was both surprising similar to, and demonstrably different from, Archean and later Proterozoic oceans. Of particular interest, we find that ferruginous and euxinic conditions co-existed during this period and that sea water trace metal inventories fluctuated dramatically in conjunction with major carbon isotope excursions. By comparing our Paleoproterozoic contribution with recent biogeochemical studies of other Precambrian black shales we can begin to track first order changes in ocean chemistry without the major time gaps that have plagued previous attempts.

Phase-specific Geochemistry of Ni: a Tracer of Geosphere-Biosphere Co-evolution?

NASA Astrophysics Data System (ADS)

Ciscato, E. R.; Vance, D.; Bontognali, T. R. R.; Poulton, S.

2016-12-01

Metalloproteome analyses and culturing studies have suggested that trace metals, such as Cu, Fe, Mo, Ni, and Zn, were selectively utilized by different organisms and specific metabolisms throughout the evolution of the biosphere. Methanogens have a particular requirement for Ni and culturing studies have shown that they fractionate Ni isotopes upon uptake. It is not clear, however, whether a resulting Ni isotopic signal can be preserved in the geological record. We have developed a new approach that enables us to analyze phase-specific authigenic trace metal enrichments, and their respective isotopic signatures, in (predominantly organic-rich) sediments from the geological record. An acid digestion step followed by high-pressure ashing allows us to separate an `organic matter + Pyrite' phase from an `HF-extractable' phase. We have applied this approach to investigate the distribution of Ni isotopes in a variety of modern sediments, including organic-rich sediments from upwelling margins and a hypersaline lagoonal setting where methanogenesis is likely to be an active process. Preliminary results on geological record samples show a δ60Ni for the `HF-extractable' phases that agrees with the average continental crust, whereas the `organic matter + Pyrite' phases are heavier and shifted in the direction of modern seawater. By combining this data with our δ60Ni dataset from modern sediments, we investigate the dynamics of Ni cycling in environments with different O2 and H2S availabilities both in the modern and throughout the past 3.2 billion years. Our phase-specific δ60Ni record is of instrumental importance in determining whether a biologically induced fractionation imparted by methanogens is indeed observable, and if it can be used as a biosignature for tracing the predominance of methanogenic pathways throughout the co-evolution of the geosphere and biosphere.

Quantification and isotopic analysis of intracellular sulfur metabolites in the dissimilatory sulfate reduction pathway

NASA Astrophysics Data System (ADS)

Sim, Min Sub; Paris, Guillaume; Adkins, Jess F.; Orphan, Victoria J.; Sessions, Alex L.

2017-06-01

Microbial sulfate reduction exhibits a normal isotope effect, leaving unreacted sulfate enriched in 34S and producing sulfide that is depleted in 34S. However, the magnitude of sulfur isotope fractionation is quite variable. The resulting changes in sulfur isotope abundance have been used to trace microbial sulfate reduction in modern and ancient ecosystems, but the intracellular mechanism(s) underlying the wide range of fractionations remains unclear. Here we report the concentrations and isotopic ratios of sulfur metabolites in the dissimilatory sulfate reduction pathway of Desulfovibrio alaskensis. Intracellular sulfate and APS levels change depending on the growth phase, peaking at the end of exponential phase, while sulfite accumulates in the cell during stationary phase. During exponential growth, intracellular sulfate and APS are strongly enriched in 34S. The fractionation between internal and external sulfate is up to 49‰, while at the same time that between external sulfate and sulfide is just a few permil. We interpret this pattern to indicate that enzymatic fractionations remain large but the net fractionation between sulfate and sulfide is muted by the closed-system limitation of intracellular sulfate. This 'reservoir effect' diminishes upon cessation of exponential phase growth, allowing the expression of larger net sulfur isotope fractionations. Thus, the relative rates of sulfate exchange across the membrane versus intracellular sulfate reduction should govern the overall (net) fractionation that is expressed. A strong reservoir effect due to vigorous sulfate reduction might be responsible for the well-established inverse correlation between sulfur isotope fractionation and the cell-specific rate of sulfate reduction, while at the same time intraspecies differences in sulfate uptake and/or exchange rates could account for the significant scatter in this relationship. Our approach, together with ongoing investigations of the kinetic isotope fractionation by key enzymes in the sulfate reduction pathway, should provide an empirical basis for a quantitative model relating the magnitude of microbial isotope fractionation to their environmental and physiological controls.

SPECTROPHOTOMETRIC DETERMINATION OF ULTRA-SMALL QUANTITIES OF NICKEL IN INDIUM (in Russian)

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

Peshkova, V.M.; Bochkova, V.M.; Astakhova, E.K.

1961-09-01

alpha -Benzil doxime permits the determination of nickel by measuring optical density in the region of maximum absortption (at 275 m mu ), after the reagent excess is removed by washing the extract with alkali. Conditions were found for the spectrophotometric determination of ultra-small quantities (down to 0.005 gamma ) of nickel with alpha -benzil dioxime in the soultion of its pure salt, in the presence of cobalt and copper. A method was developed for the determination of traces of nickel down to 5 x 10 /sup -7%/ in metallic indium. The reproducibility of method is +25%. (auth)

Pump-probe micro-spectroscopy by means of an ultra-fast acousto-optics delay line.

PubMed

Audier, Xavier; Balla, Naveen; Rigneault, Hervé

2017-01-15

We demonstrate femtosecond pump-probe transient absorption spectroscopy using a programmable dispersive filter as an ultra-fast delay line. Combined with fast synchronous detection, this delay line allows for recording of 6 ps decay traces at 34 kHz. With such acquisition speed, we perform single point pump-probe spectroscopy on bulk samples in 80 μs and hyperspectral pump-probe imaging over a field of view of 100 μm in less than a second. The usability of the method is illustrated in a showcase experiment to image and discriminate between two pigments in a mixture.

Ultra-sensitive, stable isotope assisted quantification of multiple urinary mycotoxin exposure biomarkers.

PubMed

Šarkanj, Bojan; Ezekiel, Chibundu N; Turner, Paul C; Abia, Wilfred A; Rychlik, Michael; Krska, Rudolf; Sulyok, Michael; Warth, Benedikt

2018-08-17

There is a critical need to better understand the patterns, levels and combinatory effects of exposures we are facing through our diet and environment. Mycotoxin mixtures are of particular concern due to chronic low dose exposures caused by naturally contaminated food. To facilitate new insights into their role in chronic disease, mycotoxins and their metabolites are quantified in bio-fluids as biomarkers of exposure. Here, we describe a highly sensitive urinary assay based on ultra-high performance liquid chromatography - tandem mass spectrometer (UHPLC-MS/MS) and 13 C-labelled or deuterated internal standards covering the most relevant regulated and emerging mycotoxins. Utilizing enzymatic pre-treatment, solid phase extraction and UHPLC separation, the sensitivity of the method was significantly higher (10-160x lower LODs) than in a previously described method used for comparison purpose, and stable isotopes provided compensation for challenging matrix effects. This method was in-house validated and applied to re-assess mycotoxin exposure in urine samples obtained from Nigerian children, adolescent and adults, naturally exposed through their regular diet. Owing to the methods high sensitivity, biomarkers were detected in all samples. The mycoestrogen zearalenone was the most frequently detected contaminant (82%) but also ochratoxin A (76%), aflatoxin M 1 (73%) and fumonisin B 1 (71%) were quantified in a large share of urines. Overall, 57% of 120 urines were contaminated with both, aflatoxin M 1 and fumonisin B 1 , and other co-exposures were frequent. These results clearly demonstrate the advanced performance of the method to assess lowest background exposures (pg mL -1 range) using a single, highly robust assay that will allow for the systematic investigation of low dose effects on human health. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Isotopic Tracing of Fuel Components in Particulate Emissions from Diesel Engines using Accelerator Mass Spectrometry (AMS)

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

Buchholz, B A; Mueller, C J; Garbak, J.

2001-08-02

Accelerator mass spectrometry (AMS) is an isotope-ratio measurement technique developed in the late 1970s for tracing long-lived radioisotopes (e.g., {sup 14}C half life = 5760 y). The technique counts individual nuclei rather than waiting for their radioactive decay, allowing measurement of more than 100 low-level {sup 14}C samples per day (Vogel et al, 1995). The LLNL AMS system is shown in Fig.1. The contemporary quantity of {sup 14}C in living things ({sup 14}C/C = 1.2 x 10{sup -12} or 110 fmol {sup 14}C/ g C) is highly elevated compared to the quantity of {sup 14}C in petroleum-derived products. This isotopicmore » elevation is sufficient to trace the fate of bio-derived fuel components in the emissions of an engine without the use of radioactive materials. If synthesis of a fuel component from biologically-derived source material is not feasible, another approach is to purchase {sup 14}C-labeled material (e.g., dibutyl maleate (DBM)) and dilute it with petroleum-derived material to yield a contemporary level of {sup 14}C. In each case, the virtual absence of {sup 14}C in petroleum based fuels gives a very low {sup 14}C background that makes this approach to tracing fuel components practical. Regulatory pressure to significantly reduce the particulate emissions from diesel engines is driving research into understanding mechanisms of soot formation. If mechanisms are understood, then combustion modeling can be used to evaluate possible changes in fuel formulation and suggest possible fuel components that can improve combustion and reduce PM emissions. The combustion paradigm assumes that large molecules break down into small components and then build up again during soot formation. AMS allows us to label specific fuel components, including oxygenates, trace the carbon atoms, and test this combustion modeling paradigm. Volatile and non-volatile organic fractions (VOF, NVOF) in the PM can be further separated. The VOF of the PM can be oxidized with catalysts in the exhaust stream to further decrease PM. The effectiveness of exhaust stream catalysts to oxidize products from tracer fuel components can be monitored through AMS measurement of carbon in PM. The objects of this report are: (1) Determine contribution of diesel fuel components and oxygenates to soot formation; (2) Separate volatile and non-volatile fractions of soot; (3) Test combustion paradigm that all carbon and oxygen in fuel is equal; and (4) Produce data to validate combustion modeling.« less

Melt migration and mantle chromatography, 2: a time-series Os isotope study of Mauna Loa volcano, Hawaii

NASA Astrophysics Data System (ADS)

Hauri, Erik H.; Kurz, Mark D.

1997-12-01

We have determined the major element, trace element, and Os isotopic compositions of a stratigraphic suite of tholeiitic basalts spanning >30,000 years of the eruptive history of Mauna Loa volcano. Good correlations are observed between Os isotopes and the isotopes of Sr, Nd, Pb and He. In addition, the isotopes correlate with fractionation-corrected major element abundances within this single volcano, and provide a record of increased melting of mafic material with time at Mauna Loa. Chromatographic element fractionation during melt transport is shown to be negligible based on the good correlations of the isotopes of the compatible element Os with the other incompatible element tracers. The temporal variation at Mauna Loa is best described by the translation of the volcano over a Hawaiian plume which is radially zoned in composition. The radial zonation is a predicted consequence of thermal entrainment during flow in a mantle plume conduit.

Mg isotope systematics during magmatic processes: Inter-mineral fractionation in mafic to ultramafic Hawaiian xenoliths

NASA Astrophysics Data System (ADS)

Stracke, A.; Tipper, E. T.; Klemme, S.; Bizimis, M.

2018-04-01

Observed differences in Mg isotope ratios between bulk magmatic rocks are small, often on a sub per mill level. Inter-mineral differences in the 26Mg/24Mg ratio (expressed as δ26Mg) in plutonic rocks are on a similar scale, and have mostly been attributed to equilibrium isotope fractionation at magmatic temperatures. Here we report Mg isotope data on minerals in spinel peridotite and garnet pyroxenite xenoliths from the rejuvenated stage of volcanism on Oahu and Kauai, Hawaii. The new data are compared to literature data and to theoretical predictions to investigate the processes responsible for inter-mineral Mg isotope fractionation at magmatic temperatures. Theory predicts up to per mill level differences in δ26Mg between olivine and spinel at magmatic temperatures and a general decrease in Δ26Mgolivine-spinel (=δ26Mgolivine - δ26Mgspinel) with increasing temperature, but also with increasing Cr# in spinel. For peridotites with a simple petrogenetic history by melt depletion, where increasing depletion relates to increasing melting temperatures, Δ26Mgolivine-spinel should thus systematically decrease with increasing Cr# in spinel. However, most natural peridotites, including the Hawaiian spinel peridotites investigated in this study, are overprinted by variable extents of melt-rock reaction, which disturb the systematic primary temperature and compositionally related olivine-spinel Mg isotope systematics. Diffusion, subsolidus re-equilibration, or surface alteration may further affect the observed olivine-spinel Mg isotope fractionation in peridotites, making Δ26Mgolivine-spinel in peridotites a difficult-to-apply geothermometer. The available Mg isotope data on clinopyroxene and garnet suggest that this mineral pair is a more promising geothermometer, but its application is restricted to garnet-bearing igneous (garnet pyroxenites) and metamorphic rocks (eclogites). Although the observed δ26Mg variation is on a sub per mill range in bulk magmatic rocks, the clearly resolvable inter-mineral Mg isotope differences imply that crystallization or preferential melting of isotopically distinct minerals such garnet, spinel, and clinopyroxene should cause Mg isotope fractionation between bulk melt and residue. Calculated Mg isotope variations during partial mantle melting indeed predict differences between melt and residue, but these are analytically resolvable only for melting of mafic lithologies, that is, garnet pyroxenites. Contributions from garnet pyroxenite melts may thus account for some of the isotopically light δ26Mg observed in ocean island basalts and trace lithological mantle heterogeneity. Consequently, applications for high-temperature Mg isotope fractionations are promising and diverse, and recent advances in analytical precision may allow the full petrogenetic potential inherent in the sub per mill variations in δ26Mg in magmatic rocks to be exploited.