Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

Science.gov (United States)

Cooper, George W.; Thiemens, Mark H.; Jackson, Teresa L.; Chang, Sherwood

1997-01-01

Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

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

Directory of Open Access Journals (Sweden)

Nurgul Balci

2017-08-01

Full Text Available Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62− and elemental sulfur (S° to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6 by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4 from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2. During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4

Analysis of growth and tissue replacement rates by stable sulfur isotope turnover.

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Arneson, L. S.; Macko, S. A.; Macavoy, S. E.

2003-12-01

Stable isotope analysis has become a powerful tool to study animal ecology. Analysis of stable isotope ratios of elements such as carbon, nitrogen, sulfur, hydrogen, oxygen and others have been used to trace migratory routes, reconstruct dietary sources and determine the physiological condition of individual animals. The isotopes most commonly used are carbon, due to differential carbon fractionation in C3 and C4 plants, and nitrogen, due to the approximately 3% enrichment in 15N per trophic level. Although all cells express sulfur-containing compounds, such as cysteine, methionine, and coenzyme A, the turnover rate of sulfur in tissues has not been examined in most studies, owing to the difficulty in determining the δ 34S signature. In this study, we have assessed the rate of sulfur isotopic turnover in mouse tissues following a diet change from terrestrial (7%) to marine (19%) source. Turnover models reflecting both growth rate and metabolic tissue replacement will be developed for blood, liver, fat and muscle tissues.

Diversity of sulfur isotope fractionations by sulfate-reducing prokaryotes

DEFF Research Database (Denmark)

Detmers, Jan; Brüchert, Volker; Habicht, K S

2001-01-01

Batch culture experiments were performed with 32 different sulfate-reducing prokaryotes to explore the diversity in sulfur isotope fractionation during dissimilatory sulfate reduction by pure cultures. The selected strains reflect the phylogenetic and physiologic diversity of presently known...... sulfate reducers and cover a broad range of natural marine and freshwater habitats. Experimental conditions were designed to achieve optimum growth conditions with respect to electron donors, salinity, temperature, and pH. Under these optimized conditions, experimental fractionation factors ranged from 2.......0 to 42.0 per thousand. Salinity, incubation temperature, pH, and phylogeny had no systematic effect on the sulfur isotope fractionation. There was no correlation between isotope fractionation and sulfate reduction rate. The type of dissimilatory bisulfite reductase also had no effect on fractionation...

Identifying the change in atmospheric sulfur sources in China using isotopic ratios in mosses

Science.gov (United States)

Xiao, Hua-Yun; Tang, Cong-Guo; Xiao, Hong-Wei; Liu, Xue-Yan; Liu, Cong-Qiang

2009-08-01

A considerable number of studies on rainwater sulfur isotopic ratios (δ34Srain) have been conducted to trace sulfur sources at a large number of sites in the past. If longitudinal studies on the isotope composition of precipitation sulfate were conducted, it is possible to relate that to changes in sulfur emissions. But direct measurement needs considerable labor and time. So, in this study, sulfur isotopic ratios in rainwater and mosses were analyzed at Guiyang and Nanchang to evaluate the possibility of using mosses as a substitute for rainwater. We found that present moss sulfur isotopic ratios were comparable to those of present rainwater. Additionally, we investigated the changes of atmospheric sulfur sources and sulfur concentrations using an isotopic graphic analysis at five industrial cities, two forested areas, and two remote areas in China. Mosses in industrial cities show a wide range of δ34S values, with the highest occurring at Chongqing (+3.9‰) and the lowest at Guiyang (-3.1‰). But as compared to those in forested and remote areas, δ34S values of mosses in all the five industrial cities are lower. On the basis of isotopic comparisons between past rainwater (reported in the literature) and present mosses, in the plot of δ34Smoss versus δ34Srain, six zones indicating different atmospheric sulfur change are separated by the 1:1 line and δ34S values of potential sulfur sources. Our results indicate that atmospheric sulfur pollution in most of the industrial cities decreased, while at the two forested areas, no significant changes were observed, and a new anxiousness coming from new energy sources (e.g., oil) appeared in some cities. Studies on the change of ambient SO2 concentrations support these results.

Sulfur cycling in contaminated aquifers: What can we learn from oxygen isotopes in sulfate? (Invited)

Science.gov (United States)

Knoeller, K.; Vogt, C.; Hoth, N.

2009-12-01

Bacterial reduction of dissolved sulfate (BSR) is a key process determining the natural attenuation in many contaminated aquifers. For example, in groundwater bodies affected by acid mine drainage (AMD) BSR reduces the contaminant load by producing alkalinity and facilitating a sustainable fixation of sulfur in the sediment. In aquifers contaminated with petroleum hydrocarbons sulfate may act as a terminal electron acceptor for the anaerobic oxidation of the organic contaminants to carbon dioxide and water. Due to the isotope selectivity of sulfate reducing bacteria, BSR shows the most pronounced isotope fractionation within the sulfur cycle. While sulfur displays a straightforward kinetic enrichment in the residual sulfate described by the enrichment factor epsilon (ɛ), the mechanism of oxygen isotope fractionation is still being discussed controversially. Nevertheless, it is agreed on that oxygen isotope exchange between ambient water and residual sulfate occurs during BSR in natural environments. With respect to this potential isotope exchange, the fractionation parameter theta (θ) is introduced instead of the kinetic enrichment factor epsilon (ɛ). The dual isotope system considering both sulfate-sulfur and sulfate-oxygen isotope fractionation and the respective fractionation parameters ɛ and θ provides an excellent tool for the recognition and quantification of BSR. Beyond that, the dual isotope approach may help identify and estimate interfering sulfur transformations such as re-oxidation and disproportionation processes which is especially vital for the understanding of the overall natural attenuation potential of the investigated aquifers. We present two examples from different field studies showing the benefits of applying the combination of sulfur and oxygen isotopes in dissolved sulfate to reveal the details of the sulfur cycle. The first case study is concerned with the evaluation of the potential for BSR in an AMD-affected aquifer close to an

Influence of sulfur-bearing polyatomic species on high precision measurements of Cu isotopic composition

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Pribil, M.J.; Wanty, R.B.; Ridley, W.I.; Borrok, D.M.

2010-01-01

An increased interest in high precision Cu isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has developed recently for various natural geologic systems and environmental applications, these typically contain high concentrations of sulfur, particularly in the form of sulfate (SO42-) and sulfide (S). For example, Cu, Fe, and Zn concentrations in acid mine drainage (AMD) can range from 100??g/L to greater than 50mg/L with sulfur species concentrations reaching greater than 1000mg/L. Routine separation of Cu, Fe and Zn from AMD, Cu-sulfide minerals and other geological matrices usually incorporates single anion exchange resin column chromatography for metal separation. During chromatographic separation, variable breakthrough of SO42- during anion exchange resin column chromatography into the Cu fractions was observed as a function of the initial sulfur to Cu ratio, column properties, and the sample matrix. SO42- present in the Cu fraction can form a polyatomic 32S-14N-16O-1H species causing a direct mass interference with 63Cu and producing artificially light ??65Cu values. Here we report the extent of the mass interference caused by SO42- breakthrough when measuring ??65Cu on natural samples and NIST SRM 976 Cu isotope spiked with SO42- after both single anion column chromatography and double anion column chromatography. A set of five 100??g/L Cu SRM 976 samples spiked with 500mg/L SO42- resulted in an average ??65Cu of -3.50?????5.42??? following single anion column separation with variable SO42- breakthrough but an average concentration of 770??g/L. Following double anion column separation, the average SO42-concentration of 13??g/L resulted in better precision and accuracy for the measured ??65Cu value of 0.01?????0.02??? relative to the expected 0??? for SRM 976. We conclude that attention to SO42- breakthrough on sulfur-rich samples is necessary for accurate and precise measurements of ??65Cu and may require

Synthesis of l-cysteine derivatives containing stable sulfur isotopes and application of this synthesis to reactive sulfur metabolome.

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Ono, Katsuhiko; Jung, Minkyung; Zhang, Tianli; Tsutsuki, Hiroyasu; Sezaki, Hiroshi; Ihara, Hideshi; Wei, Fan-Yan; Tomizawa, Kazuhito; Akaike, Takaaki; Sawa, Tomohiro

2017-05-01

Cysteine persulfide is an L-cysteine derivative having one additional sulfur atom bound to a cysteinyl thiol group, and it serves as a reactive sulfur species that regulates redox homeostasis in cells. Here, we describe a rapid and efficient method of synthesis of L-cysteine derivatives containing isotopic sulfur atoms and application of this method to a reactive sulfur metabolome. We used bacterial cysteine syntheses to incorporate isotopic sulfur atoms into the sulfhydryl moiety of L-cysteine. We cloned three cysteine synthases-CysE, CysK, and CysM-from the Gram-negative bacterium Salmonella enterica serovar Typhimurium LT2, and we generated their recombinant enzymes. We synthesized 34 S-labeled L-cysteine from O-acetyl-L-serine and 34 S-labeled sodium sulfide as substrates for the CysK or CysM reactions. Isotopic labeling of L-cysteine at both sulfur ( 34 S) and nitrogen ( 15 N) atoms was also achieved by performing enzyme reactions with 15 N-labeled L-serine, acetyl-CoA, and 34 S-labeled sodium sulfide in the presence of CysE and CysK. The present enzyme systems can be applied to syntheses of a series of L-cysteine derivatives including L-cystine, L-cystine persulfide, S-sulfo-L-cysteine, L-cysteine sulfonate, and L-selenocystine. We also prepared 34 S-labeled N-acetyl-L-cysteine (NAC) by incubating 34 S-labeled L-cysteine with acetyl coenzyme A in test tubes. Tandem mass spectrometric identification of low-molecular-weight thiols after monobromobimane derivatization revealed the endogenous occurrence of NAC in the cultured mammalian cells such as HeLa cells and J774.1 cells. Furthermore, we successfully demonstrated, by using 34 S-labeled NAC, metabolic conversion of NAC to glutathione and its persulfide, via intermediate formation of L-cysteine, in the cells. The approach using isotopic sulfur labeling combined with mass spectrometry may thus contribute to greater understanding of reactive sulfur metabolome and redox biology. Copyright © 2017 Elsevier Inc

Natural variations of copper and sulfur stable isotopes in blood of hepatocellular carcinoma patients

Science.gov (United States)

Balter, Vincent; Nogueira da Costa, Andre; Paky Bondanese, Victor; Jaouen, Klervia; Lamboux, Aline; Sangrajrang, Suleeporn; Vincent, Nicolas; Fourel, François; Télouk, Philippe; Gigou, Michelle; Lécuyer, Christophe; Srivatanakul, Petcharin; Bréchot, Christian; Albarède, Francis; Hainaut, Pierre

2015-01-01

The widespread hypoxic conditions of the tumor microenvironment can impair the metabolism of bioessential elements such as copper and sulfur, notably by changing their redox state and, as a consequence, their ability to bind specific molecules. Because competing redox state is known to drive isotopic fractionation, we have used here the stable isotope compositions of copper (65Cu/63Cu) and sulfur (34S/32S) in the blood of patients with hepatocellular carcinoma (HCC) as a tool to explore the cancer-driven copper and sulfur imbalances. We report that copper is 63Cu-enriched by ∼0.4‰ and sulfur is 32S-enriched by ∼1.5‰ in the blood of patients compared with that of control subjects. As expected, HCC patients have more copper in red blood cells and serum compared with control subjects. However, the isotopic signature of this blood extra copper burden is not in favor of a dietary origin but rather suggests a reallocation in the body of copper bound to cysteine-rich proteins such as metallothioneins. The magnitude of the sulfur isotope effect is similar in red blood cells and serum of HCC patients, implying that sulfur fractionation is systemic. The 32S-enrichment of sulfur in the blood of HCC patients is compatible with the notion that sulfur partly originates from tumor-derived sulfides. The measurement of natural variations of stable isotope compositions, using techniques developed in the field of Earth sciences, can provide new means to detect and quantify cancer metabolic changes and provide insights into underlying mechanisms.

Isotopic insights into microbial sulfur cycling in oil reservoirs

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Christopher G Hubbard

2014-09-01

Full Text Available Microbial sulfate reduction in oil reservoirs (biosouring is often associated with secondary oil production where seawater containing high sulfate concentrations (~28 mM is injected into a reservoir to maintain pressure and displace oil. The sulfide generated from biosouring can cause corrosion of infrastructure, health exposure risks, and higher production costs. Isotope monitoring is a promising approach for understanding microbial sulfur cycling in reservoirs, enabling early detection of biosouring, and understanding the impact of souring. Microbial sulfate reduction is known to result in large shifts in the sulfur and oxygen isotope compositions of the residual sulfate, which can be distinguished from other processes that may be occurring in oil reservoirs, such as precipitation of sulfate and sulfide minerals. Key to the success of this method is using the appropriate isotopic fractionation factors for the conditions and processes being monitored. For a set of batch incubation experiments using a mixed microbial culture with crude oil as the electron donor, we measured a sulfur fractionation factor for sulfate reduction of -30‰. We have incorporated this result into a simplified 1D reservoir reactive transport model to highlight how isotopes can help discriminate between biotic and abiotic processes affecting sulfate and sulfide concentrations. Modeling results suggest that monitoring sulfate isotopes can provide an early indication of souring for reservoirs with reactive iron minerals that can remove the produced sulfide, especially when sulfate reduction occurs in the mixing zone between formation waters containing elevated concentrations of volatile fatty acids and injection water containing elevated sulfate. In addition, we examine the role of reservoir thermal, geochemical, hydrological, operational and microbiological conditions in determining microbial souring dynamics and hence the anticipated isotopic signatures.

Stable hydrogen, oxygen and sulfur isotopes composition in different tissues of cattle

International Nuclear Information System (INIS)

Sun Fengmei; Shi Guangyu; Wang Huiwen; Yang Shuming

2012-01-01

In order to research on stable hydrogen, oxygen, sulfur isotopes composition in different tissues of cattle, as well as the breed, δ 2 H and δ 34 S values of different defatted muscle, cattle tail hair, blood, liver, also δ 2h and δ 18 O values of water from muscle were determined by isotope ratio mass spectrometry. The stable sulfur isotope composition was not affected by cattle variety, meanwhile the hydrogen was uncertain; the δ 2 H and δ 34 S values between different defatted muscle, blood, liver, cattle hair were significantly different, at the same time the δ 34 S and δ 2 H values between each tissue were not significantly correlated; the δ 2 H values were strongly correlated with the δ 18 O values of muscle water. The above results indicated that stable sulfur and hydrogen isotopes fractionation in the various tissues were discrepant, thus the proper tissue should be selected according to the purpose and object in the beef traceability. (authors)

Sulfur and Oxygen Isotopic Composition of Sulfate in the Fresh Water, King Sejong Station, King George Island, Antarctica

Science.gov (United States)

Kim, M.; Lee, I.; Lee, J.; Park, B.; Mayer, B.; Kaufman, A. J.; Park, S.; Kim, G.; Lee, K.

2008-12-01

Isotopic compositions of sulfur (δ34S) and oxygen (δ18O) were measured for the sulfate of the fresh water near the King Sejong Station, King George Island, Antarctica. Sejong station is located in the Barton peninsular of the King George Island. The geology around King Sejong station mainly composed of basalt-andesite, quart monzodiorite, and granodiorite. Lapilli tuff, conglomerate, sandstone, and siltstone occur along the southern and eastern shore of the Barton peninsula. Lapilli tuff also occurs on the highland located on southeastern part of the Barton peninsula. The δ34S values of sulfate extracted from fresh water samples at King Sejong Station range from 13.7 to 16.3 per mil excluding 1 sample. These sulfur values are very narrow in their range compared with those from anthropogenic sources. These sulfur values are 5 to 7 per mil lower than those of typical present seawater. Considering the rocks occurring near the King Sejong station, these sulfur isotopic values do not seem to be related to any evaporites of certain age. In Antarctic region the natural source of sulfate dissolved in water could be originated from marine biogenic source (DMS), sea-salt, volcanic source, or other continental sources. Most of the δ34S values of sulfate at King Sejong station seems to indicate the dominance of marine biogenic origin for the source of sulfur. The δ18O values of sulfate extracted from fresh water samples at King Sejong Station range from 1.9 to 6.4 per mil excluding 1 sample. These oxygen isotope values are lower than those of the sulfate in the present seawater by 6 per mil. However, both sulfur and oxygen isotope values strongly represent the influence of the seawater sulfate. One sample have 2.6 and -1.1 per mil in its δ34S and δ18O values, respectively, that are quite different from the isotopic values of other samples. This sample was collected in the highland far from the King Sejong station. Therefore this sample might reflect the composition of

Oxygen, hydrogen, sulfur, and carbon isotopes in the Pea Ridge magnetite-apatite deposit, southeast Missouri, and sulfur isotope comparisons to other iron deposits in the region

Science.gov (United States)

Johnson, Craig A.; Day, Warren C.; Rye, Robert O.

2016-01-01

Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ18O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ18O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes.Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ34S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition

Lectures in isotope geology

International Nuclear Information System (INIS)

Jaeger, E.; Hunziker, J.C.

1979-01-01

Designed for a introductory course in geochronology and the geochemistry of stable isotopes, this text has been written by recognized experts in the field. Emphasis is on the interpretation and on applications, and examples of these are offered along with each technique. Extraterrestrial applications have been avoided and the treatment of pure experimentation has been kept at a minimum. This text will be appreciated by geologists who want to learn more about methods used in isotope geology, how they can be applied, and how to gauge their usefulness. (orig.) [de

Sulfur contents and sulfur-isotope compositions of thiotrophic symbioses in bivalve molluscs and vestimentiferan worms

Science.gov (United States)

Vetter, R.D.; Fry, B.

1998-01-01

Total sulfur (S(TOT)), elemental sulfur (S??) and sulfur-isotope compositions (??34S) of marine animals were analyzed to determine whether these chemical characteristics could help distinguish animals with a sulfur-based, thiotrophic nutrition from animals whose nutrition is based on methanotrophy or on more normal consumption of phytoplankton-derived organic matter. The presence of S??was almost entirely confined to the symbiont-containing tissues of thiotrophs, but was sometimes undetectable in thiotrophic species where sulfide availability was probably low. When S??contents were subtracted, the remaining tissue-sulfur concentrations were similar for all nutritional groups. ??34S values were typically lower for thiotrophs than for other groups, although there was overlap in methanotroph and thiotroph values at some sites. Field evidence supported the existence of small to moderate (1 to 10???)34S fractionations in the uptake of sulfides and metabolism of thiosulfate. In general, a total sulfur content of >3% dry weight, the presence of elemental sulfur, and ??34S values less than + 5??? can be used to infer a thiotrophic mode of nutrition.

Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles

Science.gov (United States)

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

2016-04-01

Carbonyl sulfide (OCS or COS) is the most abundant gas containing sulfur in the atmosphere, with an average mixing ratio of 500 p.p.t.v. in the troposphere. OCS is suggested as a sulfur source of the stratospheric sulfate aerosols (SSA) which plays an important role in Earth's radiation budget and ozone depletion. Therefore, OCS budget should be validated for prediction of climate change, but the global OCS budget is imbalance. Recently we developed a promising new analytical method for measuring the stable sulfur isotopic compositions of OCS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ (Hattori et al., 2015). The first measurement of the δ34S value for atmospheric OCS coupled with isotopic fractionation for OCS sink reactions in the stratosphere (Hattori et al., 2011; Schmidt et al., 2012; Hattori et al., 2012) explains the reported δ34S value for background stratospheric sulfate, suggesting that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. This new method measuring δ34S values of OCS can be used to investigate OCS sources and sinks in the troposphere to better understand its cycle. It is known that some microorganisms in soil can degrade OCS, but the mechanism and the contribution to the OCS in the air are still uncertain. In order to determine sulfur isotopic enrichment factor of OCS during degradation via microorganisms, incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia and Cupriavidus, isolated from natural soil environments (Kato et al., 2008). As a result, sulfur isotope ratios of OCS were increased during degradation of OCS, indicating that reaction for OC32S is faster than that for OC33S and OC34S. OCS degradation via microorganisms is not mass-independent fractionation (MIF) process, suggesting that this

Sulfate and sulfide sulfur isotopes (δ34S and δ33S) measured by solution and laser ablation MC-ICP-MS: An enhanced approach using external correction

Science.gov (United States)

Pribil, Michael; Ridley, William I.; Emsbo, Poul

2015-01-01

Isotope ratio measurements using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) commonly use standard-sample bracketing with a single isotope standard for mass bias correction for elements with narrow-range isotope systems measured by MC-ICP-MS, e.g. Cu, Fe, Zn, and Hg. However, sulfur (S) isotopic composition (δ34S) in nature can range from at least − 40 to + 40‰, potentially exceeding the ability of standard-sample bracketing using a single sulfur isotope standard to accurately correct for mass bias. Isotopic fractionation via solution and laser ablation introduction was determined during sulfate sulfur (Ssulfate) isotope measurements. An external isotope calibration curve was constructed using in-house and National Institute of Standards and Technology (NIST) Ssulfate isotope reference materials (RM) in an attempt to correct for the difference. The ability of external isotope correction for Ssulfate isotope measurements was evaluated by analyzing NIST and United States Geological Survey (USGS) Ssulfate isotope reference materials as unknowns. Differences in δ34Ssulfate between standard-sample bracketing and standard-sample bracketing with external isotope correction for sulfate samples ranged from 0.72‰ to 2.35‰ over a δ34S range of 1.40‰ to 21.17‰. No isotopic differences were observed when analyzing Ssulfide reference materials over a δ34Ssulfide range of − 32.1‰ to 17.3‰ and a δ33S range of − 16.5‰ to 8.9‰ via laser ablation (LA)-MC-ICP-MS. Here, we identify a possible plasma induced fractionation for Ssulfate and describe a new method using external isotope calibration corrections using solution and LA-MC-ICP-MS.

Sulfur Isotope Composition of Some Polymetallic Deposits in the Republic of Macedonia

International Nuclear Information System (INIS)

Serafimovski, Todor; Tasev, Goran

2005-01-01

The attempt to obtain an exact information about the origin of sulfur and other metals present in polymetallic deposits at the territory of the Republic of Macedonia have resulted in a detailed sulfur isotope composition study, which have enclosed the following deposits: Toranica, Sasa, Zletovo, Buchim and Alshar deposit. Results obtained for the formerly mentioned deposits have shown that sulfur isotope composition β 34 S is in the range -7.52 to +2.18 per mils in Toranica, -1.22 -- +6.94 per mils in Sasa, -3.12 -- +3.40 per mils in Zletovo (without ore associated barites), +0.00 to +2.53 per mils in Buchim (the narrowest range of all studied deposits) and -6.84 to +0.351 per mils β 34 S in Alshar. Therefore, the most probably origin of primary sulfur in studied deposits from Earth's crust or eventually Upper Mantle. Such sources of sulfur and other mineralizing metals confirmed the theories about the endo gene origin of mineralization fluids, which have formed studied deposits. (Author)

Decoding mass-independent fractionation of sulfur isotopes in modern atmosphere using cosmogenic 35S: A five-isotope approach and possible implications for Archean sulfur isotope records

Science.gov (United States)

Lin, M.; Thiemens, M. H.; Shen, Y.; Zhang, X.; Huang, X.; Chen, K.; Zhang, Z.; Tao, J.

2017-12-01

The signature of sulfur isotopic mass-independent fractionation (S-MIF) observed in Archean sediments have been interpreted as a proxy of the origins and evolution of atmospheric oxygen and early life on Earth [1]. Photochemistry of SOx in the short (negative Δ36S. After eliminating combustion impacts, the obtained Δ36S/Δ33S slope of -4.0 in the modern atmosphere is close to the Δ36S/Δ33S slope (-3.6) in some records from Paleoarchean [4], an era probably with active volcanism [5]. The significant role of volcanic OCS in the Archean atmosphere has been called for in terms of its ability to provide a continual SO2 high altitude source for photolysis [2]. The strong but previously underappreciated stratospheric signature of S-MIF in tropospheric sulfates suggests that a more careful investigation of wavelength-dependent sulfur isotopic fractionation at different altitudes are required. The combustion-induced negative Δ36S may be linked to recombination reactions of elemental sulfur [6], and relevant experiments are being conducted to test the isotope effect. Although combustion is unlikely in Archean, recombination reactions may occur in other previously unappreciated processes such as volcanism and may contribute in part to the heavily depleted 36S in some Paleoarchean records [5,7]. The roles of both photochemical and non-photochemical reactions in the variability of Archean S-MIF records require further analysis in the future. Refs: [1] Farquhar et al., Science 2000; [2] Shaheen et al., PNAS 2014; [3] Lin et al., PNAS 2016; [4] Wacey et al., Precambrian Res 2015; [5] Muller et al., PNAS 2016; [6] Babikov, PNAS 2017; [7] Shen et al., EPSL, 2009.

Quantification and isotopic analysis of intracellular sulfur metabolites in the dissimilatory sulfate reduction pathway

Science.gov (United States)

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

Sulfur and lead isotope geochemistry of the orogenic gold deposits in the eastern Kunlun area, Qinghai province

International Nuclear Information System (INIS)

Feng Chengyou; Zhang Dequan; Li Daxin; She Hongquan; Zhu Huaping

2003-01-01

Based on researches on the basic geological characteristics and sulfur and lead isotopic geochemistry of four typical gold deposits, it is considered that they have many similar geo-geochemical characteristics and are all related genetically to orogenic process. Therefore, they should belong to a type of orogenic gold deposits according to the newest classification of gold deposits provided by Kerrich et al. (2000). There is a big change in the average 34 S values of the sulfides selected from different deposits, varying from -3.7‰-4.4‰ and tower-shape distribution is apparent. The lead isotope in four gold deposits is characterized by high compositions and minor changes, with 206 Pb/ 204 Pb > 18.3380, 207 Pb/ 204 Pb > 15.5555, 208 Pb/ 204 Pb >38.1796 in ores and wall-rocks, it can be concluded that the ore-forming material consisting of sulfur and lead are mainly derived from wall-rocks. Intensive subduction and collision during late Paleozoic and early Mesozoic not only formed deep faults, large-scale shear belt, and low-order folds and faults but also induced fluidization and mineralization, and resulted in formation and zonal distribution of several large or medium gold deposits in this area. (authors)

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

Science.gov (United States)

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

2005-08-01

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

Annual report 1982 of ZWO Laboratory of Isotope Geology

International Nuclear Information System (INIS)

1983-07-01

This report gives a brief account of the activities of the ZWO Laboratory of Isotope Geology during 1982. The main point of interest is the research for new possible applications of gas-mass spectrometry in geology. Kr and Xe turn out to be produced at the spontaneous fission of 238 U present in zirconium crystals. Mass-spectrometric isotope analysis has been carried out, resulting in a tentative age estimation. (Auth.)

Sulfur Isotope Exchange between S-35 Labeled Inorganic Sulfur-Compounds in Anoxic Marine-Sediments

DEFF Research Database (Denmark)

FOSSING, H.; THODEANDERSEN, S.; JØRGENSEN, BB

1992-01-01

Isotope exchange reactions between S-35-labeled sulfur compounds were studied in anoxic estuarine sediment slurries at 21-degrees-C and pH 7.4-7.7. Two experiments labeled with radioactive elemental sulfur (S-35-degrees) and one labeled with radioactive sulfate ((SO42-)-S-35) were performed as time......% of the total S-35 was recovered in the SIGMA-HS- pool in less than 1.5 h. With no detectable SIGMA-HS- (less than 1-mu-M) in the slurry, 58% of the total S-35 was observed in the pyrite pool within 1.5 h. The FeS pool received up to 31% of all S-35 added. The rapid S-35 incorporation from S-35-degrees...... into SIGMA-HS- and FeS pools was explained by isotope exchange reactions. In contrast, there was evidence that the radioactivity observed in the 'pyrite pool' was caused by adhesion of the added S-35-degrees to the FeS2 grains. In all S-35-degrees-labeled experiments we also observed oxidation...

A simple and reliable method reducing sulfate to sulfide for multiple sulfur isotope analysis.

Science.gov (United States)

Geng, Lei; Savarino, Joel; Savarino, Clara A; Caillon, Nicolas; Cartigny, Pierre; Hattori, Shohei; Ishino, Sakiko; Yoshida, Naohiro

2018-02-28

Precise analysis of four sulfur isotopes of sulfate in geological and environmental samples provides the means to extract unique information in wide geological contexts. Reduction of sulfate to sulfide is the first step to access such information. The conventional reduction method suffers from a cumbersome distillation system, long reaction time and large volume of the reducing solution. We present a new and simple method enabling the process of multiple samples at one time with a much reduced volume of reducing solution. One mL of reducing solution made of HI and NaH 2 PO 2 was added to a septum glass tube with dry sulfate. The tube was heated at 124°C and the produced H 2 S was purged with inert gas (He or N 2 ) through gas-washing tubes and then collected by NaOH solution. The collected H 2 S was converted into Ag 2 S by adding AgNO 3 solution and the co-precipitated Ag 2 O was removed by adding a few drops of concentrated HNO 3 . Within 2-3 h, a 100% yield was observed for samples with 0.2-2.5 μmol Na 2 SO 4 . The reduction rate was much slower for BaSO 4 and a complete reduction was not observed. International sulfur reference materials, NBS-127, SO-5 and SO-6, were processed with this method, and the measured against accepted δ 34 S values yielded a linear regression line which had a slope of 0.99 ± 0.01 and a R 2 value of 0.998. The new methodology is easy to handle and allows us to process multiple samples at a time. It has also demonstrated good reproducibility in terms of H 2 S yield and for further isotope analysis. It is thus a good alternative to the conventional manual method, especially when processing samples with limited amount of sulfate available. © 2017 The Authors. Rapid Communications in Mass Spectrometry Pubished by John Wiley & Sons Ltd.

Sulfur isotope homogeneity of oceanic DMSP and DMS.

Science.gov (United States)

Amrani, Alon; Said-Ahmad, Ward; Shaked, Yeala; Kiene, Ronald P

2013-11-12

Oceanic emissions of volatile dimethyl sulfide (DMS) represent the largest natural source of biogenic sulfur to the global atmosphere, where it mediates aerosol dynamics. To constrain the contribution of oceanic DMS to aerosols we established the sulfur isotope ratios ((34)S/(32)S ratio, δ(34)S) of DMS and its precursor, dimethylsulfoniopropionate (DMSP), in a range of marine environments. In view of the low oceanic concentrations of DMS/P, we applied a unique method for the analysis of δ(34)S at the picomole level in individual compounds. Surface water DMSP collected from six different ocean provinces revealed a remarkable consistency in δ(34)S values ranging between +18.9 and +20.3‰. Sulfur isotope composition of DMS analyzed in freshly collected seawater was similar to δ(34)S of DMSP, showing that the in situ fractionation between these species is small (DMS to the atmosphere results in a relatively small fractionation (-0.5 ± 0.2‰) compared with the seawater DMS pool. Because δ(34)S values of oceanic DMS closely reflect that of DMSP, we conclude that the homogenous δ(34)S of DMSP at the ocean surface represents the δ(34)S of DMS emitted to the atmosphere, within +1‰. The δ(34)S of oceanic DMS flux to the atmosphere is thus relatively constant and distinct from anthropogenic sources of atmospheric sulfate, thereby enabling estimation of the DMS contribution to aerosols.

A sulfur isotopic study of alabandites from some manganese ore deposits in Japan

International Nuclear Information System (INIS)

Sasaki, Akira; Hirowatari, Fumitoshi; Fukuoka, Masato.

1985-01-01

Alabandites from Pretertiary bedded- and Tertiary vein-type manganese deposits in Japan have been examined for their sulfur isotopic composition. delta 34 S(CDT) value ranges widely from -31 to +11 per mil in 12 specimens taken from 10 bedded type deposits. While the mineral is no more than a minor constituent in most of the deposits, the isotopic features clearly indicate that these alabandites are of bacteriogenic sedimentary origin, thus raising an important constraint for the genesis of this group of deposits. A cluster of delta 34 S around -30 per mil implies an open-system, steady-state reduction (Schwarcz and Burnie, 1973) from a source SO 4 2- with the isotopic level of ca. +20 per mil. The inferred source is likely to have been in the Triassic sea. Current conjectures upon the age of host sedimentary rocks of the deposits concerned are in favor of this view. Alabandites from the Tertiary (Miocene) vein type deposits show only a minor variation in delta 34 S, +4 to +5 per mil. The data are very similar to the average isotopic composition of sulfides of the Miocene, ''Green Tuff'' mineralization represented by the kuroko type deposits. The remarkable consistency in sulfur isotopic composition of the Green Tuff mineralization over an extensive area may require a huge, common reservoir of sulfur in some form, which still remains an enigma. (author)

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

Energy Technology Data Exchange (ETDEWEB)

Boulyga, Sergei F.; Heilmann, Jens; Heumann, Klaus G. [Johannes Gutenberg-University Mainz (Germany). Institute of Inorganic Chemistry and Analytical Chemistry

2005-08-01

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

Determination of sulfur in steels by isotope dilution mass spectrometry after dissolution with sealed tube

International Nuclear Information System (INIS)

Watanabe, Kazuo

1981-01-01

The scaled tube dissolution technique was studied for the complete conversion of sulfur in steels to sulfate. Isotope dilution mass spectrometry was used for the determination of sulfur in the sulfate. Sample (0.5 g) was dissolved in nitric acid (7 ml) and hydrochloric acid (3 ml) in a scaled borosilicate glass tube on being heated above 180 0 C overnight. Nitrate ions were removed by repeated evaporation with hydrochloric acid. The residue was dissolved in hydrochloric acid. Sulfate was reduced with a mixture of hydrochloric, hydroiodic and hypophosphorous acids; hydrogen sulfide evolved was absorbed in cadmium acetate solution, then converted to silver sulfide, which was burned to sulfur dioxide in pure oxygen at low pressure, for isotopic analysis. Analytical blank in whole procedure was 0.8 μg of sulfur. This technique was applied to the determination of sulfur in NBS low alloy steels. The principal cause of low values obtained by the open beaker dissolution technique was evaporation losses of sulfur as sulfur dioxide during the dissolution. (author)

Sulfur-induced offsets in MC-ICP-MS silicon-isotope measurements

NARCIS (Netherlands)

van den Boorn, S.; Vroon, P.Z.; van Bergen, M.J.

2009-01-01

Sample preparation methods for MC-ICP-MS silicon-isotope measurements often involve a cation-exchange purification step. A previous study has argued that this would suffice for geological materials, as the occasional enrichment of anionic species would not compromise silicon-isotope analysis. Here

3. South American symposium on isotope geology. Extended abstracts

International Nuclear Information System (INIS)

2001-10-01

This publication include papers in the fields on Methodology, thermochronology, and geochronology; Evolution of cratonic South America; Magmatic processes; Environmental geology, hydrogeology, isotopic stratigraphy and paleoclimatology; Economic Geology and Evolution of the Andean margin of South America

Sulfur isotope variability of oceanic DMSP generation and its contributions to marine biogenic sulfur emissions.

Science.gov (United States)

Oduro, Harry; Van Alstyne, Kathryn L; Farquhar, James

2012-06-05

Oceanic dimethylsulfoniopropionate (DMSP) is the precursor to dimethylsulfide (DMS), which plays a role in climate regulation through transformation to methanesulfonic acid (MSA) and non-seasalt sulfate (NSS-SO(4)(2-)) aerosols. Here, we report measurements of the abundance and sulfur isotope compositions of DMSP from one phytoplankton species (Prorocentrum minimum) and five intertidal macroalgal species (Ulva lactuca, Ulva linza, Ulvaria obscura, Ulva prolifera, and Polysiphonia hendryi) in marine waters. We show that the sulfur isotope compositions (δ(34)S) of DMSP are depleted in (34)S relative to the source seawater sulfate by ∼1-3‰ and are correlated with the observed intracellular content of methionine, suggesting a link to metabolic pathways of methionine production. We suggest that this variability of δ(34)S is transferred to atmospheric geochemical products of DMSP degradation (DMS, MSA, and NSS-SO(4)(2-)), carrying implications for the interpretation of variability in δ(34)S of MSA and NSS-SO(4)(2-) that links them to changes in growth conditions and populations of DMSP producers rather than to the contributions of DMS and non-DMS sources.

Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico

Science.gov (United States)

Jimenez, A.

2012-04-01

Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico Abigail Jimenez-Franco1*, Pura Alfonso Abella2, Carles Canet3, Eduardo González-Partida4 1 Posgrado en Ciencias de la Tierra, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 2 Departament d'Enginyeria Minera i Recursos Naturals, Universitat Politècnica de Catalunya, Av de Les Bases de Manresa 61-73, 08242 Manresa. 3Instituto de Geofísica, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 4Centro de Geociencias, Universidad Nacional Autónoma de México, Campus Juriquilla, Boulevard Juriquilla 3001, 76230 Santiago de Querétaro, Qro., Mexico The Velardeña mining district is located in north-eastern part of the state of Durango, in northern of Mexico. The ore deposit is a lead-zinc, garnet-rich skarn developed at the contact between granite porphyry dikes (Eocene) and well-laminated limestones with interbedded chert (Albian-Cenomanian). A study of sulfur isotopes has been carried out in various sulfide minerals of the ores of Velardeña, in order to: (a) constrain the possible sources of sulfur and, therefore, better understand the sulfide mineralizing processes, and (b) to estimate the temperature of the ore-forming stage of the skarn. Sulfur isotope analyses were performed in 21 pure fractions of sulfide minerals of the ore mineralization (pyrite, chalcopyrite, sphalerite and galena). The mineral separation was performed using a series of sieves, and the purity of the samples was verified under a binocular microscope. Isotopic analyses were done on a Finnigan MAT Delta C flow elemental analyzer coupled to a TC-EA, according with the method of Giesemann et al. (1974). The δ34S values of the analyzed sulfides range mostly between -0.6 and +2.6 ‰ (relative to the CDT standard). These values are indicative of a magmatic source of sulfur. A single analysis falls

Improved analytical techniques of sulfur isotopic composition in nanomole quantities by MC-ICP-MS.

Science.gov (United States)

Yu, Tsai-Luen; Wang, Bo-Shian; Shen, Chuan-Chou; Wang, Pei-Ling; Yang, Tsanyao Frank; Burr, George S; Chen, Yue-Gau

2017-10-02

We propose an improved method for precise sulfur isotopic measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in conjunction with a membrane desolvation nebulization system. The problems of sulfur loss through the membrane desolvation apparatus are carefully quantified and resolved. The method overcomes low intrinsic sulfur transmission through the instrument, which was initially 1% when operating at a desolvation temperature of 160 °C. Sulfur loss through the membrane desolvation apparatus was resolved by doping with sodium. A Na/S ratio of 2 mol mol -1 produced sulfur transmissions with 98% recovery. Samples of 3 nmol (100 ng) sulfur achieved an external precision of ±0.18‰ (2 SD) for δ 34 S and ±0.10‰ (2 SD) for Δ 33 S (uppercase delta expresses the extent of mass-independent isotopic fractionation). Measurements made on certified reference materials and in-house standards demonstrate analytical accuracy and reproducibility. We applied the method to examine microbial-induced sulfur transformation in marine sediment pore waters from the sulfate-methane transition zone. The technique is quite versatile, and can be applied to a range of materials, including natural waters and minerals. Copyright © 2017 Elsevier B.V. All rights reserved.

Gas chromatographic studies of the relative retention of the sulfur isotopes in carbonyl sulfide, carbon disulfide, and sulfur dioxide

International Nuclear Information System (INIS)

Fetzer, J.C.; Rogers, L.B.

1980-01-01

A precision gas chromatograph, coupled to a quadrupole mass spectrometer and an on-line computer, was used to study the fractionation on Porasil A of the 32 S/ 34 S isotopic pair in a variety of sulfur-containing molecules. Carbonyl sulfide (COS) yielded an average α value of 1.00074 +- 0.00017 (standard deviation) for the temperature range 25 0 C to 75 0 C. The carbon disulfide (CS 2 ) value was 1.00069 +- 0.00023 for the range 53 0 C to 103 0 C, and that for sulfur dioxide (SO 2 ) was 1.00090 +- 0.00018 for the range 62 0 C to 112 0 C. Differential thermodynamic data have been reported. A Porapak Q column showed no fractionation of this isotopic pair in these three molecules

Preparation of Authigenic Pyrite from Methane-bearing Sediments for In Situ Sulfur Isotope Analysis Using SIMS.

Science.gov (United States)

Lin, Zhiyong; Sun, Xiaoming; Peckmann, Jörn; Lu, Yang; Strauss, Harald; Xu, Li; Lu, Hongfeng; Teichert, Barbara M A

2017-08-31

Different sulfur isotope compositions of authigenic pyrite typically result from the sulfate-driven anaerobic oxidation of methane (SO4-AOM) and organiclastic sulfate reduction (OSR) in marine sediments. However, unravelling the complex pyritization sequence is a challenge because of the coexistence of different sequentially formed pyrite phases. This manuscript describes a sample preparation procedure that enables the use of secondary ion mass spectroscopy (SIMS) to obtain in situ δ 34 S values of various pyrite generations. This allows researchers to constrain how SO4-AOM affects pyritization in methane-bearing sediments. SIMS analysis revealed an extreme range in δ 34 S values, spanning from -41.6 to +114.8‰, which is much wider than the range of δ 34 S values obtained by the traditional bulk sulfur isotope analysis of the same samples. Pyrite in the shallow sediment mainly consists of 34 S-depleted framboids, suggesting early diagenetic formation by OSR. Deeper in the sediment, more pyrite occurs as overgrowths and euhedral crystals, which display much higher SIMS δ 34 S values than the framboids. Such 34 S-enriched pyrite is related to enhanced SO4-AOM at the sulfate-methane transition zone, postdating OSR. High-resolution in situ SIMS sulfur isotope analyses allow for the reconstruction of the pyritization processes, which cannot be resolved by bulk sulfur isotope analysis.

Coupled sulfur isotopic and chemical mass transfer modeling: Approach and application to dynamic hydrothermal processes

International Nuclear Information System (INIS)

Janecky, D.R.

1988-01-01

A computational modeling code (EQPSreverse arrowS) has been developed to examine sulfur isotopic distribution pathways coupled with calculations of chemical mass transfer pathways. A post processor approach to EQ6 calculations was chosen so that a variety of isotopic pathways could be examined for each reaction pathway. Two types of major bounding conditions were implemented: (1) equilibrium isotopic exchange between sulfate and sulfide species or exchange only accompanying chemical reduction and oxidation events, and (2) existence or lack of isotopic exchange between solution species and precipitated minerals, parallel to the open and closed chemical system formulations of chemical mass transfer modeling codes. All of the chemical data necessary to explicitly calculate isotopic distribution pathways is generated by most mass transfer modeling codes and can be input to the EQPS code. Routines are built in to directly handle EQ6 tabular files. Chemical reaction models of seafloor hydrothermal vent processes and accompanying sulfur isotopic distribution pathways illustrate the capabilities of coupling EQPSreverse arrowS with EQ6 calculations, including the extent of differences that can exist due to the isotopic bounding condition assumptions described above. 11 refs., 2 figs

SO2 photoexcitation mechanism links mass-independent sulfur isotopic fractionation in cryospheric sulfate to climate impacting volcanism

DEFF Research Database (Denmark)

Hattori, Shohei; Schmidt, Johan Albrecht; Johnson, Matthew Stanley

2013-01-01

Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores......, but the concentration of glacial sulfate does not distinguish between tropospheric and stratospheric eruptions. Stable sulfur isotope abundances contain additional information, and recent studies show a correlation between volcanic plumes that reach the stratosphere and mass-independent anomalies in sulfur isotopes...... plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. The model accounts for the amplitude, phases, and time development of Δ(33)S/δ(34)S and Δ(36)S/Δ(33)S found in glacial samples. We are able to identify the process controlling...

Guidelines for the use of isotopes of sulfur in soil-plant studies

International Nuclear Information System (INIS)

2003-01-01

Sulfur (S) is an essential element in plant, human and animal nutrition. This publication provides an overview of the sulfur cycle and how isotopic tracers can be used to obtain unique and precise information on the fluxes and movement of S between and within different compartments of the soil-plant system. It provides information on the theory and measurement of 35S and 34S, safety procedures using 35S, preparation of labelled S fertilizers and plant residues, estimation of the quantity of isotope required for different temporal and spatial scales, preparation digestion /extraction) and analysis of soil and plant samples and guidelines on comparative advantages with non-nuclear techniques and applications, including case studies and references. It is a timely publication in that greater attention is now being focused on S deficiencies in agriculture, which are becoming more common due to reduced atmospheric accretions from industrial sources and to the reduced use of fertilizer materials that contain sulfur as a secondary nutrient. The sub-programme in Soil and Water Management and Crop Nutrition is committed to the dissemination of information to Member States on the practical applications of nuclear techniques through the IAEA Training Course Series. The present publication is preceded by IAEA-TCS-14 (2001), Use of Isotope and Radiation Methods in Soil and Water Management and Crop Nutrition, and IAEA-TCS-16 (2002), Neutron and Gamma Probes: Their Use in Agronomy

Guidelines for the use of isotopes of sulfur in soil-plant studies

Energy Technology Data Exchange (ETDEWEB)

NONE

2003-08-01

Sulfur (S) is an essential element in plant, human and animal nutrition. This publication provides an overview of the sulfur cycle and how isotopic tracers can be used to obtain unique and precise information on the fluxes and movement of S between and within different compartments of the soil-plant system. It provides information on the theory and measurement of 35S and 34S, safety procedures using 35S, preparation of labelled S fertilizers and plant residues, estimation of the quantity of isotope required for different temporal and spatial scales, preparation digestion /extraction and analysis of soil and plant samples and guidelines on comparative advantages with non-nuclear techniques and applications, including case studies and references. It is a timely publication in that greater attention is now being focused on S deficiencies in agriculture, which are becoming more common due to reduced atmospheric accretions from industrial sources and to the reduced use of fertilizer materials that contain sulfur as a secondary nutrient. The sub-programme in Soil and Water Management and Crop Nutrition is committed to the dissemination of information to Member States on the practical applications of nuclear techniques through the IAEA Training Course Series. The present publication is preceded by IAEA-TCS-14 (2001), Use of Isotope and Radiation Methods in Soil and Water Management and Crop Nutrition, and IAEA-TCS-16 (2002), Neutron and Gamma Probes: Their Use in Agronomy.

Source of arsenic-bearing pyrite in southwestern Vermont, USA: Sulfur isotope evidence

Energy Technology Data Exchange (ETDEWEB)

Mango, Helen, E-mail: helen.mango@castleton.edu [Department of Natural Sciences, Castleton State College, 233 South Street, Castleton, VT 05735 (United States); Ryan, Peter, E-mail: pryan@middlebury.edu [Department of Geology, Middlebury College, 276 Bicentennial Way, Middlebury, VT 05753 (United States)

2015-02-01

Arsenic-bearing pyrite is the source of arsenic in groundwater produced in late Cambrian and Ordovician gray and black slates and phyllites in the Taconic region of southwestern Vermont, USA. The aim of this study is to analyze the sulfur isotopic composition of this pyrite and determine if a relationship exists between pyrite δ{sup 34}S and arsenic content. Pyrite occurs in both sedimentary/diagenetic (bedding-parallel layers and framboids) and low-grade metamorphic (porphyroblast) forms, and contains up to > 2000 ppm As. The sulfur isotopic composition of arsenic-bearing pyrite ranges from − 5.2‰ to 63‰. In the marine environment, the sulfur in sedimentary pyrite becomes increasingly enriched in {sup 34}S as the geochemical environment becomes increasingly anoxic. There is a positive correlation between δ{sup 34}S and arsenic content in the Taconic pyrite, suggesting that uptake of arsenic by pyrite increased as the environment became more reducing. This increased anoxia may have been due to a rise in sea level and/or tectonic activity during the late Cambrian and Ordovician. Low-grade metamorphism appears to have little effect on sulfur isotope composition, but does correlate with lower arsenic content in pyrite. New groundwater wells drilled in this region should therefore avoid gray and black slates and phyllites that contain sedimentary/diagenetic pyrite with heavy δ{sup 34}S values. - Highlights: • Pyrite is the source of arsenic in groundwater in the Taconic region of Vermont, USA. • As-bearing pyrite δ{sup 34}S = – 5.2 to 63‰ with higher {sup 34}S as environment becomes more anoxic. • High sea level, tectonic activity create anoxia, with incorporation of As into pyrite. • New wells should avoid slate/phyllite containing sedimentary pyrite with heavy δ{sup 34}S.

Source of arsenic-bearing pyrite in southwestern Vermont, USA: Sulfur isotope evidence

International Nuclear Information System (INIS)

Mango, Helen; Ryan, Peter

2015-01-01

Arsenic-bearing pyrite is the source of arsenic in groundwater produced in late Cambrian and Ordovician gray and black slates and phyllites in the Taconic region of southwestern Vermont, USA. The aim of this study is to analyze the sulfur isotopic composition of this pyrite and determine if a relationship exists between pyrite δ 34 S and arsenic content. Pyrite occurs in both sedimentary/diagenetic (bedding-parallel layers and framboids) and low-grade metamorphic (porphyroblast) forms, and contains up to > 2000 ppm As. The sulfur isotopic composition of arsenic-bearing pyrite ranges from − 5.2‰ to 63‰. In the marine environment, the sulfur in sedimentary pyrite becomes increasingly enriched in 34 S as the geochemical environment becomes increasingly anoxic. There is a positive correlation between δ 34 S and arsenic content in the Taconic pyrite, suggesting that uptake of arsenic by pyrite increased as the environment became more reducing. This increased anoxia may have been due to a rise in sea level and/or tectonic activity during the late Cambrian and Ordovician. Low-grade metamorphism appears to have little effect on sulfur isotope composition, but does correlate with lower arsenic content in pyrite. New groundwater wells drilled in this region should therefore avoid gray and black slates and phyllites that contain sedimentary/diagenetic pyrite with heavy δ 34 S values. - Highlights: • Pyrite is the source of arsenic in groundwater in the Taconic region of Vermont, USA. • As-bearing pyrite δ 34 S = – 5.2 to 63‰ with higher 34 S as environment becomes more anoxic. • High sea level, tectonic activity create anoxia, with incorporation of As into pyrite. • New wells should avoid slate/phyllite containing sedimentary pyrite with heavy δ 34 S

An Experimental Study of Low-Temperature Sulfurization of Carbohydrates Using Various Sulfides Reveals Insights into Structural Characteristics and Sulfur Isotope Compositions of Macromolecular Organic Matter in the Environment

Science.gov (United States)

OBeirne, M. D.; Werne, J. P.; Van Dongen, B.; Gilhooly, W., III

2017-12-01

Sulfurization of carbohydrates has been suggested as an important mechanism for the preservation of organic matter in anoxic/euxinic depositional environments. In this study, glucose was sulfurized under laboratory conditions at room temperature (24°C) using three commercially available sulfides - ammonium sulfide ([NH4]2S), sodium sulfide (Na2S), and sodium hydrosulfide (NaHS), each mixed with elemental sulfur to produce polysulfide solutions. The reaction products were analyzed using Fourier transform infrared spectroscopy (FTIR), which revealed structural differences among the products formed via the three sulfide reactants. Additionally, analysis of the bulk sulfur isotope compositions of reactants and products was used to determine the fractionation(s) associated with abiotic sulfur incorporation into organic matter. Samples from both modern (Mahoney Lake, British Colombia, Canada) and ancient (Jurassic aged Blackstone Band from the Kimmeridge Clay Formation, Dorset, United Kingdom) euxinic systems were also analyzed for comparison to laboratory samples. Results from this study provide experimental evidence for the structural and sulfur isotopic relationships of sulfurized organic matter in the geosphere.

Isotopic abundance analysis of carbon, nitrogen and sulfur with a combined elemental analyzer-mass spectrometer system

International Nuclear Information System (INIS)

Pichlmayer, F.; Blochberger, K.

1988-01-01

Stable isotope ratio measurements of carbon, nitrogen and sulfur are of growing interest as analytical tool in many fields of research, but applications were somewhat hindered in the past by the fact that cumbersome sample preparation was necessary. A method has therefore been developed, consisting in essential of coupling an elemental analyzer with an isotope mass spectrometer, enabling fast and reliable conversion of C-, N- and S-compounds in any solid or liquid sample into the measuring gases carbon dioxide, nitrogen and sulfur dioxide for on-line isotopic analysis. The experimental set-up and the main characteristics are described in short and examples of application in environmental research, food analysis and clinical diagnosis are given. (orig.)

Nitrogen, Sulfur, and Oxygen Isotope Ratios of Animal- and Plant-Based Organic Fertilizers Used in South Korea.

Science.gov (United States)

Shin, Woo-Jin; Ryu, Jong-Sik; Mayer, Bernhard; Lee, Kwang-Sik; Kim, Insu

2017-05-01

Organic fertilizers are increasingly used in agriculture in Asia and elsewhere. Tracer techniques are desirable to distinguish the fate of nutrients added to agroecosystems with organic fertilizers from those contained in synthetic fertilizers. Therefore, we determined the nitrogen, sulfur, and oxygen isotope ratios of nitrogen- and sulfur-bearing compounds in animal- and plant-based organic fertilizers (ABOF and PBOF, respectively) used in South Korea to evaluate whether they are isotopically distinct. The δN values of total and organic nitrogen for ABOF ranged from +7 to +19‰ and were higher than those of PBOF (generally fertilizer compounds in the plant-soil-water system, whereas PBOFs have similar δN values to synthetic fertilizers. However, δO values for nitrate (δO) from organic fertilizer samples (fertilizers. The δS values of total sulfur, organic sulfur compounds (e.g., carbon-bonded sulfur and hydriodic acid-reducible sulfur), and sulfate for ABOFs yielded wide and overlapping ranges of +0.3 to +6.3, +0.9 to +7.2, and -2.6 to +14.2‰, whereas those for PBOFs varied from -3.4 to +7.7, +1.4 to +9.4, and -4.1 to +12.5‰, respectively, making it challenging to distinguish the fate of sulfur compounds from ABOF and PBOF in the environment using sulfur isotopes. We conclude that the δN values of ABOFs and the O values of organic fertilizers are distinct from those of synthetic fertilizers and are a promising tool for tracing the fate of nutrients added by organic fertilizers to agroecosystems. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

RARE ISOTOPIC SPECIES OF SULFUR MONOXIDE: THE ROTATIONAL SPECTRUM IN THE THz REGION

Energy Technology Data Exchange (ETDEWEB)

Lattanzi, Valerio; Cazzoli, Gabriele; Puzzarini, Cristina, E-mail: lattanzi@mpe.mpg.de [Dipartimento di Chimica “Giacomo Ciamician,” Università di Bologna, Via Selmi 2, I-40126 Bologna (Italy)

2015-11-01

Many sulfur-bearing species have been detected in different astronomical environments and have allowed us to derive important information about the chemical and physical composition of interstellar regions. In particular, these species have also been shown to trace and probe hot-core environment time evolution. Among the most prominent sulfur-bearing molecules is SO, the sulfur monoxide radical, one of the more ubiquitous and abundant, which is also observed in its isotopic substituted species such as {sup 34}SO and S{sup 18}O. Due to the importance of this simple diatomic system, and in order to face the challenge of modern radioastronomical facilities, an extension to the THz range of the rare isotopologues of sulfur monoxide has been performed. High-resolution rotational molecular spectroscopy has been employed to extend the available data set of four isotopic species, SO, {sup 34}SO, S{sup 17}O, and S{sup 18}O, up to the 1.5 THz region. The frequency coverage and spectral resolution of our measurements allowed a better constraint of the molecular constants of the four species considered, specifically focusing on the two oxygen-substituted isotopologues. Our measurements were also employed in an isotopically invariant fit including all of the available pure rotational and ro-vibrational transitions for all of the SO isotopologues, thus enabling accurate predictions of the rotational transitions at higher frequencies. We also provide comparisons with recent works performed on the same system, demonstrating the quality of our experiment and the improvement of the data sets for all of the species considered. Transition frequencies for this system can now be used with confidence by the astronomical community well into the THz spectral region.

Quadruple sulfur isotope constraints on the origin and cycling of volatile organic sulfur compounds in a stratified sulfidic lake

Science.gov (United States)

Oduro, Harry; Kamyshny, Alexey; Zerkle, Aubrey L.; Li, Yue; Farquhar, James

2013-11-01

We have quantified the major forms of volatile organic sulfur compounds (VOSCs) distributed in the water column of stratified freshwater Fayetteville Green Lake (FGL), to evaluate the biogeochemical pathways involved in their production. The lake's anoxic deep waters contain high concentrations of sulfate (12-16 mmol L-1) and sulfide (0.12 μmol L-1 to 1.5 mmol L-1) with relatively low VOSC concentrations, ranging from 0.1 nmol L-1 to 2.8 μmol L-1. Sulfur isotope measurements of combined volatile organic sulfur compounds demonstrate that VOSC species are formed primarily from reduced sulfur (H2S/HS-) and zero-valent sulfur (ZVS), with little input from sulfate. Thedata support a role of a combination of biological and abiotic processes in formation of carbon-sulfur bonds between reactive sulfur species and methyl groups of lignin components. These processes are responsible for very fast turnover of VOSC species, maintaining their low levels in FGL. No dimethylsulfoniopropionate (DMSP) was detected by Electrospray Ionization Mass Spectrometry (ESI-MS) in the lake water column or in planktonic extracts. These observations indicate a pathway distinct from oceanic and coastal marine environments, where dimethylsulfide (DMS) and other VOSC species are principally produced via the breakdown of DMSP by plankton species.

Sulfur isotopic ratios of molybdenites from the Hida Mountains, Japan

International Nuclear Information System (INIS)

Ishihara, Shunso; Harayama, Satoru; Sasaki, Akira.

1990-01-01

Molybdenites occurring in Paleogene granitoids of the Northern Japan Alps of the Hida Mountains were analyzed for δ 34 S CDT at seven localities. The sulfur isotopic ratios vary from 3.0 to 6.4 per mille, which are within the range of ore molybdenites from the magnetite-series granitic terrane of the Sanin district, indicating that the Hida Mountains and Sanin district belong to the same metallogenic province. Porphyry-type molybdenite from the Kamioka lead-zinc mine has the δ 34 S value of 1.4 per mille. Sulfur of the molybdenite is not derived from the Jurassic Funatsu granitoids but brought up by the latest Cretaceous ilmenite-series magma, prior to the main Paleogene magnetite-series magmatism. (author)

Characterization of fluid inclusions and sulfur isotopes in the Iju porphyry copper deposit, North West of Shahr-e-Babak

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Malihe Golestani

2017-07-01

Full Text Available Introduction The Iju porphyry copper deposit is located in the southern part of the Urumieh-Dokhtar magmatic arc (Dehaj-Sarduieh belt within the Kerman copper belt (Dimitrijevic, 1973. The Porphyry Copper mineralization in the Iranian plate occurs dominantly along the Urumieh-Dokhtar arc, which has resulted from the subduction of the Arabian plate beneath the central Iran and the closure of the Neo-Tethys Ocean during the Alpine orogeny (Hassanzadeh, 1993. The Iju porphyry copper deposit with 25 million tons of ore reserves is one of the main copper deposits within the Kerman copper belt. The mining area is composed of upper Miocene volcanic and subvolcanic rocks (mineralized and barren subvolcanic rocks and quaternary deposits. Two hydrothermal alteration zones of quartz-sericite-pyrite and propylitic zones can be identified in the Iju area. The copper mineralization in the Iju deposit occurs as disseminated, stockwork and hydrothermal breccia. In the hypogene zone, the mineral paragenesis include chalcopyrite, pyrite, with minor occurrences of bornite and magnetite. This paper reports geological, mineralogical, fluid inclusion and S isotope data from the Iju deposit in order to investigate ore-bearing fluids’ characteristics and the mechanisms of ore deposition. Materials and methods Fifteen samples of syngenetic quartz+pyrite bearing veinlets within the quartz-sericite-pyrite zone were selected from different depths across the seven boreholes. Quartz was used for double-polished thin sections and pyrite was used for sulfur isotope analysis. Fluid inclusion studies were performed using the Linkam cooling and heating stage, the THMSG 600 model. The syngenetic pyrite with thermometry quartz sample was used for the sulfur isotope experiments. Stable isotope analysis was performed at the Hatch Stable Isotope Laboratory in the University of Ottawa, Canada. Results The fluid inclusions of the Iju deposit represent a wide range in the

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

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

2017-12-01

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

Neoproterozoic sulfur-isotope variation in Australia

International Nuclear Information System (INIS)

Gorjan, P.; Walter, M.R.

2000-01-01

A number of stages are apparent in sulfur-isotope geochemistry throughout the Neoproterozoic. Prior to the Sturtian glaciation (840-700 Ma) δ 34 S sulfate varied little (19 to 17.5 per mil), and δ 34 S sulfide ranged from -20 to +23 per mil. In the Bitter Springs Formation δ 34 S sulfide is greater in the non-marine portion compared to the marine portion. This can be explained by a paucity of sulfate in the non-marine waters, and is consistent with mineralogical evidence (Southgate, 1991). In the Sturtian glacial sediments δ 34 S sulfide starts below 0 per mil and rises to >30 per mil at the top of the glacial sediments. After the Sturtian glaciation δ 34 S sulfide averages ∼30 per mil (and 34 per mil for δ 34 S organic ) for the extent of silt deposition. This increase in δ 34 S sulfide also appears in China, Canada and Namibia (Gorjan et al., 2000). δ 34 S sulfate also rises but is lower than the average δ 34 S sulfate (5 sulfate nodules in the Tapley Hill Formation average 26 per mil). However, the sulfate nodules may not be preserving the original seawater δ 34 S sulfate 34 S enrichment in sulfides usually occurs in freshwater or euxinic settings, but all evidence points to a sulfate-rich and non-euxinic environment in the Sturtian post-glacial deposits (linear %C vs. %S plots; high FeS 2 :FeS ratios; low degree of pyritisation; Gorjan et al. 2000, Gorjan, 1998). Such a situation points to sulfides being formed from extremely 34 S enriched sulfate (perhaps up to 45 per mil). This global rise in δ 34 S of both sulfur fractions in the Sturtian postglacial has led us to speculate that 34 S enriched sulfate was formed beneath a stagnant, ice-covered ocean, an environment postulated by Hoffman (1998), during the Sturtian glaciation and was brought to shallower waters in an ocean-upwelling event. Sulfide depleted in 34 S may have been deposited on abyssal plains. δ 34 S sulfide and δ 34 S sulfate falls sharply at the conclusion of siltstone deposition

Measuring Sulfur Isotope Ratios from Solid Samples with the Sample Analysis at Mars Instrument and the Effects of Dead Time Corrections

Science.gov (United States)

Franz, H. B.; Mahaffy, P. R.; Kasprzak, W.; Lyness, E.; Raaen, E.

2011-01-01

The Sample Analysis at Mars (SAM) instrument suite comprises the largest science payload on the Mars Science Laboratory (MSL) "Curiosity" rover. SAM will perform chemical and isotopic analysis of volatile compounds from atmospheric and solid samples to address questions pertaining to habitability and geochemical processes on Mars. Sulfur is a key element of interest in this regard, as sulfur compounds have been detected on the Martian surface by both in situ and remote sensing techniques. Their chemical and isotopic composition can belp constrain environmental conditions and mechanisms at the time of formation. A previous study examined the capability of the SAM quadrupole mass spectrometer (QMS) to determine sulfur isotope ratios of SO2 gas from a statistical perspective. Here we discuss the development of a method for determining sulfur isotope ratios with the QMS by sampling SO2 generated from heating of solid sulfate samples in SAM's pyrolysis oven. This analysis, which was performed with the SAM breadboard system, also required development of a novel treatment of the QMS dead time to accommodate the characteristics of an aging detector.

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

Science.gov (United States)

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

2018-06-01

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

Early inner solar system origin for anomalous sulfur isotopes in differentiated protoplanets.

Science.gov (United States)

Antonelli, Michael A; Kim, Sang-Tae; Peters, Marc; Labidi, Jabrane; Cartigny, Pierre; Walker, Richard J; Lyons, James R; Hoek, Joost; Farquhar, James

2014-12-16

Achondrite meteorites have anomalous enrichments in (33)S, relative to chondrites, which have been attributed to photochemistry in the solar nebula. However, the putative photochemical reactions remain elusive, and predicted accompanying (33)S depletions have not previously been found, which could indicate an erroneous assumption regarding the origins of the (33)S anomalies, or of the bulk solar system S-isotope composition. Here, we report well-resolved anomalous (33)S depletions in IIIF iron meteorites (solar system (solar system S-isotope composition was chondritic (consistent with IAB iron meteorites, Earth, Moon, and Mars). The range of mass-independent sulfur isotope compositions may reflect spatial or temporal changes influenced by photochemical processes. A tentative correlation between S isotopes and Hf-W core segregation ages suggests that the two systems may be influenced by common factors, such as nebular location and volatile content.

SO2 photoexcitation mechanism links mass-independent sulfur isotopic fractionation in cryospheric sulfate to climate impacting volcanism

Science.gov (United States)

Hattori, Shohei; Schmidt, Johan A.; Johnson, Matthew S.; Danielache, Sebastian O.; Yamada, Akinori; Ueno, Yuichiro; Yoshida, Naohiro

2013-01-01

Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores, but the concentration of glacial sulfate does not distinguish between tropospheric and stratospheric eruptions. Stable sulfur isotope abundances contain additional information, and recent studies show a correlation between volcanic plumes that reach the stratosphere and mass-independent anomalies in sulfur isotopes in glacial sulfate. We describe a mechanism, photoexcitation of SO2, that links the two, yielding a useful metric of the explosivity of historic volcanic events. A plume model of S(IV) to S(VI) conversion was constructed including photochemistry, entrainment of background air, and sulfate deposition. Isotopologue-specific photoexcitation rates were calculated based on the UV absorption cross-sections of 32SO2, 33SO2, 34SO2, and 36SO2 from 250 to 320 nm. The model shows that UV photoexcitation is enhanced with altitude, whereas mass-dependent oxidation, such as SO2 + OH, is suppressed by in situ plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. The model accounts for the amplitude, phases, and time development of Δ33S/δ34S and Δ36S/Δ33S found in glacial samples. We are able to identify the process controlling mass-independent sulfur isotope anomalies in the modern atmosphere. This mechanism is the basis of identifying the magnitude of historic volcanic events. PMID:23417298

Fractionation of sulfur isotopes in the chemical and biochemical oxidation of sulfide to sulfate

International Nuclear Information System (INIS)

Maass, I.; Wetzel, K.; Weise, G.; Heyer, J.

1983-01-01

The behaviour of sulfur isotopes in the chemical and biochemical oxidation of marcasite (FeS 2 ) to sulfate has been investigated in rest and shaker cultures at 30 0 C. The microbiological oxidation was carried out using a mixed culture of Thiobacillus. The results show a considerably faster formation of sulfate in the biochemical oxidation in comparison with the chemical oxidation. Isotope analyses of the formed sulfates indicate no or only very small isotope fractionations depending on experimental conditions. The highest enrichment of 32 S in the sulfate is 1.7 per mille. In accordance with the results of other authors it is concluded that in both chemical and biochemical weathering of sedimentary sulfides resulting in the formation of sulfates isotope effects are not of importance. (author)

Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

Directory of Open Access Journals (Sweden)

J. N. Crowley

2012-01-01

Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

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)

Science.gov (United States)

Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

2017-01-01

Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H2) is responsible for non-quantitative H2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer–Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems.

Sulfur isotope study of a modern intertidal environment, and the interpretation of ancient sulfides

International Nuclear Information System (INIS)

Chambers, L.A.

1982-01-01

Extensive sulfur isotope distribution data for sulfides precipitated in an intertidal environment show no distinctive features when compared with isotope values for other marine, sedimentary sulfides. The fractionation ranges from α = 1.030 to α = 1.048. The pattern is characteristic for a system essentially open to sulfate, and isotope analyses of interstitial sulfates are corroborative. A population of sulfate-reducing bacteria of the order of 10 9 organisms per cc of interstitial water is indicated. Seasonal variation of the isotope distribution reflects a transient sulfide composition and a bacterial population in which the fractionation effect is indirectly controlled by temperature. The data presented for this modern shallow water environment are at variance with an earlier assessment of isotopic distributions in ancient sulfides which linked shallow water environments with limited fractionation (α =< 1.025) in a closed system. (author)

Sulfur isotope study of a modern intertidal environment, and the interpretation of ancient sulfides

Energy Technology Data Exchange (ETDEWEB)

Chambers, L.A. (Baas Becking Geobiological Lab., Canberra City (Australia))

1982-05-01

Extensive sulfur isotope distribution data for sulfides precipitated in an intertidal environment show no distinctive features when compared with isotope values for other marine, sedimentary sulfides. The fractionation ranges from ..cap alpha.. = 1.030 to ..cap alpha.. = 1.048. The pattern is characteristic for a system essentially open to sulfate, and isotope analyses of interstitial sulfates are corroborative. A population of sulfate-reducing bacteria of the order of 10/sup 9/ organisms per cc of interstitial water is indicated. Seasonal variation of the isotope distribution reflects a transient sulfide composition and a bacterial population in which the fractionation effect is indirectly controlled by temperature. The data presented for this modern shallow water environment are at variance with an earlier assessment of isotopic distributions in ancient sulfides which linked shallow water environments with limited fractionation (..cap alpha.. =< 1.025) in a closed system.

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

Science.gov (United States)

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

Sulfur isotopic and proteomic profiles of sulfate reducers grown under differential steady-states

Science.gov (United States)

Leavitt, W.; Venceslau, S.; Waldbauer, J.; Smith, D. A.; Boidi, F. J.; Bradley, A. S.

2016-12-01

Microbial sulfate reducers (MSR) drive the Earth's biogeochemical sulfur cycle. At the heart of this energy metabolism is a cascade of redox transformations coupling organic carbon and/or hydrogen oxidation to the dissimilatory reduction of sulfate to sulfide. The product sulfide is depleted in the heavier isotopes of sulfur, relative to the reactant sulfate, consistent with a normal kinetic isotope effect. However, the magnitude of the net fractionation during MSR can range over a range of 70 permil, consistent with a multi-step set of reactions. This range in MSR fractionation has been shown to mainly depend on: i) the cell-specific sulfate reduction rate (csSRR), and ii) the ambient sulfate concentration. However, the fractionation under identical conditions differs among strains (Bradley et al. 2016. Geobio), and so must also be mediated by strain-specific processes, such as the nature and quantity of individual proteins involved in sulfate reduction, electron transport, and growth. In recent work we have examined the influence of electron donor, electron acceptor, and co-limitation under controlled steady-state culture conditions in order better inform models of MSR isotope fractionation, and the physiological and isotopic response to differential environmental forcings (e.g. Leavitt et al. (2013) PNAS). Recent models of the fractionation response to MSR rate (c.f. Bradley 2016; Wing & Halevy, 2016) make specific predictions for the responses of the cellular metabolome and proteome. Here we compare the steady-state S-isotopic fractionation and proteome of `fast' versus `slow' grown D. vulgaris, using replicate chemostats under electron donor limitation. We observe clear and statistically robust changes in some key central MSR and C-metabolism enzymes, though a host of the critical energy-transfer enzymes show no statistically discernable change. We discuss these results in light of recent theoretical advances and their relevance to modern and ancient

Recycling of water, carbon, and sulfur during subduction of serpentinites: A stable isotope study of Cerro del Almirez, Spain

Science.gov (United States)

Alt, Jeffrey C.; Garrido, Carlos J.; Shanks, Wayne C.; Turchyn, Alexandra; Padrón-Navarta, José Alberto; López Sánchez-Vizcaíno, Vicente; Gómez Pugnaire, María Teresa; Marchesi, Claudio

2012-01-01

We use the concentrations and isotope compositions of water, carbon, and sulfur in serpentinites and their dehydration products to trace the cycling of volatiles during subduction. Antigorite serpentinites from the Cerro del Almirez complex, Spain, contain 9–12 wt.% H2O and 910 ± 730 ppm sulfur, and have bulk δ18O values of 8.6 ± 0.4‰, δD = − 54 ± 5‰, and δ34S = 5.0‰, consistent with serpentinization at temperatures of ~ 200 °C by seawater hydrothermal fluids in a seafloor setting. The serpentinites were dehydrated to chlorite–harzburgite (olivine + orthopyroxene + chlorite) at 700 °C and 1.6–1.9 GPa during subduction metamorphism, resulting in loss of water, and sulfur. The chlorite–harzburgites contain 5.7 ± 1.9 wt.% H2O, and have bulk δ18O = 8.0 ± 0.9‰, and δD = − 77 ± 11‰. The rocks contain 650 ± 620 ppm sulfur having δ34S = 1.2‰. Dehydration of serpentinite resulted in loss of 5 wt.% H2O having δ18O = 8–10‰ and δD = − 27 to − 65‰, and loss of 260 ppm sulfur as sulfate, having δ34S = 14.5‰. The contents and δ13C of total carbon in the two rock types overlap, with a broad trend of decreasing carbon contents and δ13C from ~ 1300 to 200 ppm and − 9.6 to − 20.2‰. This reflects mixing between reduced carbon in the rocks (210 ppm, δ13C ≈ − 26‰) and seawater-derived carbonate (δ13C ≈ − 1‰). Our results indicate: 1) Serpentinized oceanic peridotites carry significant amounts of isotopically fractionated water, carbon and sulfur into subduction zones; 2) Subduction of serpentinites to high P and T results in loss of water, and sulfur, which can induce melting and contribute to 18O, D, and 34S enrichments and oxidation of the sub-arc mantle wedge; and 3) Isotopically fractionated water, carbon, and sulfur in serpentinite dehydration products are recycled deeper into the mantle where they can contribute to isotope heterogeneities and may be significant for volatile budgets of the deep Earth.

In situ sulfur isotopes (δ{sup 34}S and δ{sup 33}S) analyses in sulfides and elemental sulfur using high sensitivity cones combined with the addition of nitrogen by laser ablation MC-ICP-MS

Energy Technology Data Exchange (ETDEWEB)

Fu, Jiali [State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074 (China); Hu, Zhaochu, E-mail: zchu@vip.sina.com [State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074 (China); The Beijing SHRIMP Center, Institute of Geology, Chinese Academy of Geological Sciences, Beijing 102206 (China); Zhang, Wen [State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074 (China); Yang, Lu [State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074 (China); National Research Council Canada, 1200 Montreal Rd., Ottawa, Ontario K1A 0R6 (Canada); Liu, Yongsheng; Li, Ming; Zong, Keqing; Gao, Shan; Hu, Shenghong [State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074 (China)

2016-03-10

The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N{sub 2} on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4–8 ml min{sup −1} nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N{sub 2} = 4 ml min{sup −1}). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d{sub 90} values of the particles in pressed powder pellets for accurate

Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: interaction of seawater with fayalite and magnetite at 200-3500C

International Nuclear Information System (INIS)

Shanks, W.C. III; Bischoff, J.L.; Rosenbauer, R.J.

1981-01-01

Sulfate reduction during seawater reaction with fayalite and with magnetite was rapid at 350 0 C, producing equilibrium assemblages of talc-pyrite-hematite-magnetite at low water/rock ratios and talc-pyrite-hematite-anhydrite at higher water/rock ratios. At 250 0 C, seawater reacting with fayalite produced detectable amounts of dissolved H 2 S. At 200 0 C, dissolved H 2 S was not detected, even after 219 days. Reaction stoichiometry indicates that sulfate reduction requires large amounts of H + , which, in subseafloor hydrothermal systems is provided by Mg metasomatism. Seawater contains sufficient Mg to supply all the H + necessary for quantitative reduction of seawater sulfate. Systematics of sulfur isotopes in the 250 and 350 0 C experiments indicate that isotopic equilibrium is reached and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H 2 S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur. (author)

Sulfur isotope evidence for the contemporary formation of pyrite in a coastal acid sulfate soil

International Nuclear Information System (INIS)

Bush, R.T.; Sullivan, L.A.; Prince, K.; White, I.

2000-01-01

The sulfur isotopic composition of pyrite (FeS 2 ), greigite (Fe 3 S 4 ) and pore-water sulfate was determined for a typical coastal acid sulfate soil (ASS). Greigite occurs only in the partially oxidised upper-most pyrite sediments as blackish clusters within vertical fissures and other macro-pores. The concentration of pyrite was an order of magnitude greater than greigite in this layer, continuing through the underlying reduced estuarine sediments. δ 34 S of pyrite (0.45 per mil) associated with greigite accumulations were distinctly different to the bulk average for pyrite (-3.7 per mil), but similar to greigite (0.9 per mil). Greigite is meta-stable under reducing conditions, readily transforming to pyrite. The transformation of iron monosulfides (including greigite) to pyrite is a sulfur-isotope conservative process and therefore, these observations indicate that pyrite is forming from greigite at the oxic/anoxic boundary

Sulfur in the tree rings in Central Europe: A negative d34S shift relative to regional pollution sources

Czech Academy of Sciences Publication Activity Database

Novák, M.; Peiffer, S.; Žák, Karel; Jačková, I.; Buzek, F.; Erbanová, L.; Přechová, E.

2007-01-01

Roč. 71, 15 S1 (2007), A725-A725 ISSN 0046-564X. [Annual V. M. Goldschmidt Conference /17./. 19.08.2007-24.08.2007, Cologne] Institutional research plan: CEZ:AV0Z30130516 Keywords : sulfur isotopes * tree rings * Central Europe Subject RIV: DB - Geology ; Mineralogy

Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

Science.gov (United States)

Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.

2012-01-01

Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation

Sulfur concentration and isotopic variation in apatites from granitic to granodioritic plutons of a Cretaceous Cordilleran Batholith

Science.gov (United States)

Economos, R. C.

2012-12-01

Apatite is a common igneous accessory mineral with a high saturation temperature which can therefore crystallize over a significant portion of magmatic compositional space. Sulfur presents an opportunity to identify zoning in apatites. Unlike other trace elements, sulfur is relatively immobile in the apatite crystal structure and can be present in typical concentrations up to 1500 - 2000 ppm (or 0.5 to 1 wt% SO3). Sulfur concentration zoning in igneous apatites from ore producing magmatic systems has been identified (Streck and Dilles, 1998), but the interpretation of the cause of this zoning remains an open question. δ34S isotopic ratios of whole apatites have been used to track isotopic evolution associated with changes in magma fO2 and eruptive degassing (Rye, 2005). The presented work combines sulfur concentration mapping in zoned apatite crystals with in-situ SIMS 34S and 32S isotope measurements. Apatites were extracted from granite to granodiorite samples from the Cadiz Valley Batholith in the central Mojave Desert. This batholith is related to the pulse of Cretaceous Cordilleran magmatism that generated large batholiths in the Sierra Nevada and the Penninsular Ranges. The Mojave segment of the Cretaceous arc is unique in their construction into a full thickness of continental crust which exerted a strong influence on magmatic compositions. Apatite grains were mounted parallel to C axes, ground until grains were approximately bisected, and analyzed by Electron Microprobe at UCLA, for CaO, P2O5, SO3 and SiO2. Grains were surveyed and those yielding anomalous SO3 contents were investigated by micron-scale concentration mapping. Typical SO3 concentrations of apatites from all samples were ~0.2 wt%, while 8 to 10% of apatite grains from two samples contained cores with concentrations ranging up to 0.5 wt%. The sulfur zoning in these samples is oscillatory, in some grains representing 5 to 6 repetitions of high and low concentrations. Based on these textures

Geological, Geochemical 1 and Rb-Sr isotopic studies on tungsten 2 ...

Indian Academy of Sciences (India)

37

Geological, Geochemical and Rb-Sr isotopic studies on tungsten. 1 mineralised ..... From the field relations it is demonstrated that SG (biotite-bearing granitic gneiss) and. 120 ..... cases Ba) and vice-versa for the low concentration. 291.

Multiple sulfur isotopes monitor fluid evolution of an Archean orogenic gold deposit

Science.gov (United States)

LaFlamme, Crystal; Sugiono, Dennis; Thébaud, Nicolas; Caruso, Stefano; Fiorentini, Marco; Selvaraja, Vikraman; Jeon, Heejin; Voute, François; Martin, Laure

2018-02-01

The evolution of a gold-bearing hydrothermal fluid from its source to the locus of gold deposition is complex as it experiences rapid changes in thermochemical conditions during ascent through the crust. Although it is well established that orogenic gold deposits are generated during time periods of abundant crustal growth and/or reworking, the source of fluid and the thermochemical processes that control gold precipitation remain poorly understood. In situ analyses of multiple sulfur isotopes offer a new window into the relationship between source reservoirs of Au-bearing fluids and the thermochemical processes that occur along their pathway to the final site of mineralisation. Whereas δ34S is able to track changes in the evolution of the thermodynamic conditions of ore-forming fluids, Δ33S is virtually indelible and can uniquely fingerprint an Archean sedimentary reservoir that has undergone mass independent fractionation of sulfur (MIF-S). We combine these two tracers (δ34S and Δ33S) to characterise a gold-bearing laminated quartz breccia ore zone and its sulfide-bearing alteration halo in the (+6 Moz Au) structurally-controlled Archean Waroonga deposit located in the Eastern Goldfields Superterrane of the Yilgarn Craton, Western Australia. Over 250 analyses of gold-associated sulfides yield a δ34S shift from what is interpreted as an early pre-mineralisation phase, with chalcopyrite-pyrrhotite (δ34S = +0.7‰ to +2.9‰) and arsenopyrite cores (δ34S = ∼-0.5‰), to a syn-mineralisation stage, reflected in Au-bearing arsenopyrite rims (δ34S = -7.6‰ to +1.5‰). This shift coincides with an unchanging Δ33S value (Δ33S = +0.3‰), both temporally throughout the Au-hosting hydrothermal sulfide paragenesis and spatially across the Au ore zone. These results indicate that sulfur is at least partially recycled from MIF-S-bearing Archean sediments. Further, the invariant nature of the observed MIF-S signature demonstrates that sulfur is derived from a

Isotopes as Tracers of the Hawaiian Coffee-Producing Regions

Science.gov (United States)

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

Sulfur isotope fractionation between fluid and andesitic melt: An experimental study

Science.gov (United States)

Fiege, Adrian; Holtz, François; Shimizu, Nobumichi; Mandeville, Charles W.; Behrens, Harald; Knipping, Jaayke L.

2014-01-01

Glasses produced from decompression experiments conducted by Fiege et al. (2014a) were used to investigate the fractionation of sulfur isotopes between fluid and andesitic melt upon magma degassing. Starting materials were synthetic glasses with a composition close to a Krakatau dacitic andesite. The glasses contained 4.55–7.95 wt% H2O, ∼140 to 2700 ppm sulfur (S), and 0–1000 ppm chlorine (Cl). The experiments were carried out in internally heated pressure vessels (IHPV) at 1030 °C and oxygen fugacities (fO2) ranging from QFM+0.8 log units up to QFM+4.2 log units (QFM: quartz–fayalite–magnetite buffer). The decompression experiments were conducted by releasing pressure (P) continuously from ∼400 MPa to final P of 150, 100, 70 and 30 MPa. The decompression rate (r) ranged from 0.01 to 0.17 MPa/s. The samples were annealed for 0–72 h (annealing time, tA) at the final P and quenched rapidly from 1030 °C to room temperature (T).The decompression led to the formation of a S-bearing aqueous fluid phase due to the relatively large fluid–melt partitioning coefficients of S. Secondary ion mass spectrometry (SIMS) was used to determine the isotopic composition of the glasses before and after decompression. Mass balance calculations were applied to estimate the gas–melt S isotope fractionation factor αg-m.No detectable effect of r and tA on αg-m was observed. However, SIMS data revealed a remarkable increase of αg-m from ∼0.9985 ± 0.0007 at >QFM+3 to ∼1.0042 ± 0.0042 at ∼QFM+1. Noteworthy, the isotopic fractionation at reducing conditions was about an order of magnitude larger than predicted by previous works. Based on our experimental results and on previous findings for S speciation in fluid and silicate melt a new model predicting the effect of fO2 on αg-m (or Δ34Sg–m) in andesitic systems at 1030 °C is proposed. Our experimental results as well as our modeling are of high importance for the interpretation of S isotope

Sulfur isotopes as a tracer for biogenic sulfate reduction in natural environments: A link between modern and ancient ecosystems. Geologica Ultraiectina (316)

NARCIS (Netherlands)

Stam, M.C.

2010-01-01

Sulfur isotopes have been widely used to trace the activity of sulfate reducing prokaryotes in modern and ancient geochemical settings and to estimate the role of this microbial metabolism in global sulfur cycling. Extensive pure culture data provide detailed insight into cellular mechanisms

Geological isotope anomalies as signatures of nearby supernovae

CERN Document Server

Ellis, Jonathan Richard; Schramm, David N; Ellis, John; Fields, Brian D; Schramm, David N

1996-01-01

Nearby supernova explosions may cause geological isotope anomalies via the direct deposition of debris or by cosmic-ray spallation in the earth's atmosphere. We estimate the mass of material deposited terrestrially by these two mechanisms, showing the dependence on the supernova distance. A number of radioactive isotopes are identified as possible diagnostic tools, such as Be-10, Al-26, Cl-36, Mn-53, Fe-60, and Ni-59, as well as the longer-lived I-129, Sm-146, and Pu-244. We discuss whether the 35 and 60 kyr-old Be-10 anomalies observed in the Vostok antarctic ice cores could be due to supernova explosions. Combining our estimates for matter deposition with results of recent nucleosynthesis yields, we calculate the expected signal from nearby supernovae using ice cores back to \\sim 300 kyr ago, and we discuss using deep ocean sediments back to several hundred Myr. In particular, we examine the prospects for identifying isotope anomalies due to the Geminga supernova explosion, and signatures of the possibility...

Pb, Sr and Nd isotope geological characteristics and its evolution of Jianchaling rock

International Nuclear Information System (INIS)

Pang Chunyong; Chen Minyang; Xu Wenxin

2003-01-01

It has been a long time debatable subject on the raw material source and its genesis of Jianchaling ultrabasic rock, because the original rock phases, the original mineral compositions, texture and structure, even part of the chemical components of the rocks had been changed completely after many periods and phases of metamorphism. According to the content of Pb, Rb, Sr, Nd elements and their Pb, Sr, Nd isotope compositions of the rocks, together with the isotope geological age of late magmatic activities, the authors analyze the evolution of Pb, Sr, Nd isotope compositions, The inferred initiate Nd isotope ratio of ultrabasic rocks is 0.510233, lower than that of meteorite unity at a corresponding period, its ε Nd(T)>O; The initiate Sr ratios inferred by the isotope geological age ranges from 0.702735 to 0.719028; Projecting the lead isotope compositions on the Pb tectonic evolution model, the result indicates that the raw material of Jianchaling ultrabasic rock coming from the deplete upper mantle. The ultrabasic magma which enrich of Mg, Ni and less S intruded the crust and formed the Jianchaling ultrabasic rock at late Proterozoic era (927 Ma±). The forming time of serpentinite is mostly equal to the granitoid intruding time, showing the intrusion o flate acidic magma caused a large scale alteration of the ultrabasic rocks and formed the meta-ultrabasic phase rock observed today. (authors)

Characterization of sulfur deposition over the period of industrialization in Japan using sulfur isotope ratio in Japanese cedar tree rings taken from stumps.

Science.gov (United States)

Ishida, Takuya; Tayasu, Ichiro; Takenaka, Chisato

2015-07-01

We characterized the sulfur deposition history over the period of industrialization in Japan based on the sulfur isotope ratio (δ(34)S) in tree rings of Japanese cedar (Cryptomeria japonica D. Don) stumps. We analyzed and compared δ(34)S values in the rings from two types of disk samples from 170-year-old stumps that had been cut 5 years earlier (older forest stand) and from 40-year-old living trees (younger forest stand) in order to confirm the validity of using stump disks for δ(34)S analysis. No differences in δ(34)S values by age were found between the sample types, indicating that stump disks can be used for δ(34)S analysis. The δ(34)S profile in tree rings was significantly correlated with anthropogenic SO2 emissions in Japan (r = -0.76, p tree rings serve as a record of anthropogenic sulfur emissions. In addition, the values did not change largely from pre-industrialization to the 1940s (+4.2 to +6.1‰). The values before the 1940s are expected to reflect the background sulfur conditions in Japan and, thus, disks containing rings formed before the 1940s contain information about the natural environmental sulfur, which is useful for biogeochemical studies.

A novel procedure for Rubidium separation and its isotope measurements on geological samples by MC-ICP-MS

Science.gov (United States)

Ma, J.; Zhang, Z.; Wei, G.; Zhang, L.

2017-12-01

A method including a novel column Rb separation procedure and high-precision Rb isotope measurement in geological materials by using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in standard-sample-bracketing (SSB) mode has been developed. Sr-Spec resin was employed, in which the distribution coefficients for Rb, K, Ba and Sr are different in nitric acid, to sequentially separate them from the matrix. The dissolved samples were loaded on the column in 3 M HNO3, the main matrix such as Al, Ca, Fe, Mg, Mn and Na were removed by rinsing with 4.5 mL HNO3, Rb and K were then sequentially eluted by 3 M HNO3 in different volumes. After that, Ba was eluted by 8 M HNO3, and Sr was finally eluted by Milli-Q water. This enable us to collect the pure Rb, K, Ba and Sr one by one with recovery close to 100% for their isotopic compositions measurement on MC-ICP-MS. We here focus on Rb isotope measurement. The measurement using MC-ICP-MS yielded an internal precision for δ87Rb of external precision was generally better than ± 0.06‰ (2SD) based on the long-term results of the Rb standard solutions NIST SRM 984. A series of geological rock standards, were analyzed using this method, and the results indicate significant Rb isotope differences in different geologic materials. This will provide a powerful tool to investigate Rb isotope fractionation during geological processes.Based on this method, Rb isotope compositions from a basaltic weathering profile were carried out. The data show the lighter Rb (85Rb) isotope is preferentially leached from the weathering profile and remains heavy Rb isotope (87Rb) in the weathered residues during the incipient weathering stage. From the moderate to advanced weathering stage, the significant variations of Rb isotope were observed and multiple factors, such as leaching, adsorption, desorption, and precipitation, should play important role in fractionating Rb isotope.

Fabrication of SO/sub 2/preparation system and calibration of PINSTECH sulfur standard for /sup 34/S/sup 32/S mass spectrometric analysis

International Nuclear Information System (INIS)

Sajjad, M.I.; Latif, Z.; Ali, M.; Qureshi, R.M.; Tasneem, M.A.; Khan, I.H.; Ahmed, M.; Ahmed, I.

1994-05-01

This report describes the fabrication and standardization of operation procedures of a SO/sub 2/ preparation system used for the extraction of sulfur dioxide gas from sulfur minerals (aqueous sulfate, elemental sulfur, and sulfides) for sulfur isotope ratio measurements on a gas source mass spectrometer for hydrological, geological and environmental applications. SO/sub 2/ preparation procedure as described by Fumitaka Yanagisawa and Hitoshi Sakai (1983) is adopted with some modifications. A chemically pure BaSO/sub 4/ powder is chosen as PINSTECH Sulfur Standard PSS-I for routine laboratory /sup 34/S analysis. PSS-1 is calibrated against the International Atomic Energy Agency (IAEA) standard Cannon Diablo Troilite (CDT) using the NBS-127 sulfur standard Sigma /sup 34/S values of PSS-1 as analyzed at PINSTECH and Institute fur Hydorlogie, Munich are found to be 14.58 +-0.07 % CDT (n=6) and 14.59+-0.15% CDT (n=2) respectively. NBS-127 is BaSO/sub 4/ powder from the National Bureau of Standards, USA and has been calibrated against CDT. Interlaboratory comparison of various standards is also documented. Using this system, the reproducibility of sulfur isotope ratio measurements is better than +-0.2 % (n=10). (author)

Fabrication of SO/sub 2/preparation system and calibration of PINSTECH sulfur standard for /sup 34/S/sup 32/S mass spectrometric analysis

Energy Technology Data Exchange (ETDEWEB)

Sajjad, M I; Latif, Z; Ali, M; Qureshi, R M; Tasneem, M A; Khan, I H; Ahmed, M; Ahmed, I

1994-05-01

This report describes the fabrication and standardization of operation procedures of a SO/sub 2/ preparation system used for the extraction of sulfur dioxide gas from sulfur minerals (aqueous sulfate, elemental sulfur, and sulfides) for sulfur isotope ratio measurements on a gas source mass spectrometer for hydrological, geological and environmental applications. SO/sub 2/ preparation procedure as described by Fumitaka Yanagisawa and Hitoshi Sakai (1983) is adopted with some modifications. A chemically pure BaSO/sub 4/ powder is chosen as PINSTECH Sulfur Standard PSS-I for routine laboratory /sup 34/S analysis. PSS-1 is calibrated against the International Atomic Energy Agency (IAEA) standard Cannon Diablo Troilite (CDT) using the NBS-127 sulfur standard Sigma /sup 34/S values of PSS-1 as analyzed at PINSTECH and Institute fur Hydorlogie, Munich are found to be 14.58 +-0.07 % CDT (n=6) and 14.59+-0.15% CDT (n=2) respectively. NBS-127 is BaSO/sub 4/ powder from the National Bureau of Standards, USA and has been calibrated against CDT. Interlaboratory comparison of various standards is also documented. Using this system, the reproducibility of sulfur isotope ratio measurements is better than +-0.2 % (n=10). (author).

Water-rock-tailings interactions and sources of sulfur and metals in the subtropical mining region of Taxco, Guerrero (southern Mexico): A multi-isotopic approach

International Nuclear Information System (INIS)

Talavera Mendoza, Oscar; Ruiz, Joaquin; Díaz Villaseñor, Elvia; Ramírez Guzmán, Alejandro; Cortés, Alejandra; Salgado Souto, Sergio Adrián; Dótor Almazán, Azucena; Rivera Bustos, Reymundo

2016-01-01

Multi-isotope (H, O, S, Sr, Pb) systems coupled with conventional (major and trace element) hydrogeochemical analysis were applied to determine the origin of water, to model water-rock-tailings interactions and for source apportionment of sulfur and associated toxic metals in the mining region of Taxco, Guerrero in southern Mexico. Oxygen and H isotopes indicate that meteoric water in the zone is rainwater undergoing varying degrees of isotopic fractionation by atmospheric evaporation whereas Sr isotopes trace the interaction of pristine water from volcanics of the regional recharge zone and subsequently flowing through sandstone and shale to spring points. Leachates form from two distinctive sources (spring water and surface water) having differential interactions with bedrocks prior to entering the tailings. Compared to pristine water, leachates are enriched in sulfate, metals (e.g. Fe, Mn, Pb and Zn) and metalloids (e.g. As). The sulfur isotopic composition of ore-sulfides, leachates, secondary precipitates, regional surface water and hypogenic sulfates is described in terms of a two-component mixing model with shale of Mexcala and limestone of Morelos formations representing the light and heavy end-members, respectively, whereas Sr isotopic composition is bracketed combining three lithogenic (Mexcala/Morelos, Tilzapotla and Taxco Schist) sources. Finally, leachates have a mixture of lead from ore-sulfides and Taxco Schist Formation (Family I) or from ore-sulfides alone (Family II). The application of multiple environmental isotopic techniques is an outstanding tool for elucidating complex interactions of water with bedrocks and tailings and for determining the source of sulfur and toxic metal from mining and other metal polluted environments. - Highlights: • We applied multi-isotope techniques to model water-bedrocks-tailings interaction. • Spring water records fractionation by evaporation and interaction with local rocks. • The sulfur cycle is modeled in

Nd and Sr isotopes: implications of provenance and geological mapping

International Nuclear Information System (INIS)

Albuquerque, Marcio Fernando dos Santos; Horbe, Adriana Maria Coimbra; Dantas, Elton Luiz

2015-01-01

XRD, Nd and Sr isotopes, major, minor and traces elements quantification were applied to rocks, lateritic crusts and soils from Sumauma Supergroup and Alto Tapajos Group, in order to indicate provenance of the rocks and using lateritic products as geologic mapping tool. For the rocks, the results showed sources related to provinces Tapajos Parima, Rondonia Juruena, Sunsas, Carajas and Amazonia Central. However, the incision of Cachimbo graben allowed which the Sumauma Supergroup erosion also were source for the Alto Tapajos Group, allied to contribution of volcanics from Colider Group. Lateritic crusts and soils are correlates to bedrocks, allowing the use as geologic mapping tool. (author)

A Learner-Centered Spiral Knowledge Approach to Teaching Isotope Geology

Science.gov (United States)

Reid, M. R.

2006-12-01

Aided by the insights I gained by participation in the Arizona Board of Regents Tri-University Collaboration on Learner-Centered Practice, I made major changes to a graduate course in isotope geology (GLG617), including: 1) implementation of a spiral knowledge approach (e.g., Bruner, 1990; Dyar et al., 2004); 2) incorporation of more learner-centered in-class activities; and 3) more explicit emphasis on skills that I regarded as important for success in geochemistry. In the geosciences, the field of isotope geology is now an essential area of inquiry with implications for geologic timescales, climate information, tracing geochemical processes, and biological evolution, to name a few. The traditional approach to teaching isotope geology suffers from the fact that learning tends to be compartmentalized by technique/approach and one subfield (e.g., stable or radiogenic isotopes) is usually favored by appearing earlier in semester. To make learning more integrated, I employed a simplified spiral learning approach so that common principles could be revisited several times over the course of the semester and, in so doing, students' grasp of the fundamental principles could be scaffolded into greater understanding. Other learner-centered changes to the course included more explicit emphasis on helping students become comfortable with interpreting data displayed graphically and explicit emphasis on helping students give and evaluate oral presentations that rely on isotope data. I also developed a detailed grading rubric for the final paper and allowed students to have a draft of their final papers evaluated and graded (guided by Huba and Freed, 2000) A number of cooperative learning activities developed specifically for this course (19 in all) enabled me to gain a better appreciation for students' learning. Activities included pair share, round-robin, small group explorations of techniques and case studies (sometimes as introduction to, sometimes as review of material

Use of sulfur and nitrogen stable isotopes to determine the importance of whitebark pine nuts to Yellowstone grizzly bears

Science.gov (United States)

Felicetti, L.A.; Schwartz, C.C.; Rye, R.O.; Haroldson, M.A.; Gunther, K.A.; Phillips, D.L.; Robbins, C.T.

2003-01-01

Whitebark pine (Pinus albicaulis) is a masting species that produces relatively large, fat- and protein-rich nuts that are consumed by grizzly bears (Ursus arctos horribilis). Trees produce abundant nut crops in some years and poor crops in other years. Grizzly bear survival in the Greater Yellowstone Ecosystem is strongly linked to variation in pine-nut availability. Because whitebark pine trees are infected with blister rust (Cronartium ribicola), an exotic fungus that has killed the species throughout much of its range in the northern Rocky Mountains, we used stable isotopes to quantify the importance of this food resource to Yellowstone grizzly bears while healthy populations of the trees still exist. Whitebark pine nuts have a sulfur-isotope signature (9.2 ?? 1.3??? (mean ?? 1 SD)) that is distinctly different from those of all other grizzly bear foods (ranging from 1.9 ?? 1.7??? for all other plants to 3.1 ?? 2.6??? for ungulates). Feeding trials with captive grizzly bears were used to develop relationships between dietary sulfur-, carbon-, and nitrogen-isotope signatures and those of bear plasma. The sulfur and nitrogen relationships were used to estimate the importance of pine nuts to free-ranging grizzly bears from blood and hair samples collected between 1994 and 2001. During years of poor pine-nut availability, 72% of the bears made minimal use of pine nuts. During years of abundant cone availability, 8 ?? 10% of the bears made minimal use of pine nuts, while 67 ?? 19% derived over 51% of their assimilated sulfur and nitrogen (i.e., protein) from pine nuts. Pine nuts and meat are two critically important food resources for Yellowstone grizzly bears.

Carbon isotope fractionation by thermophilic phototrophic sulfur bacteria: evidence for autotrophic growth in natural populations

Science.gov (United States)

Madigan, M. T.; Takigiku, R.; Lee, R. G.; Gest, H.; Hayes, J. M.

1989-01-01

Purple phototrophic bacteria of the genus Chromatium can grow as either photoautotrophs or photoheterotrophs. To determine the growth mode of the thermophilic Chromatium species, Chromatium tepidum, under in situ conditions, we have examined the carbon isotope fractionation patterns in laboratory cultures of this organism and in mats of C. tepidum which develop in sulfide thermal springs in Yellowstone National Park. Isotopic analysis (13C/12C) of total carbon, carotenoid pigments, and bacteriochlorophyll from photoautotrophically grown cultures of C. tepidum yielded 13C fractionation factors near -20%. Cells of C. tepidum grown on excess acetate, wherein synthesis of the Calvin cycle enzyme ribulose-1,5-bisphosphate carboxylase/oxygenase ribulose bisphosphate carboxylase) was greatly repressed, were isotopically heavier, fractionation factors of ca. -7% being observed. Fractionation factors determined by isotopic analyses of cells and pigment fractions of natural populations of C. tepidum growing in three different sulfide thermal springs in Yellowstone National Park were approximately -20%, indicating that this purple sulfur bacterium grows as a photoautotroph in nature.

Sulfur isotope signatures in New Zealand

International Nuclear Information System (INIS)

Cainey, J.

2001-01-01

The role of sulfur in cloud formation makes it a crucial ingredient in the global climate change debate. So it is important to be able to measure sulfur in the atmosphere and identify where it came from. (author)

Relationship between microbial sulfate reduction rates and sulfur isotopic fractionation

Science.gov (United States)

Matsu'Ura, F.

2009-12-01

Sulfate reduction is one of the common processes to obtain energy for certain types of microorganisms.They use hydrogen gas or organic substrates as electron donor and sulfates as electron acceptor, and reduce sulfates to sulfides. Sulfate reducing microbes extend across domains Archea and Bacteria, and are believed to be one of the earliest forms of terrestrial life (Shen 2004). The origin of 34S-depleted (light) sulfide sulfur, especially δ34S vials, which contain 40ml of liquid culture media slightly modified from DSMZ #63 medium.Excess amount of Fe (II) is added to the DSMZ#63 medium to precipitate sulfide as iron sulfide. The vials were incubated at 25°C, 30°C, and 37°C, respectively. 21 vials were used for one temperature and sulfide and sulfate was collected from each three glass vials at every 12 hours from 72 hours to 144 hours after start of incubation. The sulfide was precipitated as iron sulfide and the sulfate was precipitated as barite. Sulfur isotope compositions of sulfate and sulfide were measured by standard method using Delta Plus mass-spectrometer. [Results and Discussion] The fractionation between sulfide and sulfate ranged from 2.7 to 11.0. The fractionation values varied among the different incubation temperature and growth phase of D. desulfuricans. The maximum fractionation values of three incubation temperatures were 9.9, 11.0, and 9.7, for 25 °C, 30°C, and 37°C, respectively. These results were different from standard model and Canfield et al. (2006). I could not find the clear correlation between ∂34S values and incubation temperatures in this experiment. The measured fractionation values during the incubation varied with incubation stage. The fractionation values clearly increased with incubation time at every temperature, and at 25°C ∂34S value was 3.6 at the 72h and it increased to 7.9 at 144 hours. This indicated the difference of sulfate reduction rate due to the growth phase of SRB. In the early logarithmic growth phase

Geological controls on isotopic signatures of streamflow: results from a nested catchment experiment in Luxembourg (Europe)

Science.gov (United States)

Pfister, Laurent; McDonnell, Jeffrey J.; Hissler, Christophe; Martinez-Carreras, Nuria; Gourdol, Laurent; Klaus, Julian; François Iffly, Jean; Barnich, François; Stewart, Mike K.

2014-05-01

Controls of geology and topography on hydrological metrics, like summer low flow (Grant and Tague, 2004) or dynamic storage (Sayama et al., 2011), have been identified in nested catchment experiments. However, most tracer-based studies on streamflow generation have been carried out in small (10 km2) homogenous catchments (Klaus and McDonnell, 2013). The controlling effects of catchment physiography on how catchments store and release water, and how this eventually controls stream isotope behaviour over a large range of scale are poorly understood. Here, we present results from a nested catchment analysis in the Alzette River basin (Luxembourg, Europe). Our hydro-climatological network consists of 16 recording streamgauges and 21 pluviographs. Catchment areas range from 0.47 to 285 km2, with clean and mixed combinations of distinct geologies ranging from schists to marls, sandstone, dolomite and limestone. Our objective was to identify geological controls on (i) winter runoff ratios, (ii) maximum storage and (iii) isotopic signatures in streamflow. For each catchment we determined average runoff ratios from winter season precipitation-discharge double-mass curves. Maximum catchment storage was based on the dynamic storage change approach of Sayama et al. (2011). Changes in isotopic signatures of streamflow were documented along individual catchment flow duration curves. We found strong correlations between average winter runoff ratios, maximum storage and the prevailing geological settings. Catchments with impermeable bedrock (e.g. marls or schists) were characterised by small storage potential and high average filling ratios. As a consequence, these catchments also exhibited the highest average runoff ratios. In catchments underlain by permeable bedrock (e.g. sandstone), storage potential was significantly higher and runoff ratios were considerably smaller. The isotopic signatures of streamflow showed large differences between catchments. In catchments dominated by

Sulfur Isotope Trends in Archean Microbialite Facies Record Early Oxygen Production and Consumption

Science.gov (United States)

Zerkle, A.; Meyer, N.; Izon, G.; Poulton, S.; Farquhar, J.; Claire, M.

2014-12-01

The major and minor sulfur isotope composition (δ34S and Δ33S) of pyrites preserved in ~2.65-2.5 billion-year-old (Ga) microbialites record localized oxygen production and consumption near the mat surface. These trends are preserved in two separate drill cores (GKF01 and BH1-Sacha) transecting the Campbellrand-Malmani carbonate platform (Ghaap Group, Transvaal Supergroup, South Africa; Zerkle et al., 2012; Izon et al., in review). Microbialite pyrites possess positive Δ33S values, plotting parallel to typical Archean trends (with a Δ33S/δ34S slope of ~0.9) but enriched in 34S by ~3 to 7‰. We propose that these 34S-enriched pyrites were formed from a residual pool of sulfide that was partially oxidized via molecular oxygen produced by surface mat-dwelling cyanobacteria. Sulfide, carrying the range of Archean Δ33S values, could have been produced deeper within the microbial mat by the reduction of sulfate and elemental sulfur, then fractionated upon reaction with O2 produced by oxygenic photosynthesis. Preservation of this positive 34S offset requires that: 1) sulfide was only partially (50­­-80%) consumed by oxidation, meaning H2S was locally more abundant (or more rapidly produced) than O2, and 2) the majority of the sulfate produced via oxidation was not immediately reduced to sulfide, implying either that the sulfate pool was much larger than the sulfide pool, or that the sulfate formed near the mat surface was transported and reduced in another part of the system. Contrastingly, older microbialite facies (> 2.7 Ga; Thomazo et al., 2013) appear to lack these observed 34S enrichments. Consequently, the onset of 34S enrichments could mark a shift in mat ecology, from communities dominated by anoxygenic photosynthesizers to cyanobacteria. Here, we test these hypotheses with new spatially resolved mm-scale trends in sulfur isotope measurements from pyritized stromatolites of the Vryburg Formation, sampled in the lower part of the BH1-Sacha core. Millimeter

Determination of uranium isotopes in environmental samples by anion exchange in sulfuric and hydrochloric acid media

International Nuclear Information System (INIS)

Popov, L.

2016-01-01

Method for determination of uranium isotopes in various environmental samples is presented. The major advantages of the method are the low cost of the analysis, high radiochemical yields and good decontamination factors from the matrix elements, natural and man-made radionuclides. The separation and purification of uranium is attained by adsorption with strong base anion exchange resin in sulfuric and hydrochloric acid media. Uranium is electrodeposited on a stainless steel disk and measured by alpha spectrometry. The analytical method has been applied for the determination of concentrations of uranium isotopes in mineral, spring and tap waters from Bulgaria. The analytical quality was checked by analyzing reference materials. - Highlights: • The method allows cost-effective determination of U isotopes. • High amounts of environmental samples can be analyzed. • High chemical yields, energy resolution and decontamination factors were achieved. • Uranium isotope concentrations in mineral waters from Bulgaria are presented.

Assessing Pyrite-Derived Sulfate in the Mississippi River with Four Years of Sulfur and Triple-Oxygen Isotope Data.

Science.gov (United States)

Killingsworth, Bryan A; Bao, Huiming; Kohl, Issaku E

2018-05-17

Riverine dissolved sulfate (SO 4 2- ) sulfur and oxygen isotope variations reflect their controls such as SO 4 2- reduction and reoxidation, and source mixing. However, unconstrained temporal variability of riverine SO 4 2- isotope compositions due to short sampling durations may lead to mischaracterization of SO 4 2- sources, particularly for the pyrite-derived sulfate load. We measured the sulfur and triple-oxygen isotopes (δ 34 S, δ 18 O, and Δ' 17 O) of Mississippi River SO 4 2- with biweekly sampling between 2009 and 2013 to test isotopic variability and constrain sources. Sulfate δ 34 S and δ 18 O ranged from -6.3‰ to -0.2‰ and -3.6‰ to +8.8‰, respectively. Our sampling period captured the most severe flooding and drought in the Mississippi River basin since 1927 and 1956, respectively, and a first year of sampling that was unrepresentative of long-term average SO 4 2- . The δ 34 S SO4 data indicate pyrite-derived SO 4 2- sources are 74 ± 10% of the Mississippi River sulfate budget. Furthermore, pyrite oxidation is implicated as the dominant process supplying SO 4 2- to the Mississippi River, whereas the Δ' 17 O SO4 data shows 18 ± 9% of oxygen in this sulfate is sourced from air O 2 .

Measurement of C and N isotopes of geological samples using Delta V Plus Stable Isotope Ratio Mass Spectrometer via different preparatory systems

Digital Repository Service at National Institute of Oceanography (India)

Karapurkar, S.; Methar, A.; Agnihotri, R.

standard developed for routine C and N isotope analyses of various types of geological samples containing organic matter in order to assess stabilities/ reproducibility of the IRMS in different time windows....

Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters

Science.gov (United States)

Sun, Jing; Kobayashi, Tatsuaki; Strosnider, William H. J.; Wu, Pan

2017-08-01

Karst water resources, which are extremely sensitive to mining activities, are critical for the support of human societies and ecological systems in many regions worldwide. In order to determine the sources and fate of dissolved sulfate in low-pH karst waters, hydrochemical variations of karst waters with and without acid mine drainage (AMD) impacts were investigated along with stable isotope dynamics. As expected, hydrochemical characteristics and isotopic compositions of the AMD and AMD-downstream water (ADW) were dramatically different from that of the non-AMD-impacted water (NAW). The sources of sulfur isotopes in sulfate were predominantly pyrite oxidation for the AMD and ADW, and atmospheric deposition for the NAW. Based on the general isotope-balance model, the relative proportions of sulfate oxygen derived from water and air were calculated. The mean proportion of sulfate oxygen derived from water in ADW was roughly double that of AMD. This suggests that the sulfate associated with AMD is predominantly influenced by aerobic pyrite oxidation, while that of ADW is likely affected by the dissolution of pyrite under anaerobic conditions in reservoir sediment. This observation was coincident with the noted variations of hydrochemical characteristics and was supported by principal component analysis. These results provide a better understanding of how stable isotopes of sulfate and water can be used to track mining contamination in karst aquifers, which could benefit remediation planning for these distinctive systems.

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).

Science.gov (United States)

Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A; Schimmelmann, Arndt

2017-03-30

Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H 2 ) is responsible for non-quantitative H 2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer-Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems. The EA-Cr/HTC reactor was substantially modified for the conversion of halogen- and sulfur-bearing samples. The performance of the novel conversion setup for solid and liquid samples was monitored and optimized using a simultaneously operating dual-detection system of IRMS and ion trap MS. The method with several variants in the reactor, including the addition of manganese metal chips, was evaluated in three laboratories using EA-Cr/HTC-IRMS (on-line method) and compared with traditional uranium-reduction-based conversion combined with manual dual-inlet IRMS analysis (off-line method) in one laboratory. The modified EA-Cr/HTC reactor setup showed an overall H 2 -recovery of more than 96% for all halogen- and sulfur-bearing organic compounds. All results were successfully normalized via two-point calibration with VSMOW-SLAP reference waters. Precise and accurate hydrogen isotopic analysis was achieved for a variety of organics containing F-, Cl-, Br-, I-, and S-bearing heteroelements. The robust nature of the on-line EA-Cr/HTC technique was demonstrated by a series of 196 consecutive measurements with a single reactor filling. The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and

Proceedings of the symposium on isotope geology progress: technology, methods, theory and application

International Nuclear Information System (INIS)

2003-11-01

The symposium was held in Beijing, Nov. 7-11, and the proceedings collects 122 articles, the contents include: new technology and new methods on isotopic test; isotope fractionation mechanism; the early evolution of the solar system and the Earth; continental dynamics and evolution of orogenic belts; minerals, energy and water; major history events on life origin, evolution and geology; changes in the Earth's global and modern environment--the oceans, the atmosphere, rivers and lakes, karst and soil, ecological agriculture and modern environment

Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

International Nuclear Information System (INIS)

Kao, Yu-Hsuan; Wang, Sheng-Wei; Liu, Chen-Wuing; Wang, Pei-Ling; Wang, Chung-Ho; Maji, Sanjoy Kumar

2011-01-01

Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using δ 34 S [SO 4 ] and δ 18 O [SO 4 ] sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of 34 S [SO 4 ] and 18 O [SO 4 ] present in Type A, caused by microbial-mediated reduction of sulfate, and high 18 O enrichment factor (ε [SO 4 -H 2 O] ), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high δ 18 O [SO 4 ] and low δ 34 S [SO 4 ] values under mildly reducing conditions. Base on 18 O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O 2 , caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater. - Highlights: → Seawater intrusion and elevated As are the main issues of groundwater in Taiwan. → Sulfur and oxygen isotopes of sulfate were analyzed to evaluate the As mobility. → Reductive dissolution of Fe minerals and

34S/32S fractionation in sulfur cycles catalyzed by anaerobic bacteria

Science.gov (United States)

Fry, B.; Gest, H.; Hayes, J. M.

1988-01-01

Stable isotopic distributions in the sulfur cycle were studied with pure and mixed cultures of the anaerobic bacteria, Chlorobium vibrioforme and Desulfovibrio vulgaris. D. vulgaris and C. vibrioforme can catalyze three reactions constituting a complete anaerobic sulfur cycle: reduction of sulfate to sulfide (D. vulgaris), oxidation of sulfide to elemental sulfur (C. vibrioforme), and oxidation of sulfur to sulfate (C. vibrioforme). In all experiments, the first and last reactions favored concentration of the light 32S isotope in products (isotopic fractionation factor epsilon = -7.2 and -1.7%, respectively), whereas oxidation of sulfide favored concentration of the heavy 34S isotope in products (epsilon = +1.7%). Experimental results and model calculations suggest that elemental sulfur enriched in 34S versus sulfide may be a biogeochemical marker for the presence of sulfide-oxidizing bacteria in modern and ancient environments.

Oxygen isotopic fractionation during bacterial sulfate reduction

Science.gov (United States)

Balci, N.; Turchyn, A. V.; Lyons, T.; Bruchert, V.; Schrag, D. P.; Wall, J.

2006-12-01

Sulfur isotope fractionation during bacterial sulfate reduction (BSR) is understood to depend on a variety of environmental parameters, such as sulfate concentration, temperature, cell specific sulfate reduction rates, and the carbon substrate. What controls oxygen isotope fractionation during BSR is less well understood. Some studies have suggested that carbon substrate is important, whereas others concluded that there is a stoichiometric relationship between the fractionations of sulfur and oxygen during BSR. Studies of oxygen fractionation are complicated by isotopic equilibration between sulfur intermediates, particularly sulfite, and water. This process can modify the isotopic composition of the extracellular sulfate pool (δ18OSO4 ). Given this, the challenge is to distinguish between this isotopic equilibration and fractionations linked to the kinetic effects of the intercellular enzymes and the incorporation of sulfate into the bacterial cell. The δ18OSO4 , in concert with the sulfur isotope composition of sulfate (δ34SSO4), could be a powerful tool for understanding the pathways and environmental controls of BSR in natural systems. We will present δ18OSO4 data measured from batch culture growth of 14 different species of sulfate reducing bacteria for which sulfur isotope data were previously published. A general observation is that δ18OSO4 shows little isotopic change (kinetic effect during BSR and/or equilibration between sulfur intermediates and the isotopically light water (~-5‰) of the growth medium. Our present batch culture data do not allow us to convincingly isolate the magnitude and the controlling parameters of the kinetic isotope effect for oxygen. However, ongoing growth of mutant bacteria missing enzymes critical in the different steps of BSR may assist in this mission.

An Early Permian epithermal gold system in the Tulasu Basin in North Xinjiang, NW China: Constraints from in situ oxygen-sulfur isotopes and geochronology

Science.gov (United States)

Dong, Leilei; Wan, Bo; Deng, Chen; Cai, Keda; Xiao, Wenjiao

2018-03-01

The Axi and Jingxi-Yelmand gold deposits, being the largest gold deposits in the Chinese North Tianshan, NW China, are located ca. l0 km apart in the Tulasu Basin, and are hosted by the Late Devonian - Early Carboniferous Dahalajunshan Formation. In situ LA-ICP-MS titanium analyses on quartz from the Axi and Jingxi-Yelmand deposits are broadly identical. Accordingly, the calculated ore-forming temperatures by Ti-in-quartz thermometer give average temperatures of 279 °C and 294 °C, respectively. Results of in situ SIMS analyses of oxygen and sulfur isotopes on quartz and pyrite from these two deposits are similar. Temperature-corrected fluids of the Axi deposit have δ18O values of 2.6-8.1‰ and δ34S values of 0.8-2.4‰, whereas the fluids of the Jingxi-Yelmand deposit have δ18O of 6.4-8.9‰ and δ34S of -0.4 to 4.0‰. The oxygen and sulfur isotopes from the two deposits indicate a magmatic origin. LA-ICP-MS zircon U-Pb ages of Aqialehe Formation sandstone provided a lower limit for the mineralization timing of the Axi deposit (288 Ma). In situ SIMS U-Pb analyses on entrapped zircon (297 Ma) and newly recognized 284.5 Ma columnar rhyolite implies that the Jingxi-Yelmand deposit formed in the Early Permian. Based on the magmatic affinity of the ore fluids, similar age and ore-formation temperatures, we propose that the Axi and Jingxi-Yelmand deposits comprise an epithermal gold system, which was driven by the same Permian magma in the Tulasu Basin. The ore geological features together with our new results indicate that the Axi and Jingxi-Yelmand deposits are intermediate and high sulfidation type epithermal deposits, respectively.

Determination of natural alpha-emitting isotopes of uranium and thorium in environmental and geological samples

International Nuclear Information System (INIS)

Crespo, M.T.

1996-01-01

It is described the complete radiochemical procedure used for the determination of uranium and thorium isotopes in environmental and geological samples by alpha spectrometry. Source preparation methods, alpha-counting and spectral analysis are also included

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems

Energy Technology Data Exchange (ETDEWEB)

Bern, Carleton R., E-mail: cbern@usgs.gov [U.S. Geological Survey, Denver Federal Center, Denver, CO 80225 (United States); Department of Geography University of California, Santa Barbara, CA 93106-4060 (United States); Chadwick, Oliver A. [Department of Geography University of California, Santa Barbara, CA 93106-4060 (United States); Kendall, Carol [U.S. Geological Survey, Menlo Park, CA (United States); Pribil, Michael J. [U.S. Geological Survey, Denver Federal Center, Denver, CO 80225 (United States)

2015-05-01

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ{sup 34}S VCDT) of − 0.8‰. Bulk deposition on the island of Maui had a δ{sup 34}S VCDT that varied temporally, spanned a range from + 8.2 to + 19.7‰, and reflected isotopic mixing from three sources: sea-salt (+ 21.1‰), marine biogenic emissions (+ 15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+ 0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to + 2.7‰) to relatively high (+ 17.8 to + 19.3‰) soil δ{sup 34}S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from + 8.1 to + 20.3‰ and generally decreased with increasing elevation (0–2000 m), distance from the coast (0–12 km), and annual rainfall (180–5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems

International Nuclear Information System (INIS)

Bern, Carleton R.; Chadwick, Oliver A.; Kendall, Carol; Pribil, Michael J.

2015-01-01

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ 34 S VCDT) of − 0.8‰. Bulk deposition on the island of Maui had a δ 34 S VCDT that varied temporally, spanned a range from + 8.2 to + 19.7‰, and reflected isotopic mixing from three sources: sea-salt (+ 21.1‰), marine biogenic emissions (+ 15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+ 0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to + 2.7‰) to relatively high (+ 17.8 to + 19.3‰) soil δ 34 S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from + 8.1 to + 20.3‰ and generally decreased with increasing elevation (0–2000 m), distance from the coast (0–12 km), and annual rainfall (180–5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls over

Stable isotope compositions of serpentinite seamounts in the Mariana forearc: Serpentinization processes, fluid sources and sulfur metasomatism

Science.gov (United States)

Alt, J.C.; Shanks, Wayne C.

2006-01-01

The Mariana and Izu-Bonin arcs in the western Pacific are characterized by serpentinite seamounts in the forearc that provide unique windows into the mantle wedge. We present stable isotope (O, H, S, and C) data for serpentinites from Conical seamount in the Mariana forearc and S isotope data for Torishima seamount in the Izu-Bonin forearc in order to understand the compositions of fluids and temperatures of serpentinization in the mantle wedge, and to investigate the transport of sulfur from the slab to the mantle wedge. Six serpentine mineral separates have a restricted range of ??18O (6.5-8.5???). Antigorite separates have ??D values of -29.5??? to -45.5??? that reflect serpentinization within the mantle wedge whereas chrysotile has low ??D values (-51.8??? to -84.0???) as the result of re-equilibration with fluids at low temperatures. Fractionation of oxygen isotopes between serpentine and magnetite indicate serpentinization temperatures of 300-375 ??C. Two late cross-fiber chrysotile veins have higher ??18O values of 8.9??? to 10.8??? and formed at lower temperatures (as low as ???100 ??C). Aqueous fluids in equilibrium with serpentine at 300-375 ??C had ??18O = 6.5-9??? and ??D = -4??? to -26???, consistent with sediment dehydration reactions at temperatures aragonite veins in metabasalt and siltstone clasts within the serpentinite flows have ??18O = 16.7-24.5???, consistent with the serpentinizing fluids at temperatures <250 ??C. ??13C values of 0.1-2.5??? suggest a source in subducting carbonate sediments. The ??34S values of sulfide in serpentinites on Conical Seamount (-6.7??? to 9.8???) result from metasomatism through variable reduction of aqueous sulfate (??34S = 14???) derived from slab sediments. Despite sulfur metasomatism, serpentinites have low sulfur contents (generally < 164 ppm) that reflect the highly depleted nature of the mantle wedge. The serpentinites are mostly enriched in 34S (median ??34Ssulfide = 4.5???), consistent with a 34S

Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

Energy Technology Data Exchange (ETDEWEB)

Kao, Yu-Hsuan [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Sheng-Wei [Agricultural Engineering Research Center, Chungli 320, Taiwan, ROC (China); Liu, Chen-Wuing, E-mail: lcw@gwater.agec.ntu.edu.tw [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Pei-Ling [Institute of Oceanography, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Chung-Ho [Institute of Earth Sciences, Academia Sinica, Taipei 115, Taiwan, ROC (China); Maji, Sanjoy Kumar [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China)

2011-10-15

Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using {delta}{sup 34}S{sub [SO{sub 4]}} and {delta}{sup 18}O{sub [SO{sub 4]}} sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of {sup 34}S{sub [SO{sub 4]}} and {sup 18}O{sub [SO{sub 4]}} present in Type A, caused by microbial-mediated reduction of sulfate, and high {sup 18}O enrichment factor ({epsilon}{sub [SO{sub 4-H{sub 2O]}}}), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high {delta}{sup 18}O{sub [SO{sub 4]}} and low {delta}{sup 34}S{sub [SO{sub 4]}} values under mildly reducing conditions. Base on {sup 18}O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O{sub 2}, caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater. - Highlights: {yields} Seawater intrusion and elevated As are the main issues of groundwater in Taiwan

Sulfur isotope fractionation during heterogeneous oxidation of SO2 on mineral dust

Directory of Open Access Journals (Sweden)

P. Hoppe

2012-06-01

Full Text Available Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917±0.0046, which is in agreement with previous measurements of aqueous SO2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH had an overall fractionation factor of αhet = 1.0096±0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ~40%. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. All the investigated reactions showed mass-dependent fractionation of 33S relative to 34S. A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85% of sulfate production with a fractionation factor of α34 = 1.012±0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO2 by H2O2 and O3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12% of the sulfate production, and oxidation on clay minerals

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

Science.gov (United States)

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

2011-12-01

S and O isotope compositions of ocean and river sulfate, SO42-, reflect Earth surface processes and can thus be used to understand the Earth's dynamic past. It has been estimated that riverine SO42- is 22% evaporite (SO42-riv-evap), 11% oxidative weathering (SO42-riv-ow), and 54% atmospheric and agricultural pollution [1]. Two parameters are poorly constrained: 1) the ratio of SO42-riv-evap to SO42-riv-ow, and 2) the extent of human influence on SO42- flux. Furthermore, for isotopic modeling, natural riverine SO42- O and S isotope compositions, δ18OSO4-riv and δ34SSO4-riv, have large measured ranges (e.g. δ18OSO4-riv from -2% to +7% [2]) that are based on limited empirical data with variable and unconstrained influence from human activities. In the lower Mississippi River Basin (MRB) we have sampled river water SO42- biweekly since 2009. Our isotope dataset is used in conjunction with US Geological Survey and US Army Corps of Engineers SO42- concentration and river discharge data. In comparison to MRB low discharge periods, the periods of annual high water discharge are characterized by 1) a doubling in water discharge 2) a concomitant high MRB SO42- flux (>1100 kg/s) 3) an average SO42- concentration at 85% of the low discharge concentrations and 4) a more constrained variability of SO42- isotope composition. The δ18OSO4-riv ranges from +3.2% to +5.5% at high discharge and from +2.6% to +8.8% at low discharge. The δ34SSO4-riv ranges from -4.3% to -0.4 at high discharge and from -6.3% to -0.2% at low discharge. Atmospheric SO42- is estimated from 2009 National Atmospheric Deposition Program maps to contribute only ~10% of total MRB SO42-. We conclude that during annual high discharge a large river basin such as the MRB is less sensitive to variable sub-basin input and that average MRB SO42- isotope composition is best represented by a δ18OSO4-riv value of ~+4.0% and δ34SSO4-riv value of ~-3.0%. MRB SO42- concentration during high discharge is diluted less

Iron and Sulfur Species and Sulfur Isotopic Compositions of Authigenic Pyrite in Gas Hydrate-Bearing Sediments from Hydrate Ridge, Cascadia Margin (ODP Leg 204): A Proposal of Conceptual Models to Indicate the Non-Steady State Depositional and Diagenetic Processes

Science.gov (United States)

Liu, C.; Jiang, S. Y.; Su, X.

2017-12-01

Two accretionary sediment sequences from Sites 1245 and 1252 recovered during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge, Cascadia Margin were investigated to explore the non-steady state depositional and diagenetic history. Five iron species and three sulfur species were chemically extracted, and their concentrations and the sulfur isotopic compositions of pyrite were determined. After the mineral recognitions of these species and detailed comparative analyses, the aerobic history of bottom seawater has been determined. The formation of pyrite is thought to be controlled by the limited production of hydrogen sulfide relative to the supply of reactive iron. Also, the intrusion of oxygen by bioturbation would oxidize the reduced sulfur species and further suppress pyritization. To explain the geochemical relationship between pyrite and siderite and the sulfur isotope characteristics of pyrite, we propose seven conceptual models based on the variations in depositional rate and methane flux, and the models succeed in explaining the geochemical results and are validated by the observed non-steady state events. These models may contribute to the reconstruction of the non-steady state processes in other research areas in the future.

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

Science.gov (United States)

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.

Multiple sulfur-isotopic evidence for a shallowly stratified ocean following the Triassic-Jurassic boundary mass extinction

Science.gov (United States)

Luo, Genming; Richoz, Sylvain; van de Schootbrugge, Bas; Algeo, Thomas J.; Xie, Shucheng; Ono, Shuhei; Summons, Roger E.

2018-06-01

The cause of the Triassic-Jurassic (Tr-J) boundary biotic crisis, one of the 'Big Five' mass extinctions of the Phanerozoic, remains controversial. In this study, we analyzed multiple sulfur-isotope compositions (δ33S, δ34S and δ36S) of pyrite and Spy/TOC ratios in two Tr-J successions (Mariental, Mingolsheim) from the European Epicontinental Seaway (EES) in order to better document ocean-redox variations during the Tr-J transition. Our results show that upper Rhaetian strata are characterized by 34S-enriched pyrite, low Spy/TOC ratios, and values of Δ33Spy (i.e., the deviation from the mass-dependent array) lower than that estimated for contemporaneous seawater sulfate, suggesting an oxic-suboxic depositional environment punctuated by brief anoxic events. The overlying Hettangian strata exhibit relatively 34S-depleted pyrite, high Δ33Spy, and Spy/TOC values, and the presence of green sulfur bacterial biomarkers indicate a shift toward to euxinic conditions. The local development of intense marine anoxia thus postdated the Tr-J mass extinction, which does not provide support for the hypothesis that euxinia was the main killing agent at the Tr-J transition. Sulfur and organic carbon isotopic records that reveal a water-depth gradient (i.e., more 34S-, 13C-depleted with depth) in combination with Spy/TOC data suggest that the earliest Jurassic EES was strongly stratified, with a chemocline located at shallow depths just below storm wave base. Shallow oceanic stratification may have been a factor for widespread deposition of black shales, a large positive shift in carbonate δ13C values, and a delay in the recovery of marine ecosystems following the Tr-J boundary crisis.

A study of Sr and Nd isotopic geology during anatexis in the area No.8411

International Nuclear Information System (INIS)

Ying Junlong

1993-01-01

An isotopic geology study in the area No.8411 indicates that the J 1-2 sandstone is lacustrine facies sediments mainly originated from Proterozoic old continental crust. Therefore, the magmatic rocks are derived from partial melting or remelting-contamination of Proterozoic old continents in the lower crust. The initial concentration of uranium is related with the magma contamination caused by anatexis in the old sialic crust. The isotopic compositions of both uranium minerals and magmatic rocks are relatively concordant. According to the results of this study, combined with petrology, mineralogy, isotopic evolution and REE contents, it is considered that uranium is derived from the deep source and uranium source rocks are Proterozoic old continents

Platinum-group elements and gold in base metal sulfides, platinum-group minerals, and Re-Os isotope compositions of the Uitkomst complex, South Africa

Czech Academy of Sciences Publication Activity Database

Trubač, Jakub; Ackerman, Lukáš; Gauert, Ch.; Ďurišová, Jana; Hrstka, Tomáš

2018-01-01

Roč. 113, č. 2 (2018), s. 439-461 ISSN 0361-0128 R&D Projects: GA ČR GA13-15390S Institutional support: RVO:67985831 Keywords : binary alloys * copper compounds * economic geology * gold * iridium * isotopes * ore deposits * osmium * palladium * platinum * platinum metals * pyrites * Rhenium * rhenium alloys * ruthenium * solid solutions * sulfur compounds * crustal materials * mass-balance calculations * massive sulfides * mineralized zone * monosulfide solid solutions * platinum group elements * platinum group elements (PGEs) * platinum group minerals Subject RIV: DB - Geology ; Mineralogy; AC - Archeology, Anthropology, Ethnology (ARUB-Q) OBOR OECD: Geology; Archaeology (ARUB-Q) Impact factor: 2.519, year: 2016

Sulfur isotopes in coal constrain the evolution of the Phanerozoic sulfur cycle

DEFF Research Database (Denmark)

Canfield, Donald Eugene

2013-01-01

Sulfate is the second most abundant anion (behind chloride) in modern seawater, and its cycling is intimately coupled to the cycling of organic matter and oxygen at the Earth’s surface. For example, the reduction of sulfide by microbes oxidizes vast amounts of organic carbon and the subsequent......, these compositions do not deviate substantially from the modern surface-water input to the oceans. When applied to mass balance models, these results support previous interpretations of sulfur cycle operation and counter recent suggestions that sulfate has been a minor player in sulfur cycling through...... reaction of sulfide with iron produces pyrite whose burial in sediments is an important oxygen source to the atmosphere. The concentrations of seawater sulfate and the operation of sulfur cycle have experienced dynamic changes through Earth’s history, and our understanding of this history is based mainly...

Acidophilic sulfur disproportionation

Science.gov (United States)

Hardisty, Dalton S.; Olyphant, Greg A.; Bell, Jonathan B.; Johnson, Adam P.; Pratt, Lisa M.

2013-07-01

Bacterial disproportionation of elemental sulfur (S0) is a well-studied metabolism and is not previously reported to occur at pH values less than 4.5. In this study, a sediment core from an abandoned-coal-mine-waste deposit in Southwest Indiana revealed sulfur isotope fractionations between S0 and pyrite (Δ34Ses-py) of up to -35‰, inferred to indicate intense recycling of S0 via bacterial disproportionation and sulfide oxidation. Additionally, the chemistry of seasonally collected pore-water profiles were found to vary, with pore-water pH ranging from 2.2 to 3.8 and observed seasonal redox shifts expressed as abrupt transitions from Fe(III) to Fe(II) dominated conditions, often controlled by fluctuating water table depths. S0 is a common product during the oxidation of pyrite, a process known to generate acidic waters during weathering and production of acid mine drainage. The H2S product of S0 disproportionation, fractionated by up to -8.6‰, is rapidly oxidized to S0 near redox gradients via reaction with Fe(III) allowing for the accumulation of isotopically light S0 that can then become subject to further sulfur disproportionation. A mass-balance model for S0 incorporating pyrite oxidation, S0 disproportionation, and S0 oxidation readily explains the range of observed Δ34Ses-py and emphasizes the necessity of seasonally varying pyrite weathering and metabolic rates, as indicated by the pore water chemistry. The findings of this research suggest that S0 disproportionation is potentially a common microbial process at a pH < 4.5 and can create large sulfur isotope fractionations, even in the absence of sulfate reduction.

Stable isotope phenotyping via cluster analysis of NanoSIMS data as a method for characterizing distinct microbial ecophysiologies and sulfur-cycling in the environment

Directory of Open Access Journals (Sweden)

Katherine S Dawson

2016-05-01

Full Text Available Stable isotope probing (SIP is a valuable tool for gaining insights into ecophysiology and biogeochemical cycling of environmental microbial communities by tracking isotopically labeled compounds into cellular macromolecules as well as into byproducts of respiration. SIP, in conjunction with nanoscale secondary ion mass spectrometry (NanoSIMS, allows for the visualization of isotope incorporation at the single cell level. In this manner, both active cells within a diverse population as well as heterogeneity in metabolism within a homogeneous population can be observed. The ecophysiological implications of these single cell stable isotope measurements are often limited to the taxonomic resolution of paired fluorescence in situ hybridization (FISH microscopy. Here we introduce a taxonomy-independent method using multi-isotope SIP and NanoSIMS for identifying and grouping phenotypically similar microbial cells by their chemical and isotopic fingerprint. This method was applied to SIP experiments in a sulfur-cycling biofilm collected from sulfidic intertidal vents amended with 13C-acetate, 15N-ammonium, and 33S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope (13C/12C, 15N/14N, and 33S/32S and elemental ratio (C/CN and S/CN profiles, our analysis partitioned ~2200 cellular regions of interest (ROIs into 5 distinct groups. These isotope phenotype groupings are reflective of the variation in labeled substrate uptake by cells in a multispecies metabolic network dominated by Gamma- and Deltaproteobacteria. Populations independently grouped by isotope phenotype were subsequently compared with paired FISH data, demonstrating a single coherent deltaproteobacterial cluster and multiple gammaproteobacterial groups, highlighting the distinct ecophysiologies of spatially-associated microbes within the sulfur-cycling biofilm from White Point Beach, CA.

A strategy for fast screening and identification of sulfur derivatives in medicinal Pueraria species based on the fine isotopic pattern filtering method using ultra-high-resolution mass spectrometry

International Nuclear Information System (INIS)

Yang, Min; Zhou, Zhe; Guo, De-an

2015-01-01

Sulfurous compounds are commonly present in plants, fungi, and animals. Most of them were reported to possess various bioactivities. Isotopic pattern filter (IPF) is a powerful tool for screening compounds with distinct isotope pattern. Over the past decades, the IPF was used mainly to study Cl- and Br-containing compounds. To our knowledge, the algorithm was scarcely used to screen S-containing compounds, especially when combined with chromatography analyses, because the "3"4S isotopic ion is drastically affected by "1"3C_2 and "1"8O. Thus, we present a new method for a fine isotopic pattern filter (FIPF) based on the separated M + 2 ions ("1"2C_x"1H_y"1"6O_z"3"2S"1"3C_2"1"8O, "1"2C_x_+_2"1H_y"1"6O_z_+_1"3"4S, tentatively named M + 2OC and M + 2S) with an ultra-high-resolution mass (100,000 FWHM @ 400 m/z) to screen sulfur derivatives in traditional Chinese medicines (TCM).This finer algorithm operates through convenient filters, including an accurate mass shift of M + 2OC and M + 2S from M and their relative intensity compared to M. The method was validated at various mass resolutions, mass accuracies, and screening thresholds of flexible elemental compositions. Using the established FIPF method, twelve S-derivatives were found in the popular medicinal used Pueraria species, and 9 of them were tentatively identified by high-resolution multiple stage mass spectrometry (HRMS"n). The compounds were used to evaluate the sulfurous compounds' situation in commercially purchased Pueraria products. The strategy presented here provides a promising application of the IPF method in a new field. - Highlights: • We provide a new strategy for specifically screening of sulfurous compounds. • The fine isotopic pattern filter (FIPF) bases on separation of "1"3C_2+"1"8O and "3"4S. • Ultra high resolution mass (100,000 FWHM @ 400 m/z) is essential for FIPF. • IPF is applied to study the unique components of TCM for the first time. • New sulfurous components

Fluid inclusion and sulfur stable isotope evidence for the origin of the Ahangran Pb-Ag deposit

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Mohammad Maanijou

2015-10-01

Full Text Available Introduction The Ahangaran Pb-Ag deposit is located in the Hamedan province, west Iran, 25 km southeast of the city of Malayer . . The deposit lies in the strongly folded Sanandaj-Sirjan tectonic zone, in which the ore bodies occur as thin lenses and layers. The host rocks of the deposit are Early Cretaceous carbonates and sandstones that are unconformably underlain by Jurassic rocks. Ore minerals include galena, pyrite, chalcopyrite, pyrrhotite and supergene iron oxide minerals. Gangue minerals consist of barite, dolomite, chlorite, calcite and quartz. The mineralization occurs as open-space fillings, veins, veinlets, disseminations, and massive replacements. Alteration consists of silicification, sericitization, and dolomitization. In this study, we carried out studies of mineralogy, microthermometry of fluid inclusions and sulfur isotopes to determine the source of sulfur and the physico-chemical conditions of formation. Materials and methods Seventy samples of different host rocks, alteration, and mineralization were collected from surface outcrops and different tunnels. Twenty of the samples were prepared for mineralogical studies at Tarbiat Modarres University in Tehran and 25 for petrological studies at the University of Bu-Ali Sina. Fluid-inclusion studies were done on 5 samples of quartz and calcite at Pouya Zamin Azin Company in Tehran using a Linkam THM 600 model heating-freezing stage (with a range of -196 to 480ºC. The accuracy and precision of the homogenization measurements are about ±1°C. Salinity estimates were determined from the last melting temperatures of ice, utilizing the equations by Bodnar and Vityk (1994 and for CO2 fluids using equations by Chen (1972. Nine samples of sulfides and barite were crushed and separated by handpicking under binocular microscope and powdered with agate mortar and pestle. About one gram of each sample was sent to the Stable Isotope and ICP/MS Laboratory of Queen’s University, Canada for

Biogenic sulfur and the acidity of rainfall in remote areas of Canada

International Nuclear Information System (INIS)

Nriagu, J.O.; Holdway, D.A.; Coker, R.D.

1987-01-01

Sulfur released from any given natural or anthropogenic source carries an isotopic signature that can be used to trace its flow through the environment. Measurements of the concentration and isotopic composition of sulfur in weekly bulk precipitation samples collected over a 4-year period at a remote location in location in northern Ontario were recorded. The long-term isotopic data and the measurement on the production and release of dimethyl sulfide from boreal wetlands show that biogenic sources can account for up to 30% of the acidifying sulfur burden in the atmosphere in remote areas of Canada. The data suggest that significant biological reemission of anthropogenic sulfur is occurring. The role of this process in the continuing acidification of the environment for years to come must be a matter of concern

Sulfur analysis by inductively coupled plasma-mass spectrometry: A review

Energy Technology Data Exchange (ETDEWEB)

Giner Martínez-Sierra, J.; Galilea San Blas, O.; Marchante Gayón, J.M.; García Alonso, J.I., E-mail: jiga@uniovi.es

2015-06-01

In recent years the number of applications of sulfur (S) analysis using inductively coupled plasma mass spectrometry (ICP-MS) as detector has increased significantly. In this article we describe in some depth the application of ICP-MS for S analysis with emphasis placed on the sulfur-specific detection by hyphenated techniques such as LC, GC, CE and LA coupled on-line to ICP-MS. The different approaches available for sulfur isotope ratio measurements by ICP-MS are also detailed. Particular attention has been paid to the quantification of peptides/proteins and the analysis of metallopeptides/metalloproteins via sulfur by LC–ICP-MS. Likewise, the speciation analysis of metal-based pharmaceuticals and metallodrugs and non-metal selective detection of pharmaceuticals via S are highlighted. Labeling procedures for metabolic applications are also included. Finally, the measurement of natural variations in S isotope composition with multicollector ICP-MS instruments is also covered in this review. - Highlights: • Emphasis placed on the sulfur-specific detection by chromatographic techniques coupled on-line to ICP-MS. • Different instrumental approaches available for sulfur measurements by ICP-MS. • Quantification of proteins and the analysis of metalloproteins via sulfur by LC-ICP-MS. • Labelling procedures for metabolic applications are also included. • The measurement of natural variations in S isotope composition with multicollector ICP-MS.

Geological characteristics and genesis of Niangnianggong gold-silver deposit in Liaoning Province, China

International Nuclear Information System (INIS)

Hou Zhenyuan

2013-01-01

Based on the analysis of geological characteristics and genesis of Niangnianggong deposit, this paper suggested that the deposit is controlled by the EW direction faults and belongs to quartz vein type. Average value of δ 34 S of the ore is 2.19‰, and the variation ranges from 1.6‰ to 4.9‰, which shows the feature of hydrothermal sulfur. The result of lead isotope is fall into original lead zone, which shows the feature of primeval lead system. The result of H-O isotope is close to meteoric line, which means the participation of precipitations. Rb-Sr age of ore is 186.6 Ma, which is similar to the age of diorite dike. Multi-disciplinary analysis concludes that the deposit is a quartz vein type deposit with composite hydrothermal origin. (author)

Mineralization, geochemistry, fluid inclusion and sulfur stable isotope studies in the carbonate hosted Baqoroq Cu-Zn-As deposit (NE Anarak

Directory of Open Access Journals (Sweden)

Mohammad Ali Jazi

2015-10-01

bacterial sulfate reduction or by nonbacterial sulfate reduction through a reaction with organic materialin the sedimentary rocks (thermochemical sulfate reduction. However, the narrow range of δ34S and positive values indicates that they were not produced by bacterial sulfate reduction.Partial thermochemical reduction of sulfates has apparently produced light sulfurvalues (~ 21‰ lighter and it has been effective inthe deposition of ore minerals. Organic matter occurs as graphite in the Baqoroq formation in proximity of Baqoroq deposit (Cherepovsky et al., 1982. Discussion Epigenetic, stratabound and discordant Cu-Zn-As mineralization in the Baqoroq deposit occurs as open space filling of upper Cretaceous rocks. Host rock is partially dolomitized by ascending warm, saline fluids. Seawater sulfates were the source of the sulfidesulfur and the sulfate in the barite. The reduced sulfur was generated by partial thermochemical reduction and it was effective inthe deposition ofthe ore minerals. Based onthe evidence of carbonate host rocks, the absence of igneous activity, the open space filling texture, mineralogy, dolomite alteration, ore geochemistry (As and Sb high content and absence of Bi, microthermometric data of ore bearing fluid and sulfur isotope values, the Baqoroq deposit is very similar to the carbonate hosted copper deposits in Africa and in particular the Tsumeb deposit in Namibia. The Baqoroqdepositmay have been produced bymetamorphicfluids during orogenyrelated to theclosureof the Neo-Tethys ocean. References Cherepovsky, N., Plyaskin, V., Zhitinev, N., Kokorin, Y., Susov, M., Melnikov, B. and Aistov, L., 1982. Report on detailed geological prospecting in Anarak area (Central Iran Nakhlak locality. Geological Survey of Iran and Technoexport Company, Tehran. Report 14, 196 pp. Jazi, M.A., Karimpour, M.H., Malekzadeh, A. and Rahimi, B., 2015. Stratigraphic, lithological and structural controls in placement of Nakhlak deposit (northeast of Esfahan. Advanced

The application of an isotopic ratio technique to a study of the atmospheric oxidation of sulfur dioxide in the plume from a coal fired power plant

International Nuclear Information System (INIS)

Newman, L.; Forrest, J.; Manowitz, B.

1975-01-01

The extent of oxidation of sulfur dioxide to sulfate in the plume of a coal fired plant has been studied by using sampling with a single engine aircraft. A technique employing isotopic ratio measurements was utilized in conjunction with simultaneous concentration measurements of sulfur dioxide and sulfate. The use of sulfur hexafluroide as a conservative tracer was explored. The heterogeneous mechanism postulated in an oil fired plume study appears to pertain to the coal fired plume. However, the extent of oxidation seldom exceeded 5% and is limited by the relatively low particulate content of the coal fired plume. Evidence is presented for the apparent dropping out of sulfate from the plume. Implications pertaining to the ambient oxidation of sulfur dioxide are presented. (author)

Chemical methods for Sm-Nd separation and its application in isotopic geological dating

International Nuclear Information System (INIS)

Guo Qifeng.

1990-01-01

Three chemical methods for Sm-Nd separation are mainly desribed: low chromatography of butamone-ammonium thiocyanate for hight concentration Sm and Nd separation, P 240 column chromatography for medium concentration Sm-Nd separation, and pressure ion exchange for low concentration Sm-Nd. The first Sm-Nd synchrone obtained in China with Sm-Nd methods is introduced and Sm-Nd isotopic geological dating in Early Archaean rocks in eastern Hebei has been determined

The determination of initial ratio of strontium isotope in rocks and its geological application

International Nuclear Information System (INIS)

Ying Junlong; Zhao Puyun; Lin Xiulan

1989-04-01

The method to determine the initial ratio of strontium isotopes existed in rocks of poor rubidium and rich strontium and main carrier minerals is introduced. The initial ratio obtained from this method is equivalent to that acquired by Rb-Sr isochrone. Based on this result, information on regional rock genesis and mineralization regularities can be provided. It has great significance in the research on activities of ancient continental margin and material sources as well as their evolution. The migration of rock, and ore-forming materials, matallogenetic mechanism and its distribution in the space and time evolution are studied by using these data. In conclusion, the determination of strontium isotopes has broad prospects in the geological research

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile

Science.gov (United States)

Zopfi, Jakob; Böttcher, Michael E.; Jørgensen, Bo Barker

2008-02-01

The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S 0 was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H 2S. At the shelf stations, on the other hand, pyrite was significantly depleted in 34S relative to its potential precursors FeS and S 0. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ 34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the

Sulfur in serpentinized oceanic peridotites: Serpentinization processes and microbial sulfate reduction

Science.gov (United States)

Alt, J.C.; Shanks, Wayne C.

1998-01-01

The mineralogy, contents, and isotopic compositions of sulfur in oceanic serpentinites reflect variations in temperatures and fluid fluxes. Serpentinization of serpentinization of Iberian Margin peridotites occurred at low temperatures (???20??-200??C) and high water/rock ratios. Complete serpentinization and consumption of ferrous iron allowed evolution to higher fO2. Microbial reduction of seawater sulfate resulted in addition of low-??34S sulfide (-15 to -43???) and formation of higher-sulfur assemblages that include valleriite and pyrite. The high SO4/total S ratio of Hess Deep serpentinites (0.89) results in an increase of total sulfur and high ??34S of total sulfur (mean ??? 8???). In contrast, Iberian Margin serpentinites gained large amounts of 34S-poor sulfide (mean total S = 3800 ppm), and the high sulfide/total S ratio (0.61) results in a net decrease in ??34S of total sulfur (mean ??? -5???). Thus serpentinization is a net sink for seawater sulfur, but the amount fixed and its isotopic composition vary significantly. Serpentinization may result in uptake of 0.4-14 ?? 1012 g S yr-1 from the oceans, comparable to isotopic exchange in mafic rocks of seafloor hydrothermal systems and approaching global fluxes of riverine sulfate input and sedimentary sulfide output.

Stable isotope variation as a tool to trace the authenticity of beef

International Nuclear Information System (INIS)

Boner, M.; Foerstel, H.

2004-01-01

Organic beef coming principally from Germany was analysed for the hydrogen, carbon, oxygen, nitrogen and sulfur stable isotopic composition to test the possibility of tracing back the geographical origin. Since there is a well-known pattern of D/H and 18 O/ 16 O in meteoric water and in ground water, there is an existing link to tissue water in the beef. By including the stable isotope ratios of the other elements of life further information is available: soils show different isotope ratios of 15 N/ 14 N and 34 S/ 32 S depending on the geological composition, cultivation and atmospheric sulfur deposition. As organic farming is mainly obliged to use only their produced fodder, that ratio is reflected in the beef as well. Different organic beef samples from various German farms have been collected and analysed over nearly two years. To check the differentiation of foreign beef, samples from Argentina and Chile were also included in the study. The analyses of meat samples indicate that it is possible to trace back the region (e.g. Argentina and Germany) by using isotopes of oxygen and hydrogen. A local geographical differentiation can be done by using the stable isotopes of nitrogen and sulfur, as was demonstrated for three farms in Colonia Bay. An optimal differentiation also depends on the quality of further information (e.g. the season, kind of cattle breeding or the declaration of the local geographical origin). Certainly authenticity of beef is not only linked with the geographical origin but can also reflect the differentiation of organic and conventional farming. The fodder of organic cattle farming consists mainly of C 3 plants and the use of C 4 plants is more usual in conventional cattle farming. A 13 C/ 12 C ratio above -20 permille appears as a limit for organic farming. Increased values have to be controlled based on their authenticity. (orig.)

A strategy for fast screening and identification of sulfur derivatives in medicinal Pueraria species based on the fine isotopic pattern filtering method using ultra-high-resolution mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Yang, Min [National Engineering Laboratory for TCM Standardization Technology, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Shanghai 201203 (China); Zhou, Zhe [ThermoFisher Scientific China Co., Ltd, No 6 Building, 27 Xinjinqiao Road, Shanghai 201206 (China); Guo, De-an, E-mail: daguo@simm.ac.cn [National Engineering Laboratory for TCM Standardization Technology, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Shanghai 201203 (China)

2015-09-24

Sulfurous compounds are commonly present in plants, fungi, and animals. Most of them were reported to possess various bioactivities. Isotopic pattern filter (IPF) is a powerful tool for screening compounds with distinct isotope pattern. Over the past decades, the IPF was used mainly to study Cl- and Br-containing compounds. To our knowledge, the algorithm was scarcely used to screen S-containing compounds, especially when combined with chromatography analyses, because the {sup 34}S isotopic ion is drastically affected by {sup 13}C{sub 2} and {sup 18}O. Thus, we present a new method for a fine isotopic pattern filter (FIPF) based on the separated M + 2 ions ({sup 12}C{sub x}{sup 1}H{sub y}{sup 16}O{sub z}{sup 32}S{sup 13}C{sub 2}{sup 18}O, {sup 12}C{sub x+2}{sup 1}H{sub y}{sup 16}O{sub z+1}{sup 34}S, tentatively named M + 2OC and M + 2S) with an ultra-high-resolution mass (100,000 FWHM @ 400 m/z) to screen sulfur derivatives in traditional Chinese medicines (TCM).This finer algorithm operates through convenient filters, including an accurate mass shift of M + 2OC and M + 2S from M and their relative intensity compared to M. The method was validated at various mass resolutions, mass accuracies, and screening thresholds of flexible elemental compositions. Using the established FIPF method, twelve S-derivatives were found in the popular medicinal used Pueraria species, and 9 of them were tentatively identified by high-resolution multiple stage mass spectrometry (HRMS{sup n}). The compounds were used to evaluate the sulfurous compounds' situation in commercially purchased Pueraria products. The strategy presented here provides a promising application of the IPF method in a new field. - Highlights: • We provide a new strategy for specifically screening of sulfurous compounds. • The fine isotopic pattern filter (FIPF) bases on separation of {sup 13}C{sub 2}+{sup 18}O and {sup 34}S. • Ultra high resolution mass (100,000 FWHM @ 400 m/z) is essential

Isotopically labeled sulfur compounds and synthetic selenium and tellurium analogues to study sulfur metabolism in marine bacteria

Directory of Open Access Journals (Sweden)

Nelson L. Brock

2013-05-01

Full Text Available Members of the marine Roseobacter clade can degrade dimethylsulfoniopropionate (DMSP via competing pathways releasing either methanethiol (MeSH or dimethyl sulfide (DMS. Deuterium-labeled [2H6]DMSP and the synthetic DMSP analogue dimethyltelluriopropionate (DMTeP were used in feeding experiments with the Roseobacter clade members Phaeobacter gallaeciensis DSM 17395 and Ruegeria pomeroyi DSS-3, and their volatile metabolites were analyzed by closed-loop stripping and solid-phase microextraction coupled to GC–MS. Feeding experiments with [2H6]DMSP resulted in the incorporation of a deuterium label into MeSH and DMS. Knockout of relevant genes from the known DMSP demethylation pathway to MeSH showed in both species a residual production of [2H3]MeSH, suggesting that a second demethylation pathway is active. The role of DMSP degradation pathways for MeSH and DMS formation was further investigated by using the synthetic analogue DMTeP as a probe in feeding experiments with the wild-type strain and knockout mutants. Feeding of DMTeP to the R. pomeroyi knockout mutant resulted in a diminished, but not abolished production of demethylation pathway products. These results further corroborated the proposed second demethylation activity in R. pomeroyi. Isotopically labeled [2H3]methionine and 34SO42−, synthesized from elemental 34S8, were tested to identify alternative sulfur sources besides DMSP for the MeSH production in P. gallaeciensis. Methionine proved to be a viable sulfur source for the MeSH volatiles, whereas incorporation of labeling from sulfate was not observed. Moreover, the utilization of selenite and selenate salts by marine alphaproteobacteria for the production of methylated selenium volatiles was explored and resulted in the production of numerous methaneselenol-derived volatiles via reduction and methylation. The pathway of selenate/selenite reduction, however, proved to be strictly separated from sulfate reduction.

Zoning Of Pollutant Dispersion Came From IJEN Crater In The Downstream Region Of BANYUPUTIH River Using Oxygen-18 (18O) Natural Isotope Technique

International Nuclear Information System (INIS)

Susiati, Heni; Yarianto, S.B.S.; Sjarmufni, A.; Suprijadi; Wibagyo

2002-01-01

The research should be arranged for natural isotope composition of Oxygen-18 ( 18 O) in the water catchments of Banyupahit -Banyuputih river. Aim of the research are determine zoning of pollutant dispersion and be clarified that the pollution really come from lien crater as more surely above mentioned by the result of investigation previously. Research method be used field survey and characteristic analysis of Oksigen-18 isotope. Zoning of pollutant dispersion in the downstream side covers settlement. agricultural, plantation, and sugar factory area have conducted by analyzing Oksigen-18 isotope characteristic. Based on the result of the research pollutant dispersion area in the downstream region. the Eastern side of water catchments area were categorized as pollution level l was more dominant rather than in the Western side and pollution level II came from water pound area of Banyuputih. This phenomena caused of an irrigation system using by Liwung Water Pound of Banyuputih river which should be polluted by Sulfur. Geological factor in the Eastern (lithology) were most of sand rock also induce the dispersion of Sulfur rather than in the Western area. Present research has clarified previous investigation that Banyupahit river were polluted by Sulfur as a result of ijen crater leakage

New geologic, fluid inclusion and stable isotope studies on the controversial Igarapé Bahia Cu-Au deposit, Carajás Province, Brazil

Science.gov (United States)

Dreher, Ana M.; Xavier, Roberto P.; Taylor, Bruce E.; Martini, Sérgio L.

2008-02-01

contribution of reduced and oxydized sulfur is also evident. Oxygen isotopic ratios in magnetite, quartz, and siderite yield calculated temperatures of ˜400°C and δ18O-enriched compositions (5 to 16.5 per mil) for the ore-forming fluids that suggest a magmatic input and/or an interaction with 18O-rich, probably sedimentary rocks. The late veins of the Igarapé Bahia deposit area were formed from saline aqueous fluids (2 to 60 wt% NaCl + CaCl2 equiv) with δ18Ofluid compositions around 0 per mil that indicate contribution from meteoric fluids. With respect to geological features, Igarapé Bahia bears similarity with syngenetic, volcanic-hosted massive sulfide (VHMS)-type deposits, as indicated by the volcano-sedimentary geological context, stratabound character, and association with submarine volcanic flows, hyaloclastite, and exhalative beds such as BIF and chert. On the other hand, the highly saline ore fluids and the mineral assemblage, dominated by magnetite and chalcopyrite, with associated gold, U- and LREE-minerals and scarce pyrite, indicate that Igarapé Bahia belongs to the Fe oxide Cu-Au (IOCG) group of deposits. The available geochronologic data used to attest syngenetic or epigenetic origins for the mineralization are either imprecise or may not represent the main mineralization episode but a later, superimposed event. The C, S, and O isotopic results obtained in this study do not clearly discriminate between fluid sources. However, recent B isotope data obtained on tourmaline from the matrix of the fragmental rock ore unit (Xavier, Wiedenbeck, Dreher, Rhede, Monteiro, Araújo, Chemical and boron isotopic composition of tourmaline from Archean and Paleoproterozoic Cu-Au deposits in the Carajás Mineral Province, 1° Simpósio Brasileiro de Metalogenia, Gramado, Brazil, extended abstracts, CD-ROM, 2005) provide strong evidence of the involvement of a marine evaporitic source in the hydrothermal system of Igarapé Bahia. Evaporite-derived fluids may explain the

Geochemistry of silicon isotopes

Energy Technology Data Exchange (ETDEWEB)

Ding, Tiping; Li, Yanhe; Gao, Jianfei; Hu, Bin [Chinese Academy of Geological Science, Beijing (China). Inst. of Mineral Resources; Jiang, Shaoyong [China Univ. of Geosciences, Wuhan (China).

2018-04-01

Silicon is one of the most abundant elements in the Earth and silicon isotope geochemistry is important in identifying the silicon source for various geological bodies and in studying the behavior of silicon in different geological processes. This book starts with an introduction on the development of silicon isotope geochemistry. Various analytical methods are described and compared with each other in detail. The mechanisms of silicon isotope fractionation are discussed, and silicon isotope distributions in various extraterrestrial and terrestrial reservoirs are updated. Besides, the applications of silicon isotopes in several important fields are presented.

Toward a unifying model for the late Neoproterozoic sulfur cycle

Science.gov (United States)

Johnston, D. T.; Gill, B. C.; Ries, J. B.; OBrien, T.; Macdonald, F. A.

2011-12-01

The latest Proterozoic has always fascinated Earth historians. Between the long identified enigmas surrounding the sudden appearance of animals and the more recent infatuation with large-sale geochemical anomalies (i.e. the Shuram - Wonaka event), the closing 90 million years of the Proterozoic - the Ediacaran - houses a number of important and unanswered questions. Detailed redox geochemistry and stable isotope reconstructions of stratigraphic units covering this time interval have begun to unravel some of it's mysteries, however much remains to be explained. The sulfur cycle, with it's intimate links to both the marine carbon cycle (through remineralization reactions) and overall oxidant budgets (via seawater sulfate), sits poised to provide a sharp tool to track environmental change. Previous work has recognized this potential, and serves as a point of entrance for our current work. However what is lacking - and the goal of this study - is to place quantitative constraints the geochemical evolution of marine basins through this interval. Here we will present multiple sulfur isotope data from pyrite and sulfates through Ediacaran stratigraphy from the Yukon, Russia and Namibia. To maximize the utility of sulfur isotope studies, we have focused on Ediacaran stratigraphic sections from multiple continents that record both the Shuram anomaly and contain rich fossil records. These sections provide, when interpreted together, a fresh opportunity to revisit the geochemical setting that gave rise to animals. Importantly, the inclusion of multiple sulfur isotope data allows us to place further constraints on the mechanisms underpinning isotopic variability. For instance, when coupled with new experimental data, tighter constraints are provided on how fractionation scales with sulfate concentrations. This may allow for decoupling changes in biological fractionations from modifications to the global sulfur cycle (i.e. changes in seawater sulfate concentrations or the vigor

Source Of Hydrogen Sulfide To Sulfidic Spring And Watershed Ecosystems In Northern Sierra De Chiapas, Mexico Based On Sulfur And Carbon Isotopes

Science.gov (United States)

Rosales Lagarde, L.; Boston, P. J.; Campbell, A.

2013-12-01

At least four watersheds in northern Sierra de Chiapas, Mexico are fed by conspicuous karst sulfide-rich springs. The toxic hydrogen sulfide (H2S) in these springs nurtures rich ecosystems including especially adapted microorganisms, invertebrates and fish. Sulfur and carbon isotopic analysis of various chemical species in the spring water are integrated within their hydrogeologic context to evaluate the hydrogen sulfide source. Constraining the H2S origin can also increase the understanding of this compound effect in the quality of the nearby hydrocarbon reservoirs, and the extent to which its oxidation to sulfuric acid increases carbonate dissolution and steel corrosion in surface structures. The SO42-/H2S ratio in the spring water varies from 70,000 to 2 meq/L thus sulfate is the dominant species in the groundwater system. This sulfate is mainly produced from anhydrite dissolution based on its isotopic signature. The Δ SO42--H2S range of 16 spring water samples (30-50 ‰) is similar to the values determined by Goldhaber & Kaplan (1975) and Canfield (2001) for low rates of bacterial sulfate reduction suggesting that this is the most important mechanism producing H2S. Although the carbon isotopes do not constrain the nature of the organic matter participating in this reaction, this material likely comes from depth, perhaps as hydrocarbons, due to the apparent stability of the system. The organic matter availability and reactivity probably control the progress of sulfate reduction. The subsurface environments identified in the area also have different sulfur isotopic values. The heavier residual sulfate isotopic value in the Northern brackish springs (δ34S SO42- ≥ 18 ‰) compared to the Southern springs (δ34S SO42- ~18 ‰) suggests sulfate reduction is particularly enhanced in the former, probably by contribution of organic matter associated with oil produced water. In comparison, the composition of the Southern aquifer is mainly influenced by halite

Formation of black and white smokers in the North Fiji Basin: Sulfur and lead isotope constraints

Science.gov (United States)

Kim, J.; Lee, I.; Lee, K.; Yoo, C.; Ko, Y.

2004-12-01

The hydrothermal chimneys were recovered from 16o50¡_S triple junction area in the North Fiji Basin. The chimney samples are divided into three groups according to their mineralogy and metal contents; 1) Black smoker, 2) White smoker, 3) Transitional type. Black smoker chimneys are mainly composed of chalcopyrite and pyrite, and are enriched in high temperature elements such as Cu, Co, Mo, and Se. White smoker chimneys consist of sphalerite and marcasite with trace of pyrite and chalcopyrite, and are enriched in low temperature elements (Zn, Cd, Pb, As, and Ga). Transitional chimneys show intermediate characteristics in mineralogy and composition between black and white smokers. Basaltic rocks sampled from the triple junction show wide variation in geochemistry. Trace elements composition of basaltic rocks indicates that the magma genesis in the triple junction area was affected by mixing between N-MORB and E-MORB sources. The sulfur and lead isotope compositions of hydrothermal chimneys show distinct differences between the black and white smokers. Black smokers are depleted in 34S (Øä34S = +0.4 to +4.8) and are low in lead isotope composition (206Pb/204Pb = 18.082 to 18.132; 207Pb/204Pb = 15.440 to 15.481; 208Pb/204Pb = 37.764 to 37.916) compared to white smoker and transitional chimneys (Øä34S = +2.4 to +5.6; 206Pb/204Pb = 18.122 to 18.193; 207Pb/204Pb = 15.475 to 15.554; 208Pb/204Pb = 37.882 to 38.150). The heavier sulfur isotopic fractionation in white smoker can be explained by boiling of hydrothermal fluids and mixing with ambient seawater. The lead isotope compositions of the hydrothermal chimneys indicate that the metal in black and white smokers come from hydrothermal reaction with N-MORB and E-MORB, respectively. Regarding both black and white smoker are located in the same site, the condition of phase separation of hydrothermal fluid that formed white smokers might result from P-T condition of high temperature reaction zone below the hydrothermal

Understanding wetland sub-surface hydrology using geologic and isotopic signatures

Directory of Open Access Journals (Sweden)

P. Sahu

2009-07-01

Full Text Available This paper attempts to utilize hydrogeology and isotope composition of groundwater to understand the present hydrological processes prevalent in a freshwater wetland, source of wetland groundwater, surface water/groundwater interaction and mixing of groundwater of various depth zones in the aquifer. This study considers East Calcutta Wetlands (ECW – a freshwater peri-urban inland wetland ecosystem located at the lower part of the deltaic alluvial plain of South Bengal Basin and east of Kolkata city. This wetland is well known over the world for its resource recovery systems, developed by local people through ages, using wastewater of the city. Geological investigations reveal that the sub-surface geology is completely blanketed by the Quaternary sediments comprising a succession of silty clay, sand of various grades and sand mixed with occasional gravels and thin intercalations of silty clay. At few places the top silty clay layer is absent due to scouring action of past channels. In these areas sand is present throughout the geological column and the areas are vulnerable to groundwater pollution. Groundwater mainly flows from east to west and is being over-extracted to the tune of 65×10³ m³/day. δ¹⁸O and δD values of shallow and deep groundwater are similar indicating resemblance in hydrostratigraphy and climate of the recharge areas. Groundwater originates mainly from monsoonal rain with some evaporation prior to or during infiltration and partly from bottom of ponds, canals and infiltration of groundwater withdrawn for irrigation. Relatively high tritium content of the shallow groundwater indicates local recharge, while the deep groundwater with very low tritium is recharged mainly from distant areas. At places the deep aquifer has relatively high tritium, indicating mixing of groundwater of shallow and deep aquifers. Metals such as copper, lead, arsenic, cadmium, aluminium, nickel and chromium are also

Understanding wetland sub-surface hydrology using geologic and isotopic signatures

Science.gov (United States)

Sikdar, P. K.; Sahu, P.

2009-07-01

This paper attempts to utilize hydrogeology and isotope composition of groundwater to understand the present hydrological processes prevalent in a freshwater wetland, source of wetland groundwater, surface water/groundwater interaction and mixing of groundwater of various depth zones in the aquifer. This study considers East Calcutta Wetlands (ECW) - a freshwater peri-urban inland wetland ecosystem located at the lower part of the deltaic alluvial plain of South Bengal Basin and east of Kolkata city. This wetland is well known over the world for its resource recovery systems, developed by local people through ages, using wastewater of the city. Geological investigations reveal that the sub-surface geology is completely blanketed by the Quaternary sediments comprising a succession of silty clay, sand of various grades and sand mixed with occasional gravels and thin intercalations of silty clay. At few places the top silty clay layer is absent due to scouring action of past channels. In these areas sand is present throughout the geological column and the areas are vulnerable to groundwater pollution. Groundwater mainly flows from east to west and is being over-extracted to the tune of 65×103 m3/day. δ18O and δD values of shallow and deep groundwater are similar indicating resemblance in hydrostratigraphy and climate of the recharge areas. Groundwater originates mainly from monsoonal rain with some evaporation prior to or during infiltration and partly from bottom of ponds, canals and infiltration of groundwater withdrawn for irrigation. Relatively high tritium content of the shallow groundwater indicates local recharge, while the deep groundwater with very low tritium is recharged mainly from distant areas. At places the deep aquifer has relatively high tritium, indicating mixing of groundwater of shallow and deep aquifers. Metals such as copper, lead, arsenic, cadmium, aluminium, nickel and chromium are also present in groundwater of various depths. Therefore

Decoupling of Neoarchean sulfur sources recorded in Algoma-type banded iron formation

Science.gov (United States)

Diekrup, David; Hannington, Mark D.; Strauss, Harald; Ginley, Stephen J.

2018-05-01

Neoarchean Algoma-type banded iron formations (BIFs) are widely viewed as direct chemical precipitates from proximal volcanic-hydrothermal vents. However, a systematic multiple sulfur isotope study of oxide-facies BIF from a type locality in the ca. 2.74 Ga Temagami greenstone belt reveals mainly bacterial turnover of atmospheric elemental sulfur in the host basin rather than deposition of hydrothermally cycled seawater sulfate or sulfur from direct volcanic input. Trace amounts of chromium reducible sulfur that were extracted for quadruple sulfur isotope (32S-33S-34S-36S) analysis record the previously known mass-independent fractionation of volcanic SO2 in the Archean atmosphere (S-MIF) and biological sulfur cycling but only minor contributions from juvenile sulfur, despite the proximity of volcanic sources. We show that the dominant bacterial metabolisms were iron reduction and sulfur disproportionation, and not sulfate reduction, consistent with limited availability of organic matter and the abundant ferric iron deposited as Fe(OH)3. That sulfur contained in the BIF was not a direct volcanic-hydrothermal input, as expected, changes the view of an important archive of the Neoarchean sulfur cycle in which the available sulfur pools were strongly decoupled and only species produced photochemically under anoxic atmospheric conditions were deposited in the BIF-forming environment.

Accurate determination of sulfur in gasoline and related fuel samples using isotope dilution ICP-MS with direct sample injection and microwave-assisted digestion.

Science.gov (United States)

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

2004-09-01

Inductively coupled plasma isotope-dilution mass spectrometry (ICP-IDMS) with direct injection of isotope-diluted samples into the plasma, using a direct injection high-efficiency nebulizer (DIHEN), was applied for accurate sulfur determinations in sulfur-free premium gasoline, gas oil, diesel fuel, and heating oil. For direct injection a micro-emulsion consisting of the corresponding organic sample and an aqueous 34S-enriched spike solution with additions of tetrahydronaphthalene and Triton X-100, was prepared. The ICP-MS parameters were optimized with respect to high sulfur ion intensities, low mass-bias values, and high precision of 32S/34S ratio measurements. For validation of the DIHEN-ICP-IDMS method two certified gas oil reference materials (BCR 107 and BCR 672) were analyzed. For comparison a wet-chemical ICP-IDMS method was applied with microwave-assisted digestion using decomposition of samples in a closed quartz vessel inserted into a normal microwave system. The results from both ICP-IDMS methods agree well with the certified values of the reference materials and also with each other for analyses of other samples. However, the standard deviation of DIHEN-ICP-IDMS was about a factor of two higher (5-6% RSD at concentration levels above 100 mircog g(-1)) compared with those of wet-chemical ICP-IDMS, mainly due to inhomogeneities of the micro-emulsion, which causes additional plasma instabilities. Detection limits of 4 and 18 microg g(-1) were obtained for ICP-IDMS in connection with microwave-assisted digestion and DIHEN-ICP-IDMS, respectively, with a sulfur background of the used Milli-Q water as the main limiting factor for both methods.

Accurate determination of sulfur in gasoline and related fuel samples using isotope dilution ICP-MS with direct sample injection and microwave-assisted digestion

Energy Technology Data Exchange (ETDEWEB)

Heilmann, Jens; Boulyga, Sergei F.; Heumann, Klaus G. [Johannes Gutenberg-University, Institute of Inorganic Chemistry and Analytical Chemistry, Mainz (Germany)

2004-09-01

Inductively coupled plasma isotope-dilution mass spectrometry (ICP-IDMS) with direct injection of isotope-diluted samples into the plasma, using a direct injection high-efficiency nebulizer (DIHEN), was applied for accurate sulfur determinations in sulfur-free premium gasoline, gas oil, diesel fuel, and heating oil. For direct injection a micro-emulsion consisting of the corresponding organic sample and an aqueous {sup 34}S-enriched spike solution with additions of tetrahydronaphthalene and Triton X-100, was prepared. The ICP-MS parameters were optimized with respect to high sulfur ion intensities, low mass-bias values, and high precision of {sup 32}S/{sup 34}S ratio measurements. For validation of the DIHEN-ICP-IDMS method two certified gas oil reference materials (BCR 107 and BCR 672) were analyzed. For comparison a wet-chemical ICP-IDMS method was applied with microwave-assisted digestion using decomposition of samples in a closed quartz vessel inserted into a normal microwave system. The results from both ICP-IDMS methods agree well with the certified values of the reference materials and also with each other for analyses of other samples. However, the standard deviation of DIHEN-ICP-IDMS was about a factor of two higher (5-6% RSD at concentration levels above 100 {mu}g g{sup -1}) compared with those of wet-chemical ICP-IDMS, mainly due to inhomogeneities of the micro-emulsion, which causes additional plasma instabilities. Detection limits of 4 and 18 {mu}g g{sup -1} were obtained for ICP-IDMS in connection with microwave-assisted digestion and DIHEN-ICP-IDMS, respectively, with a sulfur background of the used Milli-Q water as the main limiting factor for both methods. (orig.)

Quantitative Reconstruction of Sulfur Deposition Using a Mixing Model Based on Sulfur Isotope Ratios in Tree Rings.

Science.gov (United States)

Ishida, Takuya; Tayasu, Ichiro; Takenaka, Chisato

2015-11-01

Quantification of sulfur (S) deposition is critical to deciphering the environmental archive of S in terrestrial ecosystems. Here we propose a mixing model that quantifies S deposition based on the S isotope ratio (δS) in tree rings. We collected samples from Japanese cedar ( D. Don) stumps from two sites: one near Yokkaichi City (YOK), which is well known for having the heaviest S air pollution in the world, and one at Inabu-cho (INA) in central Japan, which has been much less affected by air pollution. The δS profiles at both sites are consistent with S air pollution and contributions of anthropogenic S. The minimum value in YOK is lower than the δS values of anthropogenic S or any other possible source. Because the δS in the tree rings is affected by fractionation in the forest ecosystems, we used a mixing model to account for the isotope effects and to distinguish the sources of S. Based on the model results, we infer that the peak of S emissions at YOK occurred sometime between the late 1960s and early 1970s (489 mmol m yr). This estimated value is comparable with the highest reported values in Europe. This is the first quantitative estimate of anthropogenic input of S in forest systems based on δS in tree rings. Our results suggest that tree ring data can be used when monitoring stations of atmospheric S are lacking and that estimates of S deposition using δS in tree rings will advance our understanding of the local-scale S dynamics and the effect of human activities on it. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Isotopic exchange of carbon-bound hydrogen over geologic timescales

Science.gov (United States)

Sessions, Alex L.; Sylva, Sean P.; Summons, Roger E.; Hayes, John M.

2004-04-01

The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50-100°C) exchange likely occurs on timescales of 104 to 108 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (exchange in ancient (>350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity. Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ∼75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D2O indicate that the number of D atoms incorporated during

Application and evaluation of the mass spectrometric isotope dilution technique in the determination of rare earths in geological materials

International Nuclear Information System (INIS)

Moraes, N.M.P. de.

1988-01-01

Establishment of the experimental procedures employed in the rare earth element determination of geological samples by mass spectrometric isotope dilution analysis is discussed in the present work. The procedures involve preparation and calibration of the isotope tracers isotope dilution, dissolution in a teflon pressure vessel, chemical separation and isotope analysis using a fully automated Micromass VG ISOTOPES model 354 thermal ionization mass spectrometer. For the initial chemical separation of total rare earths the cationic resin was employed and HC1 and HNO 3 acids as eluents. In the second step rare earths elements were separated into individual (La, Ce and Nd) and subgroups (Sm-Eu-Gd, Yb-Er-Dy) fractions using the same cationic resin and α-HIBA as eluent. Nine elements La, Ce, Nd, Sm, Eu, Gd, Dy, Er and Yb are determined by this method in the ''United States Geological Survey'' (USGS) standard samples GSP-1, AGV-1 and G-2, with an overall precision of +- 1 to 2% and an accuracy of 5%. The concentration of rare earth element determined in the standard sample PCC-1 showed that the total analytical blanks are in submicrogram levels. The concentration of rare earth elements in the same USGS standard samples were also determined by Instrumental neutron activation analysis, neutron activation analysis with chemical separation before irradiation and inductively coupled argon plasma spectroscopy. The chemical procedures employed for these methods are the same as that used for mass spectrometric isotope dilution. Based on the results obtained, each method was evaluated pointing out their merits and defects. The study clearly showed that the chemical procedure employed for all these techniques was satisfactory. (author) [pt

Isotopes in heterogeneous catalysis

CERN Document Server

Hargreaves, Justin SJ

2006-01-01

The purpose of this book is to review the current, state-of-the-art application of isotopic methods to the field of heterogeneous catalysis. Isotopic studies are arguably the ultimate technique in in situ methods for heterogeneous catalysis. In this review volume, chapters have been contributed by experts in the field and the coverage includes both the application of specific isotopes - Deuterium, Tritium, Carbon-14, Sulfur-35 and Oxygen-18 - as well as isotopic techniques - determination of surface mobility, steady state transient isotope kinetic analysis, and positron emission profiling.

The geological, isotopic, botanical, invertebrate, and lower vertebrate contexts for aripithecus ramidus

Energy Technology Data Exchange (ETDEWEB)

Woldegabriel, Giday [Los Alamos National Laboratory; Ambrose, Stanley H [UNIV OF ILLINOIS; Barboni, Doris [CEREGE, FRANCE; Bonneffille, Raymond [CEREGE, FRANCE; Bremond, Laurent [MONTPELLIER, FRANCE; Currie, Brian [MIAMI UNIV, OXFORD, OHIO; Degusta, David [STANFORD UNIV.; Hart, William K [MIAMI UNIV, OXFORD, OHIO; Murray, Alison M [UNIV OF ALBERTA; Renne, Paul R [UC/BERKELEY; Jolly - Saad, M C [NANTERRE, FRANCE; Stewart, Kathlyn M [CANADA; White, Tim D [UC/BERKELEY

2009-01-01

Sediments containing Ardipithecus ramidus were deposited 4.4 million years ago on an alluvial floodplain in Ethiopia's western Afar rift. The Lower Aramis Member hominid-bearing unit, now exposed across a >9-kilometer structural arc, is sandwiched between two volcanic tuffs that have nearly identical {sup 40}Ar/{sup 39}Ar ages. Geological data presented here, along with floral, invertebrate, and vertebrate paleontological and taphonomic evidence associated with the hominids, suggest that they occupied a wooded biotope over the western three-fourths of the paleotransect. Phytoliths and oxygen and carbon stable isotopes of pedogenic carbonates provide evidence of humid cool woodlands with a grassy substrate.

Determination of trace sulfur in biodiesel and diesel standard reference materials by isotope dilution sector field inductively coupled plasma mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Amais, Renata S. [Group of Applied Instrumental Analysis, Department of Chemistry, Federal University of São Carlos, São Carlos, SP (Brazil); Long, Stephen E. [Chemical Sciences Division, National Institute of Standards and Technology, Charleston, SC (United States); Nóbrega, Joaquim A. [Group of Applied Instrumental Analysis, Department of Chemistry, Federal University of São Carlos, São Carlos, SP (Brazil); Christopher, Steven J., E-mail: steven.christopher@nist.gov [Chemical Sciences Division, National Institute of Standards and Technology, Charleston, SC (United States)

2014-01-02

Graphical abstract: -- Highlights: •Sulfur mass fractions are measured below 10 mg kg{sup −1} in diesel fuel materials. •SF-ICP-MS resolves molecular interferences, including oxygen and sulfur hydrides. •A detection limit of 0.7 mg kg{sup −1} (in the fuel sample) was obtained. -- Abstract: A method is described for quantification of sulfur at low concentrations on the order of mg kg{sup −1} in biodiesel and diesel fuels using isotope dilution and sector field inductively coupled plasma mass spectrometry (ID-SF-ICP-MS). Closed vessel microwave-assisted digestion was employed using a diluted nitric acid and hydrogen peroxide decomposition medium to reduce sample dilution volumes. Medium resolution mode was employed to eliminate isobaric interferences at {sup 32}S and {sup 34}S related to polyatomic phosphorus and oxygen species, and sulfur hydride species. The method outlined yielded respective limits of detection (LOD) and limits of quantification (LOQ) of 0.7 mg kg{sup −1} S and 2.5 mg kg{sup −1} S (in the sample). The LOD was constrained by instrument background counts at {sup 32}S but was sufficient to facilitate value assignment of total S mass fraction in NIST SRM 2723b Sulfur in Diesel Fuel Oil at 9.06 ± 0.13 mg kg{sup −1}. No statistically significant difference at a 95% confidence level was observed between the measured and certified values for certified reference materials NIST SRM 2773 B100 Biodiesel (Animal-Based), CENAM DRM 272b and NIST SRM 2723a Sulfur in Diesel Fuel Oil, validating method accuracy.

238 series isotopes at different soil depths and disequilibrium over various geology and soil classifications along transects in selected parts of Ireland

International Nuclear Information System (INIS)

McAulay, I.R.; Hayes, A.

1996-01-01

Sampling of soils was carried out along linear transects in selected regions of the country, a technique known as Transect Sampling. This was a controlled rather than a random sampling technique. The transects were located in regions which were previously known to contain high levels of the 226 Ra isotope, from the 238 U series. The soil sampling was carried out at selected sites along these transects. At each transect site, two different soil depths were examined and the soil samples collected were identified as the top and bottom soil samples. This transect data set, consisting of the isotope activity levels and the influencing variables transect geology and soil types, provided a data base for investigation. Comparisons were made between the soil isotope activity levels measured at different soil depths. An examination of the 238 U decay series showed the existence of disequilibrium. Relationships between the disequilibrium data and the associated geology and soil types were investigated. (author)

A study on hydrogen, oxygen, carbon, sulfur and lead isotopes in the rich uranium deposit No.201

International Nuclear Information System (INIS)

Li Yuexiang; Li Tiangang; Tong Hongshou; Feng Mingyue; Xu Zhan

1995-01-01

The uranium deposit No.201 located in Indonesian granite is one of the richest uranium deposits of granite type in China. An attempt is made to investigate the sources of ore-forming solutions and ore-forming materials, and to presume the environment of ore formation in the light of the study on composition of stable isotopes such as hydrogen, oxygen, carbon, sulfur and lead. The research results indicate that the ore-forming fluids in the deposit is mainly composed of meteoric water, the ore-forming materials principally came from pre-Yanshanian granite Massif and possibly, partly from the lower crust, and metallogenesis was undertaken under relatively stable physicochemical conditions

A study on hydrogen, oxygen, carbon, sulfur and lead isotopes in the rich uranium deposit No.201

Energy Technology Data Exchange (ETDEWEB)

Yuexiang, Li; Tiangang, Li; Hongshou, Tong; Mingyue, Feng; Zhan, Xu [Beijing Research Inst. of Uranium Geology (China)

1995-09-01

The uranium deposit No.201 located in Indonesian granite is one of the richest uranium deposits of granite type in China. An attempt is made to investigate the sources of ore-forming solutions and ore-forming materials, and to presume the environment of ore formation in the light of the study on composition of stable isotopes such as hydrogen, oxygen, carbon, sulfur and lead. The research results indicate that the ore-forming fluids in the deposit is mainly composed of meteoric water, the ore-forming materials principally came from pre-Yanshanian granite Massif and possibly, partly from the lower crust, and metallogenesis was undertaken under relatively stable physicochemical conditions.

Geochemical, Sulfur Isotopic Characteristics and Source Contributions of Size-Aggregated Aerosols Collected in Baring Head, New Zealand.

Science.gov (United States)

Li, J.; Michalski, G. M.; Davy, P.; Harvey, M.; Wilkins, B. P.; Katzman, T. L.

2017-12-01

Sulfate aerosols are critical to the climate, human health, and the hydrological cycle in the atmosphere, yet the sources of sulfate in aerosols are not completely understood. In this work, we evaluated the sources of sulfate in size-aggregated aerosols from the Southern Pacific Ocean and the land of New Zealand using geochemical and isotopic analyses. Aerosols were collected at Baring Head, New Zealand between 6/30/15 to 8/4/16 using two collectors, one only collects Southern Pacific Ocean derived aerosols (open-ocean collector), the other collects aerosols from both the ocean and the land (all-direction collector). Each collector is equipped with two filters to sample size-aggregated aerosols (fine aerosols: NSS-SO42-, 70%), while coarse aerosols are dominated by sea-salt sulfate. However, some NSS-SO42- was also observed in coarse aerosols collected in summer, suggesting the presence of accumulation mode NSS-SO42- aerosols, which is possibly due to high summer biogenic DMS flux. The sources of sulfur in NSS-SO42- could be further determined by their d34S values. DMS emission is likely the sole sulfur source in the open-ocean collector as it shows constant DMS-like d34S signatures (15-18‰) throughout the year. Meanwhile, the d34S of NSS-SO42- in the all-direction collector display a seasonal trend: summer time d34S values are higher and DMS-like (15-18‰), indicating DMS emission is the dominant sulfur source; winter time d34S values are lower ( 6-12‰), therefore the sulfur is likely sourced from both DMS emission and terrestrial S input with low d34S values, such as volcanic activities, fossil fuel and wood burning.

Dynamics of biogeochemical sulfur cycling in Mono Lake

Science.gov (United States)

Phillips, A. A.; Fairbanks, D.; Wells, M.; Fullerton, K. M.; Bao, R.; Johnson, H.; Speth, D. R.; Stamps, B. W.; Miller, L.; Sessions, A. L.

2017-12-01

Mono Lake, California is a closed-basin soda lake (pH 9.8) with high sulfate (120mM), and is an ideal natural laboratory for studying microbial sulfur cycling. Mono Lake is typically thermally stratified in summer while mixing completely in winter. However, large snowmelt inputs may induce salinity stratification that persists for up to five years, causing meromixis. During the California drought of 2014-16, the lake has mixed thoroughly each winter, but the abundant 2017 snowmelt may usher in a multi-year stratification. This natural experiment provides an opportunity to investigate the temporal relationship between microbial sulfur cycling and lake biogeochemistry. We analyzed water samples from five depths at two stations in May of 2017, before the onset of meromixis. Water column sulfate isotope values were generally constant with depth, centering at a δ34SVCDT of 17.39 ± 0.06‰. Organic sulfur isotopes were consistently lighter than lake sulfate, with a δ34SVCDT of 15.59 ± 0.56‰. This significant offset between organic and inorganic sulfur contradicts the minimal isotope effect associated with sulfate assimilation. Sediment push core organic values were further depleted, ranging between δ34SVCDT of -8.94‰ and +0.23‰, implying rapid turnover of Mono Lake sulfur pools. Both lipid biomarkers and 16S rRNA gene amplicons identify Picocystis salinarum, a unicellular green alga, as the dominant member of the microbial community. However, bacterial biomarkers and 16S rRNA genes point to microbes capable of sulfur cycling. We found that dsrA increased with depth (R2 = 0.9008, p reducers and sulfide oxidizers after >1 year of stratification. We saw no evidence in May of 2017 of sulfate reducing bacteria across the oxycline. Additionally, no sulfide was detectable in lake bottom waters despite oxygen below 6.25 µM. Preliminary results suggest a dynamic interplay between sulfide oxidation, sulfate reduction, and the onset of lake stratification. Additional

Sulfur isotopes of host strata for Howards Pass (Yukon–Northwest Territories) Zn-Pb deposits implicate anaerobic oxidation of methane, not basin stagnation

Science.gov (United States)

Johnson, Craig A.; Slack, John F.; Dumoulin, Julie A.; Kelley, Karen Duttweiler; Falck, Hendrik

2018-01-01

A new sulfur isotope stratigraphic profile has been developed for Ordovician-Silurian mudstones that host the Howards Pass Zn-Pb deposits (Canada) in an attempt to reconcile the traditional model of a stagnant euxinic basin setting with new contradictory findings. Our analyses of pyrite confirm the up-section 34S enrichment reported previously, but additional observations show parallel depletion of carbonate 13C, an increase in organic carbon weight percent, and a change in pyrite morphology. Taken together, the data suggest that the 34S enrichment reflects a transition in the mechanism of pyrite formation during diagenesis, not isotopic evolution of a stagnant water mass. Low in the stratigraphic section, pyrite formed mainly in the sulfate reduction zone in association with organic matter–driven bacterial sulfate reduction. In contrast, starting just below the Zn-Pb mineralized horizon, pyrite formed increasingly within the sulfate-methane transition zone in association with anaerobic oxidation of methane. Our new insights on diagenesis have implications for (1) the setting of Zn-Pb ore formation, (2) the reliability of redox proxies involving metals, and (3) the source of ore sulfur for Howards Pass, and potentially for other stratiform Zn-Pb deposits contained in carbonaceous strata.

About the variation mechanism of the isotopic composition of oxygen and carbon through the geological ages

International Nuclear Information System (INIS)

Torquato, J.R.F.; Frischkorn, H.

1982-01-01

The variations of the Δ 180 ratio found in the carbonates are shown as being of the primary origin. In addition it is shown that these values can be preserved, through the geological ages, even it one considers the carbonates to be worked over again. Are given some subsidies about the study of the paleoenvironments through the analysis of the isotopic composition of the carbon. (A.B.) [pt

Transboundary transport of anthropogenic sulfur in PM2.5 at a coastal site in the Sea of Japan as studied by sulfur isotopic ratio measurement

International Nuclear Information System (INIS)

Inomata, Yayoi; Ohizumi, Tsuyoshi; Take, Naoko; Sato, Keiichi; Nishikawa, Masataka

2016-01-01

Sulfur isotopic ratios (δ"3"4S) in size separated aerosol particles (PM2.5 and coarse particles) were measured at Niigata-Maki facing the Sea of Japan. Non-sea salt δ"3"4S (δ"3"4S_n_s_s) in PM2.5 showed seasonal variations with relatively high values in winter (1.0–3.9‰ in spring, 2.8–4.5‰ in summer, 1.3–4.5‰ in autumn, 3.7–5.7‰ in winter). Taking into consideration air mass transport routes, δ"3"4S_n_s_s in the air masses which originated in the Asian continent and were transported over the Sea of Japan to the monitoring sites were higher than those values for air masses which were transported over the Japanese islands after leaving the Asian continent for each season. Considering that the δ"3"4S_n_s_s in sulfuric acid derived from domestic emissions in Japan are lower than those of δ"3"4S_n_s_s in coal, the lower δ"3"4S_n_s_s for the air mass transported over the Japanese islands suggest that sulfuric acid in PM2.5 modified the δ"3"4S_n_s_s due to aerosol mixing with sulfuric acid in Japan. Material balance calculations suggested that the relative contribution of transboundary transport in winter was also higher than for other seasons (40–75% in spring, 51–63% in summer, 45–73% in autumn, and 53–81% in winter). In particular, the contribution to the air masses which were transported directly from the Asian continent was relatively large (75% in spring, 59% in autumn, 78% in winter) in comparison with that for the air masses which were transported over Japan. - Highlights: • δ"3"4Snss in PM2.5 is effective to estimate contribution of anthropogenic sulfur. • δ"3"4Snss have characterized with seasonal variation with high values in winter. • The contribution of transboundary transport is 39-81% at the site facing to the Sea of Japan. • δ"3"4Snss in PM2.5 are modified during transport with mixing of domestic sources. • Map of δ"3"4S distribution originated from coal in Northeast Asia is developed.

Transboundary transport of anthropogenic sulfur in PM2.5 at a coastal site in the Sea of Japan as studied by sulfur isotopic ratio measurement

Energy Technology Data Exchange (ETDEWEB)

Inomata, Yayoi, E-mail: inomata@acap.asia [Asia Center for Air Pollution Research, 1182, Sowa, Niigata, Niigata 950-2144 (Japan); Ohizumi, Tsuyoshi [Asia Center for Air Pollution Research, 1182, Sowa, Niigata, Niigata 950-2144 (Japan); Niigata Prefectural Institute of Public Health and Environmental Sciences, 314-1, Sowa, Niigata, Niigata 950-2144 (Japan); Take, Naoko; Sato, Keiichi [Asia Center for Air Pollution Research, 1182, Sowa, Niigata, Niigata 950-2144 (Japan); Nishikawa, Masataka [National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba, Ibaraki 305-8506 (Japan); Tokyo University of Science, 12-1, Ichigaya Funakawara, Shinjuku, Tokyo 162-0826 (Japan)

2016-05-15

Sulfur isotopic ratios (δ{sup 34}S) in size separated aerosol particles (PM2.5 and coarse particles) were measured at Niigata-Maki facing the Sea of Japan. Non-sea salt δ{sup 34}S (δ{sup 34}S{sub nss}) in PM2.5 showed seasonal variations with relatively high values in winter (1.0–3.9‰ in spring, 2.8–4.5‰ in summer, 1.3–4.5‰ in autumn, 3.7–5.7‰ in winter). Taking into consideration air mass transport routes, δ{sup 34}S{sub nss} in the air masses which originated in the Asian continent and were transported over the Sea of Japan to the monitoring sites were higher than those values for air masses which were transported over the Japanese islands after leaving the Asian continent for each season. Considering that the δ{sup 34}S{sub nss} in sulfuric acid derived from domestic emissions in Japan are lower than those of δ{sup 34}S{sub nss} in coal, the lower δ{sup 34}S{sub nss} for the air mass transported over the Japanese islands suggest that sulfuric acid in PM2.5 modified the δ{sup 34}S{sub nss} due to aerosol mixing with sulfuric acid in Japan. Material balance calculations suggested that the relative contribution of transboundary transport in winter was also higher than for other seasons (40–75% in spring, 51–63% in summer, 45–73% in autumn, and 53–81% in winter). In particular, the contribution to the air masses which were transported directly from the Asian continent was relatively large (75% in spring, 59% in autumn, 78% in winter) in comparison with that for the air masses which were transported over Japan. - Highlights: • δ{sup 34}Snss in PM2.5 is effective to estimate contribution of anthropogenic sulfur. • δ{sup 34}Snss have characterized with seasonal variation with high values in winter. • The contribution of transboundary transport is 39-81% at the site facing to the Sea of Japan. • δ{sup 34}Snss in PM2.5 are modified during transport with mixing of domestic sources. • Map of δ{sup 34}S distribution originated

Stable isotope compositions of serpentinite seamounts in the Mariana forearc: Serpentinization processes, fluid sources and sulfur metasomatism

Science.gov (United States)

Alt, J.C.; Shanks, Wayne C.

2006-01-01

The Mariana and Izu-Bonin arcs in the western Pacific are characterized by serpentinite seamounts in the forearc that provide unique windows into the mantle wedge. We present stable isotope (O, H, S, and C) data for serpentinites from Conical seamount in the Mariana forearc and S isotope data for Torishima seamount in the Izu-Bonin forearc in order to understand the compositions of fluids and temperatures of serpentinization in the mantle wedge, and to investigate the transport of sulfur from the slab to the mantle wedge. Six serpentine mineral separates have a restricted range of ??18O (6.5-8.5???). Antigorite separates have ??D values of -29.5??? to -45.5??? that reflect serpentinization within the mantle wedge whereas chrysotile has low ??D values (-51.8??? to -84.0???) as the result of re-equilibration with fluids at low temperatures. Fractionation of oxygen isotopes between serpentine and magnetite indicate serpentinization temperatures of 300-375 ??C. Two late cross-fiber chrysotile veins have higher ??18O values of 8.9??? to 10.8??? and formed at lower temperatures (as low as ???100 ??C). Aqueous fluids in equilibrium with serpentine at 300-375 ??C had ??18O = 6.5-9??? and ??D = -4??? to -26???, consistent with sediment dehydration reactions at temperatures arc lavas. ?? 2006 Elsevier B.V. All rights reserved.

The precise measurement of TL isotopic compositions by MC-ICPMS: Application to the analysis of geological materials and meteorites.

Science.gov (United States)

Rehkämper, Mark; Halliday, Alex N.

1999-07-01

The precision of Tl isotopic measurements by thermal ionization mass spectrometry (TIMS) is severely limited by the fact that Tl possesses only two naturally occurring isotopes, such that there is no invariant isotope ratio that can be used to correct for instrumental mass discrimination. In this paper we describe new chemical and mass spectrometric techniques for the determination of Tl isotopic compositions at a level of precision hitherto unattained. Thallium is first separated from the geological matrix using a two-stage anion-exchange procedure. Thallium isotopic compositions are then determined by multiple-collector inductively coupled plasma-mass spectrometry with correction for mass discrimination using the known isotopic composition of Pb that is admixed to the sample solutions. With these procedures we achieve a precision of 0.01-0.02% for Tl isotope ratio measurements in geological samples and this is a factor of ≥3-4 better than the best published results by TIMS. However, without adequate precautions, experimental artifacts can be generated that result in apparent Tl isotopic fractionations of up to one per mil. Analysis of five terrestrial samples indicate the existence of Tl isotopic variations related to natural fractionation processes on the Earth. Two of the three igneous rocks analyzed in this study display Tl isotopic compositions indistinguishable from our laboratory standard, the reference material NIST-997 Tl. A third sample, however, is characterized by ɛ Tl ≈ 2.5 ± 1.5, where ɛ Tl represents the deviation of the 205Tl/ 203Tl ratio of the sample relative to NIST-997 Tl in parts per 10 4. Even larger deviations were identified for two ferromanganese crusts from the Pacific Ocean, which display ɛ Tl-values of +5.0 ± 1.5 and +11.7 ± 1.3. We suggest that the large variability of Tl isotopic compositions in the latter samples are caused by low-temperature processes related to the formation of the Fe-Mn crusts by precipitation and

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central Chile

DEFF Research Database (Denmark)

Zopfi, Jakob; Michael E., Böttcher; Jørgensen, Bo Barker

2008-01-01

suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition...... of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the bottom water composition due to intracellular isotope exchange reactions during microbial sulfur transformations....

Determination of sulfur isotopic composition for the study of iron sulfides origin, biotic or abiotic, in anoxic corrosion

International Nuclear Information System (INIS)

Grousset, Sophie

2016-01-01

The first goal of this project was to develop a methodology based on the study of the sulfur isotopic composition enabling the determination of iron sulfides origin, biotic or abiotic, within the corrosion products layers (CPL). Then, the aim was to apply this methodology to real corrosion systems in order to determine the mechanisms of iron sulfides formation. Sulfur isotopic analyses methodologies, adapted to micrometric iron sulfides layers observed in real corrosion systems, were developed in nanoSIMS and ToF-SIMS. The study of iron sulfides formed in anoxic carbonated medium with or without sulphate-reducing bacteria validated the use of these methods for the determination of iron sulfides origin. The application of these methods coupled with the precise characterization of irons sulfides formed in the real corrosion systems show two kind of corrosion pattern. In pattern 1, the iron sulfides are localized in the external part of the CPL. They result from the Fe 2+ migration from the metal surface to areas rich in biotic S 2- . In this pattern, corrosion rates are lower than 20 μm/year for laboratory systems, and lower than 5 μm/year for archaeological objects. In pattern 2, the large presence of conductive phases in the CPL results in the delocalization of electrons, and so a disequilibrium of the charges at the metal's surface. That leads to the migration of biotic S 2- in the CPL till the metal where they precipitate in iron sulphides. This pattern shows high corrosion rates (∼100 μm/an) that might be resulting from the accumulation of bio-corrosion and chloride corrosion mechanisms. (author) [fr

The investigation on physico-chemical conditions of sulfides and sulfates based on petrographic and sulfur - oxygen stable isotope studies from the Darreh-Zar porphyry copper deposit, Kerman

Directory of Open Access Journals (Sweden)

Anis Parsapoor

2014-04-01

Full Text Available The Darreh-Zar porphyry copper deposit, located in the Urumieh – Dokhtar magmatic belt, lies about 10 km southeast of Sar-Cheshmeh porphyry copper deposit. The ore body with hydrothermally altered zones including potassic, chlorite-sericite, sericite, argillic and propylitic all related to the Darreh-Zar porphyry stock intruded the Eocene volcanic rocks. Pyrite, chalcopyrite, molybdenite, with different textures as disseminated and veinlet, are the major sulfide minerals and chalcocite and covellite are considered as the secondary minerals. Sulfur isotopic composition of the sulfates and sulfides studied fall on the magmatic values. Two different origins may be suggested for the gypsums studied: 1- hydration of anhydrite and 2- oxidation of pyrite during supergene enrichment. The stable isotopic data calculated on couple minerals (pyrite-anhydrite point to the formation temperature of about 485-515οC for the fluids involved in mineralization. The fluid responsible for mineralization suggests magmatic sources for all sulfide phases and reduced aqueous sulfur species. Isotopic zoning, based on the δ34S pyrite values, divided the area into the east and the west parts with negative and positive correlation against the depth, respectively. Also, a negative correlation is observed between the Cu and the δ34S in the eastern portion of the area.

Stable Isotope Group 1982 progress report

International Nuclear Information System (INIS)

Stewart, M.K.

1983-06-01

The work of the Stable Isotope Group of the Institute of Nuclear Sciences during 1982, in the fields of isotope geology, isotope hydrology, geochronology, isotope biology and mass spectrometer instrumentation, is described

Applications of stable isotope tracers to air pollution problems

International Nuclear Information System (INIS)

Kelly, W.R.

1985-01-01

One of the fundamental environmental problems facing the United States is how to effect acid rain abatement in the northeast United States and southeastern Canada in a cost effective manner. There are several key scientific questions that must be addressed in order to design an effective strategy. These questions include the following: (1) where do pollutants from a specified source area go., (2) what chemical transformations occur during transport., and (3) where and how are these pollutants deposited. One approach to address these questions is the use of enriched stable isotopes as intentional tracers of aerosol and sulfur emissions. Isotopic tracers can determine the location and pathways of pollutants in the environment and trace pollutants back to their original source. For an element with n isotopes, it is possible to intentionally tag n-2 sources. (For example, Nd, which has seven isotopes, could be used to tag 5 different aerosol sources). To trace sulfur compounds, the two minor isotopes of sulfur, 33 S and 36 S, could be used. Methods developed at NBS using high precision mass spectrometry permits the detection of the small changes in isotopic composition brought about by the intentional tagging at a source. This may make possible the identification of a source at a particular sampling site

Isotopic and elemental chemistry of sedimentary pyrite: A combined analytical and statistical approach to a novel planetary biosignature

Science.gov (United States)

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

Stable Isotope Group 1983 progress report

International Nuclear Information System (INIS)

Stewart, M.K.

1984-06-01

The work of the Stable Isotope Group of the Institute of Nuclear Sciences in the fields of isotope geology, isotope hydrology, geochronology, isotope biology and related fields, and mass spectrometer instrumentation, during 1983, is described

Isotopic marking and tracers

International Nuclear Information System (INIS)

Morel, F.

1997-01-01

The use of radioactive isotopes as tracers in biology has been developed thanks to the economic generation of the required isotopes in accelerators and nuclear reactors, and to the multiple applications of tracers in the life domain; the most usual isotopes employed in biology are carbon, hydrogen, phosphorus and sulfur isotopes, because these elements are present in most of organic molecules. Most of the life science knowledge appears to be dependent to the extensive use of nuclear tools and radioactive tracers; the example of the utilization of radioactive phosphorus marked ATP to study the multiple reactions with proteins, nucleic acids, etc., is given

Compilation of the Dakota Aquifer Project isotope data and publications: The Isotope Hydrology Program of the Isotope Sciences Division

International Nuclear Information System (INIS)

Davisson, M.L.; Smith, D.K.; Hudson, G.B.; Niemeyer, S.; Macfarlane, P.A.; Whittemore, D.O.

1995-01-01

In FY92 the then Nuclear Chemistry Division embarked on a scientific collaboration with the Kansas Geological Survey (KGS) to characterize with isotope techniques groundwater of the Dakota Formation of Kansas. The Dakota Formation is a Cretaceous-aged marine sandstone hosting potable groundwater in most regions of Kansas whose use will serve to partially offset the severe overdraft problems in the overlying Ogallala Formation. The isotope characterization of the Dakota groundwater has generated data that delineates sources, ages, and subsurface controls on the water quality. Initial interpretations of the data have been published in abstract volumes of (1) the 1993 Geological Society of America National Meeting, (2) the 8th International Conference on Geochronology, Cosmochronology and Isotope Geology, and (3) the 1994 Dakota Aquifer Workshop and Clinic. Copies of all abstracts are included in this brief review. One report will focus on the sources and ages of the groundwater, and the other will focus on the subsurface controls on the natural water quality

Geological history of uranium

International Nuclear Information System (INIS)

Niini, Heikki

1989-01-01

Uranium is widely distributed in continental geological environments. The order of magnitude of uranium abundance in felsitic igneous rocks is 2-15 ppm, whereas it is less than 1 ppm in mafic rocks. Sedimentary rocks show a large range: from less than 0.1 ppm U in certain evaporites to over 100 ppm in phosphate rocks and organogenic matter. The content of U in seawater varies from 0.0005 to 0.005 ppm. The isotopic ratio U-238/U-235 is presently 137.5+-0.5, having gradually increased during geological time. The third natural isotope is U-234. On the basis of three fundamental economic criteria for ore reserves assessment (geological assurance, technical feasibility, and the grade and quantity of the deposits), the author finally comes to the following conclusions: Although the global uranium ores are not geologically renewable but continuously mined, they still, due to exploration and technical development, will tend to progressively increase for centuries to come

Geology, mineralogy and ore fluid characteristics of the Masjed Daghi gold bearing veins system, NW Iran

Directory of Open Access Journals (Sweden)

Susan Ebrahimi

2017-11-01

Full Text Available Introduction The Masjed- Daghi gold deposit lies in an area of widespread Cenozoic volcanic and plutonic rocks at the intersection of the Alborz- Azarbaijan and Urumieh- Dokhtar belts. The area was covered by a detailed exploration program, including geological maps at 1:1,000 scales (~8 km², several hundred meters of trenches and systematic sampling for Au, Ag, Pb, Zn, Cu, As, Hg analysis, and 16 diamond drill holes at a total of 1200 meters (Mohammadi et al, 2005. The vein type gold deposit in Masjed- Daghi is closely associated with a porphyry type Cu-Au deposit. Our study focuses on the gold bearing veins system in an attempt to understand the characteristics of ore fluids and mechanisms of ore formation, and to develop exploration criteria for Masjed Daghi and similar occurrences in Alborz and other Cenozoic magmatic assemblages in Iran. Materials and methods Various rock types, alteration assemblages and mineral parageneses were characterized by transmitting and reflected light microscopy, X-ray diffraction (XRD and electron microprobe analysis. Microprobe analyses were performed using a JEOL 8600 Superprobe electron microprobe at Saskatchewan University. Operating conditions were an accelerating voltage of 15 kV and a beam current of 50 nA. Representative samples from drill holes were selected for fluid inclusion studies. Fluid inclusion data were obtained using a fluid Inc. adapted USGS gas flow heating and freezing system at the Department of Geological Science at the University of Saskatchewan, Canada. To investigate the source of ore fluids, representative sulfidic samples from drill holes were selected for sulfur isotope studies. Isotopic analyses were performed using a Thermo Finnigan DeltaPlus at the G.G. Hatch Stable Isotope Laboratories, University of Ottawa. The standard error of analyses is less than ±0.1 per mil. Results Auriferous quartz veins in Masjed- Daghi are associated with porphyry style mineralization. Various

Trace uranium analysis in geological sample by isotope dilution-alpha spectrometry and comparison with other techniques

International Nuclear Information System (INIS)

Shihomatsu, H.M.; Iyer, S.S.

1988-12-01

Establishment of uranium determination in geological samples by alpha spectrometric isotope dilution technique using 233 U tracer is described in the present work. The various steps involved in the method namely, preparation of the sample, electrodeposition, alpha spectrometry, isotope dilution, calculation of the concentration and error statistics are discussed in detail. The experimental parameters for the electrodeposition of uranium, like current density, pH concentration of the electrolyte solution, deposition time, electrode distance were all optimised based on the efficiency of the deposition. The total accuracy and precision of the IDAS using 233 U tracer in the determination of uranium in mineral and granite samples were of the order of 1 to 2% for the concentration range of 50-1500 ppm of U. Our results are compared with those obtained by others workers using similar and different techniques. (author) [pt

The influence of sulfur and hair growth on stable isotope diet estimates for grizzly bears.

Directory of Open Access Journals (Sweden)

Garth Mowat

Full Text Available Stable isotope ratios of grizzly bear (Ursus arctos guard hair collected from bears on the lower Stikine River, British Columbia (BC were analyzed to: 1 test whether measuring δ34S values improved the precision of the salmon (Oncorhynchus spp. diet fraction estimate relative to δ15N as is conventionally done, 2 investigate whether measuring δ34S values improves the separation of diet contributions of moose (Alces alces, marmot (Marmota caligata, and mountain goat (Oreamnos americanus and, 3 examine the relationship between collection date and length of hair and stable isotope values. Variation in isotope signatures among hair samples from the same bear and year were not trivial. The addition of δ34S values to mixing models used to estimate diet fractions generated small improvement in the precision of salmon and terrestrial prey diet fractions. Although the δ34S value for salmon is precise and appears general among species and areas, sulfur ratios were strongly correlated with nitrogen ratios and therefore added little new information to the mixing model regarding the consumption of salmon. Mean δ34S values for the three terrestrial herbivores of interest were similar and imprecise, so these data also added little new information to the mixing model. The addition of sulfur data did confirm that at least some bears in this system ate marmots during summer and fall. We show that there are bears with short hair that assimilate >20% salmon in their diet and bears with longer hair that eat no salmon living within a few kilometers of one another in a coastal ecosystem. Grizzly bears are thought to re-grow hair between June and October however our analysis of sectioned hair suggested at least some hairs begin growing in July or August, not June and, that hair of wild bears may grow faster than observed in captive bears. Our hair samples may have been from the year of sampling or the previous year because samples were collected in summer when

The influence of sulfur and hair growth on stable isotope diet estimates for grizzly bears.

Science.gov (United States)

Mowat, Garth; Curtis, P Jeff; Lafferty, Diana J R

2017-01-01

Stable isotope ratios of grizzly bear (Ursus arctos) guard hair collected from bears on the lower Stikine River, British Columbia (BC) were analyzed to: 1) test whether measuring δ34S values improved the precision of the salmon (Oncorhynchus spp.) diet fraction estimate relative to δ15N as is conventionally done, 2) investigate whether measuring δ34S values improves the separation of diet contributions of moose (Alces alces), marmot (Marmota caligata), and mountain goat (Oreamnos americanus) and, 3) examine the relationship between collection date and length of hair and stable isotope values. Variation in isotope signatures among hair samples from the same bear and year were not trivial. The addition of δ34S values to mixing models used to estimate diet fractions generated small improvement in the precision of salmon and terrestrial prey diet fractions. Although the δ34S value for salmon is precise and appears general among species and areas, sulfur ratios were strongly correlated with nitrogen ratios and therefore added little new information to the mixing model regarding the consumption of salmon. Mean δ34S values for the three terrestrial herbivores of interest were similar and imprecise, so these data also added little new information to the mixing model. The addition of sulfur data did confirm that at least some bears in this system ate marmots during summer and fall. We show that there are bears with short hair that assimilate >20% salmon in their diet and bears with longer hair that eat no salmon living within a few kilometers of one another in a coastal ecosystem. Grizzly bears are thought to re-grow hair between June and October however our analysis of sectioned hair suggested at least some hairs begin growing in July or August, not June and, that hair of wild bears may grow faster than observed in captive bears. Our hair samples may have been from the year of sampling or the previous year because samples were collected in summer when bears were

Carbon-13 kinetic isotope effects in the decarbonylations of lactic acid containing 13C at the natural abundance level

International Nuclear Information System (INIS)

Zielinski, M.; Czarnota, G.; Papiernik-Zielinska, H.

1992-01-01

The 13 C kinetic isotope fractionation in the decarbonylation of lactic acid of natural isotopic composition by sulfuric acid has been studied in the temperature range of 20-80 deg C. The 13 C (1) isotope separation in the decarbonylation of lactic acid by concentrated sulfuric acid depends strongly on the temperature above 40 deg C. Below this temperature the 13 C isotope effect in the decarbonylation of lactic acid by concentrated sulfuric acid is normal similarly as has been found in the decarbonylation of lactic [1- 14 C] acid. The experimental values of k (12C) /k (13C) ratios of isotopic rate constants for 12 C and 13 C are close to, but slightly higher than theoretical 13 C-kinetic isotope effects calculated (neglecting tunneling) under the asumption that the C (1) -OH bond is broken in the rate-controlling step of the dehydration reaction. Dilution of concentrated sulfuric acid with water up to 1.4 molar (H 2 O)/(H 2 SO 4 ) ratio caused the increase of the 13 C isotope fractionation from 1.0273 found in concentrated sulfuric acid at 80.5 deg C to 1.0536±0.0008 (at 80.6 deg C). A discussion of the abnormally high temperature dependence of 14 C and 13 C isotope fractionation in this reaction and the discussion of the problem of relative 14 C/ 13 C kinetic isotope effects is given. (author) 18 refs.; 2 tabs

Serpentinization of abyssal peridotites from the MARK area, Mid-Atlantic Ridge: Sulfur geochemistry and reaction modeling

Science.gov (United States)

Alt, J.C.; Shanks, Wayne C.

2003-01-01

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated ??34Ssulfide (3.7 to 12.7???). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400??C alone cannot account for both the high sulfur contents and high ??34Ssulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (???400??C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ???300??C. Serpentinization produces highly reducing conditions and significant amounts of H2 and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in 13C (up to 4.5???) at temperatures above 250??C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 ?? 1012 g seawater S yr-1. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates. ?? 2003 Elsevier Science Ltd.

Platinum stable isotope analysis of geological standard reference materials by double-spike MC-ICPMS.

Science.gov (United States)

Creech, J B; Baker, J A; Handler, M R; Bizzarro, M

2014-01-10

We report a method for the chemical purification of Pt from geological materials by ion-exchange chromatography for subsequent Pt stable isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) using a 196 Pt- 198 Pt double-spike to correct for instrumental mass bias. Double-spiking of samples was carried out prior to digestion and chemical separation to correct for any mass-dependent fractionation that may occur due to incomplete recovery of Pt. Samples were digested using a NiS fire assay method, which pre-concentrates Pt into a metallic bead that is readily dissolved in acid in preparation for anion-exchange chemistry. Pt was recovered from anion-exchange resin in concentrated HNO 3 acid after elution of matrix elements, including the other platinum group elements (PGE), in dilute HCl and HNO 3 acids. The separation method has been calibrated using a precious metal standard solution doped with a range of synthetic matrices and results in Pt yields of ≥90% with purity of ≥95%. Using this chemical separation technique, we have separated Pt from 11 international geological standard reference materials comprising of PGE ores, mantle rocks, igneous rocks and one sample from the Cretaceous-Paleogene boundary layer. Pt concentrations in these samples range from ca. 5 ng g -1 to 4 μg g -1 . This analytical method has been shown to have an external reproducibility on δ 198 Pt (permil difference in the 198 Pt/ 194 Pt ratio from the IRMM-010 standard) of ±0.040 (2 sd) on Pt solution standards (Creech et al., 2013, J. Anal. At. Spectrom. 28, 853-865). The reproducibility in natural samples is evaluated by processing multiple replicates of four standard reference materials, and is conservatively taken to be ca. ±0.088 (2 sd). Pt stable isotope data for the full set of reference materials have a range of δ 198 Pt values with offsets of up to 0.4‰ from the IRMM-010 standard, which are readily resolved with this technique. These

Measurement of in situ sulfur isotopes by laser ablation multi-collector ICPMS: opening Pandora’s Box

Science.gov (United States)

Ridley, William I.; Pribil, Michael; Koenig, Alan E.; Slack, John F.

2015-01-01

Laser ablation multi-collector ICPMS is a modern tool for in situ measurement of S isotopes. Advantages of the technique are speed of analysis and relatively minor matrix effects combined with spatial resolution sufficient for many applications. The main disadvantage is a more destructive sampling mechanism relative to the ion microprobe technique. Recent advances in instrumentation allow precise measurement with spatial resolutions down to 25 microns. We describe specific examples from economic geology where increased spatial resolution has greatly expanded insights into the sources and evolution of fluids that cause mineralization and illuminated genetic relations between individual deposits in single mineral districts.

Sulfur (32S, 33S, 34S, 36S) and oxygen (16O, 17O, 18O) isotopi primary sulfate produced from combustion processes

International Nuclear Information System (INIS)

Lee, C.C.W.; Savarino, J.; Thiemens, M.H.; Cachier, H.

2002-01-01

The recent discovery of an anomalous enrichment in 17 O isotope in atmospheric sulfate has opened a new way to investigate the oxidation pathways of sulfur in the atmosphere. From laboratory investigations, it has been suggested that the wet oxidation of sulfur in rain droplets was responsible for the excess 17 O. In order to confirm this theory, sulfur and oxygen isotope ratios of different primary sulfates produced during fossil fuel combustion have been investigated and are reported. None of these samples exhibits any anomalous oxygen or sulfur isotopic content, as compared to urban sulfate aerosols. These results, in agreement with the laboratory investigations, reinforce the idea of an aqueous origin for the oxygen-17 anomaly found in tropospheric sulfates

Chemical and isotopic characteristics of the warm and cold waters of the Luigiane Spa near Guardia Piemontese (Calabria, Italy) in a complex faulted geological framework

International Nuclear Information System (INIS)

Vespasiano, Giovanni; Apollaro, Carmine; Muto, Francesco; Dotsika, Elissavet; De Rosa, Rosanna; Marini, Luigi

2014-01-01

upflow and limited cooling. The upward part of both hydrogeological circuits is controlled by local low- and high-angle fault systems as well as by the tectonic window of Guardia Piemontese, where the Verbicaro Unit crops out and the Cetraro Unit approaches the surface. The reconstruction of this conceptual model has been made possible thanks to the adoption of a “local” approach integrating previously existing and new geological, hydrogeological and geochemical data and including the use of sulfur isotope data. This last technique has proven most important, as it enabled us to recognize the Upper Triassic fingerprint of dissolved sulfate, once the effects of bacterial sulfate reduction had been properly taken into account

Earth's Coming of Age: Isotopically Tracking the Global Transformation from the Hadean to the Geologically Modern Earth

Science.gov (United States)

Bennett, V. C.; Nutman, A. P.

2017-12-01

Some of the strongest direct evidence that documents fundamental changes in the chemistry and organisation of Earth's interior derives from radiogenic isotopic compositions that include both long-lived (particularly 176Lu-176Hf and 147Sm-143Nd) and short-lived, i.e., now extinct parent isotope, systems (182Hf-182W, 146Sm-142Nd). Changes in patterns of isotopic evolution are linked to changes in mantle dynamics such that tracking these signatures in geologically well-characterised rocks can be used to discover the the nature and evolution of tectonic processes. Over the past decade, intensive geochemical investigations by various groups focussing on the oldest (> 4.0 Ga to 3.6 Ga) rock record, as preserved in several localities, have revealed isotopic distinctions in the early Earth compared with those in Proterozoic and younger rocks. For example, whilst the major and trace element compositions of Eoarchean gneisses have analogs in younger rocks in accord with a continuum of crust formation processes, radiogenic isotopic signatures from both long and short half-life decay schemes record an image of the Earth in transition from early differentiation processes, likely associated with planetary accretion and formation, to more modern style characterised by plate tectonics. The emerging image is that many Eoarchean rocks possess extinct nuclide anomalies in the form of 142Nd and 182Hf isotopic signatures that are absent in modern terrestrial samples; these signatures are evidence of chemical fractionation processes occuring within the first ca. 10-300 million years of Solar System history. In addition, viewing the global database, patterns of long-half life isotope signatures i.e., 143Nd and 176Hf differ from those seen in younger (modern Earth.

Stable isotope fractionation during bacterial sulfate reduction is controlled by reoxidation of intermediates

Science.gov (United States)

Mangalo, Muna; Meckenstock, Rainer U.; Stichler, Willibald; Einsiedl, Florian

2007-09-01

Bacterial sulfate reduction is one of the most important respiration processes in anoxic habitats and is often assessed by analyzing the results of stable isotope fractionation. However, stable isotope fractionation is supposed to be influenced by the reduction rate and other parameters, such as temperature. We studied here the mechanistic basics of observed differences in stable isotope fractionation during bacterial sulfate reduction. Batch experiments with four sulfate-reducing strains ( Desulfovibrio desulfuricans, Desulfobacca acetoxidans, Desulfonatronovibrio hydrogenovorans, and strain TRM1) were performed. These microorganisms metabolize different carbon sources (lactate, acetate, formate, and toluene) and showed broad variations in their sulfur isotope enrichment factors. We performed a series of experiments on isotope exchange of 18O between residual sulfate and ambient water. Batch experiments were conducted with 18O-enriched (δ 18O water = +700‰) and depleted water (δ 18O water = -40‰), respectively, and the stable 18O isotope shift in the residual sulfate was followed. For Desulfovibrio desulfuricans and Desulfonatronovibrio hydrogenovorans, which are both characterized by low sulfur isotope fractionation ( ɛS > -13.2‰), δ 18O values in the remaining sulfate increased by only 50‰ during growth when 18O-enriched water was used for the growth medium. In contrast, with Desulfobacca acetoxidans and strain TRM1 ( ɛS factor ( ɛS exchange with water during sulfate reduction. However, this neither takes place in the sulfate itself nor during formation of APS (adenosine-5'-phosphosulfate), but rather in intermediates of the sulfate reduction pathway. These may in turn be partially reoxidized to form sulfate. This reoxidation leads to an incorporation of oxygen from water into the "recycled" sulfate changing the overall 18O isotopic composition of the remaining sulfate fraction. Our study shows that such incorporation of 18O is correlated with the

Anaerobic methane oxidation and a deep H2S sink generate isotopically heavy sulfides in Black Sea sediments

DEFF Research Database (Denmark)

Jørgensen, BB; Bottcher, ME; Luschen, H.

2004-01-01

to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth's history. Copyright (C) 2004 Elsevier Ltd...

Use of isotopic sulfur to determine whitebark pine consumption by Yellowstone bears: a reassessment

Science.gov (United States)

Schwartz, Charles C.; Teisberg, Justin E.; Fortin, Jennifer K.; Haroldson, Mark A.; Servheen, Christopher; Robbins, Charles T.; van Manen, Frank T.

2014-01-01

Use of naturally occurring stable isotopes to estimate assimilated diet of bears is one of the single greatest breakthroughs in nutritional ecology during the past 20 years. Previous research in the Greater Yellowstone Ecosystem (GYE), USA, established a positive relationship between the stable isotope of sulfur (δ34S) and consumption of whitebark pine (Pinus albicaulis) seeds. That work combined a limited sample of hair, blood clots, and serum. Here we use a much larger sample to reassess those findings. We contrasted δ34S values in spring hair and serum with abundance of seeds of whitebark pine in samples collected from grizzly (Ursus arctos) and American black bears (U. americanus) in the GYE during 2000–2010. Although we found a positive relationship between δ34S values in spring hair and pine seed abundance for grizzly bears, the coefficients of determination were small (R2 ≤ 0.097); we failed to find a similar relationship with black bears. Values of δ34S in spring hair were larger in black bears and δ34S values in serum of grizzly bears were lowest in September and October, a time when we expect δ34S to peak if whitebark pine seeds were the sole source of high δ34S. The relationship between δ34S in bear tissue and the consumption of whitebark pine seeds, as originally reported, may not be as clean a method as proposed. Data we present here suggest other foods have high values of δ34S, and there is spatial heterogeneity affecting the δ34S values in whitebark pine, which must be addressed.

Isotope determination of sulfur by mass spectrometry in soil samples

Directory of Open Access Journals (Sweden)

Alexssandra Luiza Rodrigues Molina Rossete

2012-12-01

Full Text Available Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-, which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2- concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms was carried out by isotope ratio mass spectrometry (IRMS. In this work, the labeled material (K2(34SO4 was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.

Influence of the enzyme dissimilatory sulfite reductase on stable isotope fractionation during sulfate reduction

Science.gov (United States)

Mangalo, Muna; Einsiedl, Florian; Meckenstock, Rainer U.; Stichler, Willibald

2008-03-01

The stable isotopes of sulfate are often used as a tool to assess bacterial sulfate reduction on the macro scale. However, the mechanisms of stable isotope fractionation of sulfur and oxygen at the enzymatic level are not yet fully understood. In batch experiments with water enriched in 18O we investigated the effect of different nitrite concentrations on sulfur isotope fractionation by Desulfovibrio desulfuricans. With increasing nitrite concentrations, we found sulfur isotope enrichment factors ranging from -11.2 ± 1.8‰ to -22.5 ± 3.2‰. Furthermore, the δ18O values in the remaining sulfate increased from approximately 50-120‰ when 18O-enriched water was supplied. Since 18O-exchange with ambient water does not take place in sulfate, but rather in intermediates of the sulfate reduction pathway (e.g. SO32-), we suggest that nitrite affects the steady-state concentration and the extent of reoxidation of the metabolic intermediate sulfite to sulfate during sulfate reduction. Given that nitrite is known to inhibit the production of the enzyme dissimilatory sulfite reductase, our results suggest that the activity of the dissimilatory sulfite reductase regulates the kinetic isotope fractionation of sulfur and oxygen during bacterial sulfate reduction. Our novel results also imply that isotope fractionation during bacterial sulfate reduction strongly depends on the cell internal enzymatic regulation rather than on the physico-chemical features of the individual enzymes.

The Chicxulub event - sulfur-bearing minerals and lithologies

Science.gov (United States)

Strauss, H.; Deutsch, A.

2003-04-01

Evaporates form a major target lithology at the Chicxulub impact site. One of the postulated effects of the impact event at the Cretaceous/Tertiary boundary is the impact-induced dissociation of anhydrite to form sulfur-oxides and a solid residue; large isotope fractionation effects in sulfur should accompany this process. We have analyzed the sulfur isotope composition of (i) annealed anhydrite clasts in impact melt breccias of PEMEX core Yucatan-6 N 19, (ii) unshocked anhydrite from the CSDP well Yaxcopoil-1, which belong to the megabreccia below the suevite layer (YAX-1 1369, and 1376 m depth), and (iii) sulfide grains of hydrothermal origin in a finest-grained breccia, which transects a large limestone block of this megabreccia at a depth of 1369 m. Samples of groups (i) and (ii) yielded δ34S values between 18.0 and 19.8 ppm CDT (unweighted mean is 18.3 ppm, n=7), with one slightly lower value of 15.3 ppm for an anhydrite clast in Y-6 N19/Part 6. These data are in agreement with the δ34S value for the Late Cretaceous seawater (Strauss 1999). The δ34S obviously remained unchanged despite the fact that textural features indicate a severe annealing of the clasts in the impact melt. Sulfides of group (iii) show δ34S values around 41 ppm CDT (n=7), which are quite unusual values if these minerals are of non-biogenic origin. In contrast, δ34S for the yellow glass from the K/T boundary at Haiti range from 1.5 to 13.2 ppm (Chaussidon et al. 1996). Using this preliminary evidence, we conclude that only distant ejecta lithologies, and probably secondary material inside the crater, may display impact-related fractionation of sulfur isotopes. This observation is consistent with petrologic data, modeling results as well as of shock recovery and annealing experiments: anhydrite obviously is quite resistant to shock-related dissociation.

Volcanogenic Sulfur on Earth and Io: Composition and Spectroscopy

Science.gov (United States)

Kargel, J.S.; Delmelle, P.; Nash, D.B.

1999-01-01

The causes of Io's variegated surface, especially the roles of sulfur, and the geochemical history of sulfur compounds on Io are not well understood. Suspecting that minor impurities in sulfur might be important, we have investigated the major and trace element chemistry and spectroscopic reflectance of natural sulfur from a variety of terrestrial volcanic-hydrothermal environments. Evidence suggests that Io may be substantially coated with impure sulfur. On Earth, a few tenths of a percent to a few percent of chalcophile trace elements (e.g., As and Se) comonly occur in sulfur and appear to stabilize material of yellow, brown, orange, and red hues, which may persist even at low temperatures. Percentage levels of chalcophile impurities are reasonably expected to occur on Io in vapor sublimate deposits and flows derived from such deposits. Such impurities join a host of other mechanisms that might explain Io's reds and yellows. Two-tenths to two percent opaque crystalline impurities, particularly pyrite (FeS2), commonly produces green, gray, and black volcanic sulfur on Earth and might explain areas of Io having deposits of these colors. Pyrite produces a broad absorption near 1 ??m that gradually diminishes out to 1.6 ??m - similar but not identical to the spectrum of Io seen in Galileo NIMS data. Percentage amounts of carbonaceous impurities and tens of percent SiO2 (as silicates) also strongly affect the spectral properties of Earth's sulfur. Io's broad absorption between 0.52 and 0.64 ??m remains unexplained by these data but could be due to sodium sulfides, as suggested previously by others, or to As, Se, or other impurities. These impurities and others, such as P and Cl (which could exist on Io's surface in amounts over 1% that of sulfur), greatly alter the molecular structure of molten and solid sulfur. Minor impurities could impact Io's geology, such as the morphology of sulfur lava flows and the ability of sulfur to sustain high relief. We have not found

Quantification of Sulfur by the Wet Oxidation for the Determination of 35S

International Nuclear Information System (INIS)

Lee, Heung N.; Kang, Sang Hoon; Ahn, Hong Joo; Han, Sun Ho; Jee, Kwang Yong

2006-01-01

Natural sulfur contains four stable isotopes. The main isotopes are 32 S (95.02%) and 34 S (4.21%). Beside the stable isotopes, there exist also a radioactive one 35 S (T 1/2 = 87.4 d, Emax = 167 keV, pure β - emitter). Sulfur- 35 is one of the cosmogenic radionuclides generated by cosmic rays through spallation of argon atoms. 35 S for the labeled compound such as 35 S-thiourea is produced from the pile irradiation of the neutron ( 35 Cl(n,p) 35 S). Most 35 S produced by cosmic rays is rapidly converted to sulfur dioxide (SO 2 ) and sulfate (SO 4 2- ), and attached on the ambient aerosols. The quantities of 35 S do not present a significant external exposure hazard since the low-energy emissions barely penetrate the outer dead layer of skin. For uptakes of inorganic sulfur, 15% is assumed to be retained with a 20 day biological half-life and 5% retained with a 2,000 day biological half-life. The remaining 80% is assumed to be rapidly excreted. Because of its relatively weak emission, 35 S is primarily an internal radiation hazard. TLDs are not effective and Geiger-Muller detectors can measure to low efficiency (∼10%) for detecting 35 S. Therefore, it is important to use careful handling and frequent monitoring, either with survey meters with thin- windows probes or by taking wipe samples and counting in a liquid scintillation counter (LSC)

Nd and Sr isotopes: implications of provenance and geological mapping; Isotopos de Nd e Sr: implicacoes de proveniencia e mapeamento geologico

Energy Technology Data Exchange (ETDEWEB)

Albuquerque, Marcio Fernando dos Santos; Horbe, Adriana Maria Coimbra; Dantas, Elton Luiz, E-mail: mgeoroots@gmail.com, E-mail: ahorbe@unb.br, E-mail: elton@unb.br [Universidade de Brasilia (UnB), DF (Brazil). Instituto de Geociencias

2015-07-01

XRD, Nd and Sr isotopes, major, minor and traces elements quantification were applied to rocks, lateritic crusts and soils from Sumauma Supergroup and Alto Tapajos Group, in order to indicate provenance of the rocks and using lateritic products as geologic mapping tool. For the rocks, the results showed sources related to provinces Tapajos Parima, Rondonia Juruena, Sunsas, Carajas and Amazonia Central. However, the incision of Cachimbo graben allowed which the Sumauma Supergroup erosion also were source for the Alto Tapajos Group, allied to contribution of volcanics from Colider Group. Lateritic crusts and soils are correlates to bedrocks, allowing the use as geologic mapping tool. (author)

Isotope ratio analysis by a combination of element analyzer and mass spectrometer

International Nuclear Information System (INIS)

Pichlmayer, F.

1987-06-01

The use of stable isotope ratios of carbon, nitrogen and sulfur as analytical tool in many fields of research is of growing interest. A method has therefore been developed, consisting in essential of coupling an Elemental Analyzer with an Isotope Mass Spectrometer, which enables the gas preparation of carbon dioxide, nitrogen and sulfur dioxide from any solid or liquid sample in a fast and easy way. Results of carbon isotope measurements in food analysis are presented, whereat it is possible to check origin and treatment of sugar, oils, fats, mineral waters, spirituous liquors etc. and to detect adulterations as well. Also applications in the field of environmental research are given. (Author)

Sulfur and carbon isotope biogeochemistry of a rewetted brackish fen

Science.gov (United States)

Koebsch, Franziska; Gehre, Matthias; Winkel, Matthias; Koehler, Stefan; Koch, Marian; Jurasinski, Gerald; Spitzy, Alejandro; Liebner, Susanne; Sachs, Torsten; Schmiedinger, Iris; Kretzschmann, Lisett; Saborowski, Anke; Böttcher, Michael E.

2015-04-01

Sea coast line exhibited a significant excess of sulfate. Preliminary sulfur isotope analysis of pore water sulfate from a location nearest to this profile revealed an enrichment in 34S (24.9 to 41.8o ) in comparison to Baltic Sea sulfate (21o ). This confirms high degrees of net sulfate reduction. Considering the yet high sulfate concentrations we hypothesize that local processes might supply additional sulfate and that the sulfide produced from sulfate reduction might either be lost by upwards diffusion towards the atmosphere or converted into other S compounds such as pyrite or organic compounds. The isotopic signatures of methane (δ13C: -68 to -57o and δ2H: -133 to -157o respectively) indicated acetoclastic methanogenesis to be the most dominant methane production pathway. However, estimated fractionation factors are comparatively high (1.050-1.065). Enrichment of heavy 13C in methane at the top of the sediment was either caused by methane oxidation or variation in substrate availability (e. g. due to peat degradation). The interpretation of our data in the light of further results will provide deeper insights into metabolic pathways and possible interactions between both coupled element cycles for coastal ecosystems.

Determination of marble provenance: limits of isotopic analysis

International Nuclear Information System (INIS)

Germann, K.; Holzmann, G.; Winkler, F.J.

1980-01-01

Provenance determination of Thessalian stelae marbles using the C/O isotopic analysis proved to be misleading, as the isotopic composition even in very small quarrying areas is heterogeneous and isotopic coincidence of marbles from very distant sources occurs. Therefore additional geological features must be taken into consideration and preference should be given to combinations of both petrographical and geochemical properties. Geological field work to establish the range of possible marble sources and the variability within these sources is one of the prerequisites of provenance studies. (author)

Isotope characterisation of historical alabaster quarries in Western Europe.

Science.gov (United States)

Kloppmann, Wolfram; Leroux, Lise; Bromblet, Philippe; Cooper, Anthony H.; Nestler, Angela; Guerrot, Catherine; Montech, Anne-Thérèse; Worley, Noel

2015-04-01

ranging from the 14th to 16th century from the Louvre Museum, Cleveland Museum of Fine Arts, the Petit Palais Museum in Avignon and several regional collections and monuments. Burke W. H., Denison R. E., Hetherington E. A., Koepnick R. B., Nelson H. F., and Otto J. B. (1982) Variation of seawater 87Sr/86Sr throughout Phanerozoic time. Geology 10, 516-519. Claypool G. E., Holser W. T., Kaplan I. R., Sakai H., and Zak I. (1980) The age curves of sulfur and oxygen isotopes in marine sulfate and their mutual interpretation. Chem. Geol. 28, 199-260. Denison R. E., Kirkland D. W., and Evans R. (1998) Using strontium isotopes to determine the age and origin of gypsum and anhydrite beds. J. Geol. 106, 1-17. Kloppmann W., Leroux L., Bromblet P., Guerrot C., Proust E., Cooper A. H., Worley N., Smeds S. A., and Bengtsson H. (2014) Tracing Medieval and Renaissance Alabaster Works of Art Back to Quarries: A Multi-Isotope (Sr, S, O) Approach. Archaeometry 56, 203-219.

Systematic sulfur stable isotope and fluid inclusion studies on veinlet groups in the Sarcheshmeh porphyry copper deposit: based on new data

Directory of Open Access Journals (Sweden)

Mohammad Maanijou

2012-10-01

Full Text Available Mineralization occurred by intrusion of granodioritic stock of middle Miocene in volcano–sedimenrary rocks in Sarcheshmeh of early Tertiary age. This research is based on samples of new drilled boreholes and benches of 2500m elevation. Based on mineralogy and crosscutting relationships, at least four groups of veinlets pertaining to four stages of mineralization were recognized. Sulfur isotope studies in the Sarcheshmeh porphyry copper deposit were conducted on pyrite, chalcopyrite, molybdenite and anhydrites of four groups of veinlets. The δ34S values in the sulfides and sulfates range from -2.2 to 1.27‰ and from 10.2 to 14.5 ‰, respectively. The average δ34S value in the sulfides is 1‰ and that for the sulfates is about 13‰. Considering these results, it can be concluded that the sulfides made up of a fluid that its sulfur has a magmatic origin. Also, fluid inclusions of different veinlet groups were studied, showing high temperature, high salinity and the occurrence of boiling in the mineralizing fluids. Moreover, these studies indicate presence of three types of fluids including magmatic, meteoritic and mixture of these two fluids in alteration and mineralizion processes.

Stable isotope studies. Progress report, August 1, 1974--July 31, 1975

International Nuclear Information System (INIS)

Flynn, G.W.; Hsu, D.S.Y.; Preses, J.M.; Spindel, W.; Weston, R.E.

1975-01-01

Progress is reported in the following studies: selective two-step laser-induced photodissociation, unimolecular processes induced by multiple-photon absorption, and vibrational energy transfer processes involving isotopic species of sulfur dioxide. These laser-induced chemical reactions can possibly be applied to isotope separation

Stable isotope geochemistry. 3. rev. and enl. ed.

International Nuclear Information System (INIS)

Hoefs, J.

1987-01-01

Stable Isotope Geochemistry is an authoritative book comprising theoretical and experimental principles; surveying important fractionation mechanisms affecting the most important elements; discussing the natural variations of geologically important reservoirs. This updated 3rd edition, with a completely rewritten and extended main part, contains two new chapters on stable isotope composition of mantle material and on changes of the ocean during the geological past. (orig.)

Sulfur in zircons: A new window into melt chemistry

Science.gov (United States)

Tang, H.; Bell, E. A.; Boehnke, P.; Barboni, M.; Harrison, T. M.

2017-12-01

The abundance and isotopic composition of sulfur are important tools for exploring the photochemistry of the atmosphere, the thermal history of mantle and igneous rocks, and ancient metabolic processes on the early Earth. Because the oldest terrestrial samples are zircons, we developed a new in-situ procedure to analyze the sulfur content of zircons using the CAMECA ims 1290 at UCLA. We analyzed zircons from three metaluminous/I-type granites (reduced and oxidized Peninsular range and Elba), which exhibit low sulfur abundance with the average of 0.5ppm, and one peraluminous/S-type zircon (Strathbogie Range), which shows an elevated sulfur level with the average of 1.5ppm. Additionally, we found that sulfur content ranges between 0.4 and 2.3 ppm in young volcanic zircons (St. Lucia). Our analyses of zircons from the Jack Hills, Western Australia, whose ages range between 3.4 and 4.1 Ga, show a variety of sulfur contents. Three out of the ten zircons are consistent with the sulfur contents of S-type zircons; the rest have low sulfur contents, which are similar to those of I-type zircons. The high sulfur content in some of these Jack Hills zircons can be interpreted as indicating their origin in either a S-type granite or a volcanic reservoir. We favor the former interpretation since the Ti-in-zircon temperatures of our Jack Hills zircons is lower than those of volcanic zircons. Future work will be undertaken to develop a systematic understanding of the relationship between melt volatile content, melt chemistry, and zircon sulfur content.

Isotopes in day to day life

Science.gov (United States)

1984-06-01

Developments are reported in the use of isotopic labeling and isotope irradiation in agriculture, medical science, hydrology, geochemistry, geophysics, environment pollution detection, and industries. Radioisotope instruments are described as well as techniques for gamma radiography, neutron radiography, and autoradiography. Isotope dating in geology and archaeology is covered. Basic scientific research topics in various areas are listed.

Stable carbon, nitrogen and sulfur isotopes in non-carbonate fractions of cold-seep carbonates

Science.gov (United States)

Feng, Dong; Peng, Yongbo; Peckmann, Jörn; Roberts, Harry; Chen, Duofu

2017-04-01

Sulfate-driven anaerobic oxidation of methane (AOM) supports chemosynthesis-based communities and limits the release of methane from marine sediments. This process promotes the formation of carbonates close to the seafloor along continental margins. The geochemical characteristics of the carbonate minerals of these rocks are increasingly understood, questions remain about the geochemical characteristics of the non-carbonate fractions. Here, we report stable carbon, nitrogen and sulfur isotope patterns in non-carbonate fractions of seep carbonates. The authigenic carbonates were collected from three modern seep provinces (Black Sea, Gulf of Mexico, and South China Sea) and three ancient seep deposits (Marmorito, northern Italy, Miocene; SR4 deposit of the Lincoln Creek Formation and Whiskey Creek, western Washington, USA, Eocene to Oligocene). The δ13C values of non-carbonate fractions range from ˜-25‰ to -80‰ VPDB. These values indicate that fossil methane mixed with varying amounts of pelagic organic matter is the dominant source of carbon in these fractions. The relatively small offset between the δ34S signatures of the non-carbonate fractions and the respective sulfide minerals suggests that locally produced hydrogen sulfide is the main source of sulfur in seep environments. The δ15N values of the non-carbonate fractions are generally lower than the corresponding values of deep-sea sediments, suggesting that organic nitrogen is mostly of a local origin. This study reveals the potential of using δ13C, δ15N, δ34S values to discern seep and non-seep deposits. In cases where δ13Ccarbonate values are only moderately low due to mixing processes and lipid biomarkers have been erased in the course of burial, it is difficult to trace back AOM owing to the lack of other records. This problem is even more pronounced when authigenic carbonate is not available in ancient seep environments. Acknowledgments: The authors thank BOEM and NOAA for their years' support

Mineralogical, textural, sulfur and lead isotope constraints on the origin of Ag-Pb-Zn mineralization at Bianjiadayuan, Inner Mongolia, NE China

Science.gov (United States)

Zhai, Degao; Liu, Jiajun; Cook, Nigel J.; Wang, Xilong; Yang, Yongqiang; Zhang, Anli; Jiao, Yingchun

2018-04-01

The Bianjiadayuan Ag-Pb-Zn deposit (4.81 Mt. @157.4 g/t Ag and 3.94% Pb + Zn) is located in the Great Hinggan Range Pb-Zn-Ag-Cu-Mo-Sn-Fe polymetallic metallogenic belt, NE China. Vein type Pb-Zn-Ag ore bodies are primarily hosted by slate, adjacent to a Sn ± Cu ± Mo mineralized porphyry intrusion. The deposit is characterized by silver-rich ores with Ag grades up to 3000 g/t. Four primary paragenetic sequences are recognized: (I) arsenopyrite + pyrite + quartz, (II) main sulfide + quartz, (III) silver-bearing sulfosalt + quartz, and (IV) boulangerite + calcite. A subsequent supergene oxidation stage has also been identified. Hydrothermal alteration consists of an early episode of silicification, two intermediate episodes (propylitic and phyllic), and a late argillic episode. Silver mineralization primarily belongs to the late paragenetic sequence III. Freibergite is the dominant and most important Ag-mineral in the deposit. Detailed ore mineralogy of Bianjiadayuan freibergite reveals evidence of chemical heterogeneity down to the microscale. Silver-rich sulfosalts in the late paragenetic sequence III are largely derived from a series of retrograde and solid-state reactions that redistribute Ag via decomposition and exsolution during cooling, illustrating that documentation of post-mineralization processes is essential for understanding silver ore formation. Sulfur and lead isotope compositions of sulfides, and comparison with those of local various geological units, indicate that the ore-forming fluids, lead, and other metals have a magmatic origin, suggesting a close genetic association between the studied Ag-Pb-Zn veins and the local granitic intrusion. Fluid cooling coupled with decreases in fO2 and fS2 are the factors inferred to have led to a decrease of silver solubility in the hydrothermal fluid, and successively promoted extensive Ag deposition.

Isotopic data from proterozoic sediment-hosted sulfide deposits of Brazil: Implications for their metallogenic evolution and for mineral exploration

International Nuclear Information System (INIS)

Misi, Aroldo; Coelho, Carlos E.S.; Franca Rocha, Washington J.S.; Gomez, Adriana S.R.; Cunha, Iona A.; Iyer, Sundaram S.; Tassinari, Colombo C.G.; Kyle, J. Richard

1998-01-01

Geological, petrographic, fluid inclusions studies and isotopic data of seven Proterozoic sediment-hosted Pb-Zn-Ag sulfide deposits of Brazil, permit the estimation of the age of the hosting sequence and the mineralization, the nature of the sulfur and metal sources, the temperature range of sulfide formation and the environment of deposition of the mineral deposits. The studies suggest that they were formed during periods of extensional tectonics: Growth faults or reactivated basement faults were responsible for localized circulation of metal-bearing fluids within the sedimentary sequences. In most cases, sulfides were formed by the reduction of sedimentary sulfates. Linear structures are important controls for sulfide concentration in these Proterozoic basins. (author)

Glacial/interglacial wetland, biomass burning, and geologic methane emissions constrained by dual stable isotopic CH4 ice core records

Science.gov (United States)

Bock, Michael; Schmitt, Jochen; Beck, Jonas; Seth, Barbara; Chappellaz, Jérôme; Fischer, Hubertus

2017-07-01

Atmospheric methane (CH4) records reconstructed from polar ice cores represent an integrated view on processes predominantly taking place in the terrestrial biogeosphere. Here, we present dual stable isotopic methane records [δ13CH4 and δD(CH4)] from four Antarctic ice cores, which provide improved constraints on past changes in natural methane sources. Our isotope data show that tropical wetlands and seasonally inundated floodplains are most likely the controlling sources of atmospheric methane variations for the current and two older interglacials and their preceding glacial maxima. The changes in these sources are steered by variations in temperature, precipitation, and the water table as modulated by insolation, (local) sea level, and monsoon intensity. Based on our δD(CH4) constraint, it seems that geologic emissions of methane may play a steady but only minor role in atmospheric CH4 changes and that the glacial budget is not dominated by these sources. Superimposed on the glacial/interglacial variations is a marked difference in both isotope records, with systematically higher values during the last 25,000 y compared with older time periods. This shift cannot be explained by climatic changes. Rather, our isotopic methane budget points to a marked increase in fire activity, possibly caused by biome changes and accumulation of fuel related to the late Pleistocene megafauna extinction, which took place in the course of the last glacial.

A measuring system for the fast simultaneous isotope ratio and elemental analysis of carbon, hydrogen, nitrogen and sulfur in food commodities and other biological material.

Science.gov (United States)

Sieper, Hans-Peter; Kupka, Hans-Joachim; Williams, Tony; Rossmann, Andreas; Rummel, Susanne; Tanz, Nicole; Schmidt, Hanns-Ludwig

2006-01-01

The isotope ratio of each of the light elements preserves individual information on the origin and history of organic natural compounds. Therefore, a multi-element isotope ratio analysis is the most efficient means for the origin and authenticity assignment of food, and also for the solution of various problems in ecology, archaeology and criminology. Due to the extraordinary relative abundances of the elements hydrogen, carbon, nitrogen and sulfur in some biological material and to the need for individual sample preparations for H and S, their isotope ratio determination currently requires at least three independent procedures and approximately 1 h of work. We present here a system for the integrated elemental and isotope ratio analysis of all four elements in one sample within 20 min. The system consists of an elemental analyser coupled to an isotope ratio mass spectrometer with an inlet system for four reference gases (N(2), CO(2), H(2) and SO(2)). The combustion gases are separated by reversible adsorption and determined by a thermoconductivity detector; H(2)O is reduced to H(2). The analyser is able to combust samples with up to 100 mg of organic material, sufficient to analyse samples with even unusual elemental ratios, in one run. A comparison of the isotope ratios of samples of water, fruit juices, cheese and ethanol from wine, analysed by the four-element analyser and by classical methods and systems, respectively, yielded excellent agreements. The sensitivity of the device for the isotope ratio measurement of C and N corresponds to that of other systems. It is less by a factor of four for H and by a factor of two for S, and the error ranges are identical to those of other systems. Copyright (c) 2006 John Wiley & Sons, Ltd.

French days on stable isotopes

International Nuclear Information System (INIS)

2000-01-01

These first French days on stable isotopes took place in parallel with the 1. French days of environmental chemistry. Both conferences had common plenary sessions. The conference covers all aspects of the use of stable isotopes in the following domains: medicine, biology, environment, tracer techniques, agronomy, food industry, geology, petroleum geochemistry, cosmo-geochemistry, archaeology, bio-geochemistry, hydrology, climatology, nuclear and particle physics, astrophysics, isotope separations etc.. Abstracts available on CD-Rom only. (J.S.)

Chemical and isotopic compositions of water and dissolved sulfate from shallow wells on Vulcano Island, Aeolian Archipelago, Italy

Energy Technology Data Exchange (ETDEWEB)

Cortecci, G.; Dinelli, E.; Boschetti, T. [University of Bologna (Italy). Dept. of Earth and Geological Environmental Sciences; Bolognesi, L. [International Institute for Geothermal Research, Pisa (Italy); Ferrara, G. [University of Pisa (Italy). Dept. of Earth Sciences

2001-02-01

Twenty-two cold and thermal waters from shallow wells sampled in June 1995 in the Vulcano Porto area, Vulcano Island, were analyzed for major and minor chemical constituents, oxygen and hydrogen isotopes and tritium contents, and sulfur isotopes in the dissolved sulfate. The sulfur isotopic composition of the dissolved sulfate ranges between + 0.6 and + 6.5 per mille (mean + 3.7{+-}1.7 per mille), and is interpreted as deriving mainly from fumarolic SO{sub 2} undergoing oxidation in deep and shallow aquifers, with possible minor contributions from oxidation of H{sub 2}S. Dissolution of secondary anhydrite may have been a minor source of the isotopically heavy aqueous sulfate in the cold groundwaters. The chemical and isotopic features of the waters support previous interpretative hydrologic models of Vulcano Porto, which comprise a number of aquifers fed basically by two major end-members, i.e. meteoric water and crater-type fumarolic inputs, the latter in the form of absorbed emissions or condensate. These data, along with the sulfur isotopes of aqueous sulfate, exclude involvement of seawater in the recharge of the groundwater system of the island. (author)

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Directory of Open Access Journals (Sweden)

Natascha Riedinger

2017-05-01

Full Text Available The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates (SRR. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT. Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydroxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron

Urbanization impact on sulfur content of groundwater revealed by the study of urban speleothem-like deposits: Case study in Paris, France.

Science.gov (United States)

Pons-Branchu, E; Roy-Barman, M; Jean-Soro, L; Guillerme, A; Branchu, P; Fernandez, M; Dumont, E; Douville, E; Michelot, J L; Phillips, A M

2017-02-01

Speleothem-like deposits that develop underground in urban areas are an archive of the environmental impact of anthropic activities that has been little studied so far. In this paper, the sulfate content in shallow groundwater from northern Paris (France) is compared with the sulfur content in two 300-year-old urban carbonate deposits that grew in a historical underground aqueduct. The present-day waters of the aqueduct have very high sulfur and calcium contents, suggesting pollution from gypsum dissolution. However, geological gypsum levels are located below the water table. Sulfur content was measured by micro-X-ray fluorescence in these very S-rich carbonate deposits (0.5 to 1% of S). A twofold S increase during the second half of the 1800s was found in both samples. These dates correspond to two major periods of urbanization above the site. We discus three possible S sources: anthropic sources (industries, fertilizers…), volcanic eruptions and input within the water through gypsum brought for urbanization above the studied site (backfill with quarry waste) since the middle of the 19th century. For the younger second half of the studied section, S input from gypsum brought during urbanization was confirmed by the study of isotopic sulfur composition (δ 34 S=+15.2‰ at the top). For the oldest part, several sulfur peaks could be related to early industrial activity in Paris, that caused high local air pollution, as reported in historical archives but also to historical gypsum extraction. This study provides information on the origin and timing of the very high SO 4 2- levels measured nowadays within the shallow groundwater, thus demonstrating the interest in using carbonate deposits in urban areas as a proxy for the history of urbanization or human activities and their impact on water bodies. Copyright © 2016 Elsevier B.V. All rights reserved.

Scattering of low-energetic pions on the sulfur isotopes 32S and 34S

International Nuclear Information System (INIS)

Krell, S.

1990-01-01

At the Paul-Scherrer Institute PSI in Villingen/Switzerland the scattering of positive and negative pions of 50 MeV kinetic energy on the sulfur isotopes 32 S, 34 S was measured with the new installed low-energy pion spectrometer LEPS. Elastic cross sections were measured for scattering angles of 5deg-123deg for both pion polarities and for both isotopes. Because of the good resolution of 500 keV it was also possible to measure the inelastic scattering to single excited nuclear states of 45deg-123deg. Aim of the analyses was the testing of the basing reaction model, the test of the effective pion-nucleon interaction in the nucleus, as well as the extraction of neutron density distributions and neutron transition densities in 34 S. At the N=Z nucleus 32 S, the nuclear structure of which is known from the electron scattering, by means of the elastic scattering the effective πN interaction was fixed. The validity of the impulse approximation at 50 MeV was proved by the quantitative reproduction of the 2 1 + scattering data on 32 S by parameter-free DWIA calculations. For the 4 1 + and the 3 1 + excitations in 32 S the expected isoscalar character was confirmed. For the nucleus 34 S the analysis of the eleastic scattering yields a neutron skin of Δr np =0.03(1)fm. The scattering to the 2 1 + yields a neutron moment of M n =16.6(10)efm 2 respectively a ratio of proton to neutron moment of M n /M p =1.19(9), which corresponds to a collective isoscalar excitation. Against this for the 2 2 + excitation a ratio for the moments of M n /M p =-0.4(2) is determined, what means that to this not collective, proton-dominated excitation neutron and proton wave functions contribute antiphasically, as it is typical for isovectorial excitations. (orig./HSI) [de

Multiple S and O isotope constraints on O2 at 2.25 Ga

Science.gov (United States)

Killingsworth, B.; Sansjofre, P.; Philippot, P.; Thomazo, C.; Cartigny, P.; Lalonde, S.

2017-12-01

The composition of Earth's atmosphere around the time of the Great Oxidation Event (GOE) at the Archean-Proterozoic boundary is of great interest for reconstructing the redox evolution of the Earth. Sulfate has been shown to be a valuable recorder of isotopic signals of atmospheric O2 but its records are sparse around the time of the GOE. To constrain O2 around the GOE, we have measured quadruple sulfur and triple oxygen isotopes of sulfate from barite in sedimentary drill core from the Turee Creek Group, Australia from 2.25 Ga. A combined sulfur and oxygen approach for estimating the triple oxygen isotope composition of O2 at 2.25 Ga will be presented and its implications for the Paleoproterozoic atmosphere will be discussed.

New Applications of Cosmogenic Radioactive Isotopes to Study Water Travel Times

Science.gov (United States)

Visser, A.; Thaw, M.; Deinhart, A.; Bibby, R. K.; Esser, B.

2017-12-01

The travel time of water moving through a landscape influences nutrient dynamics and biogeochemical cycles. Constraining water travel times helps to understand the functioning of the critical zone. Water travel times cannot be observed directly but can be constrained by measurements of cosmogenic radioactive isotopes. We studied a small (4.6 km2) subalpine (1660-2117 m) catchment in a Mediterranean climate (8 °C, 1200 mm/yr) in the California Sierra Nevada to assess subsurface water storage dynamics and investigate flow paths and flow velocities. We analyzed a combination of three cosmogenic radioactive isotopes with half-lives varying from 87 days (sulfur-35), 2.6 years (sodium-22) to 12.3 years (tritium) in precipitation and stream samples. Water stable isotopes and solute chemistry aided the interpretation of the cosmogenic isotopes. Tritium samples (1L) are analyzed by noble gas mass spectrometry after helium-3 accumulation. Samples for sulfur-35 and sodium-22 are collected by processing 20-1000 L of water through an anion and cation exchange column in-situ. Sulfur-35 is analyzed by liquid scintillation counting after chemical purification and precipitation. Sodium-22 is analyzed by gamma counting after eluting the cations into a 4L Marinelli beaker. Monthly collected precipitation samples show variability of deposition rate for tritium and sulfur-35. Sodium-22 levels in cumulative yearly precipitation samples are consistent with recent studies in the US and Japan. The observed variability of deposition rates complicates direct use as decaying age tracers. The level and variability of tritium in monthly stream samples indicate a mean residence time on the order of 10 years and only small contributions of younger water during high flow conditions. Sulfur-35 and sodium-22 concentrations were critically interpreted considering possible uptake by vegetation and cation exchange. Detections of sodium-22 confirm a small fraction of younger (water. Low concentrations

Geochemical and stable isotopic constraints on the generation and passive treatment of acidic, Fe-SO{sub 4} rich waters

Energy Technology Data Exchange (ETDEWEB)

Matthies, Romy, E-mail: rmatthies@uwaterloo.ca [School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU (United Kingdom); Aplin, Andrew C., E-mail: andrew.aplin@ncl.ac.uk [School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU (United Kingdom); Boyce, Adrian J., E-mail: a.boyce@suerc.gla.ac.uk [Scottish Universities Environment Research Centre, East Kilbride, G75 0QF (United Kingdom); Jarvis, Adam P., E-mail: a.p.jarvis@ncl.ac.uk [School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU (United Kingdom)

2012-03-15

Reducing and Alkalinity Producing Systems (RAPS) remediate net-acidic metalliferous mine drainage by creating anoxic conditions in which bacterial sulfate reduction (BSR) raises alkalinity and drives the precipitation of iron and other chalcophilic elements as sulfides. We report chemical and stable isotopic data from a study monitoring the biogeochemical processes involved in the generation of mine waters and their remediation by two RAPS. Sulfur isotopes show that sulfate in all mine waters has a common source (pyrite oxidation), whilst oxygen isotopes show that oxidation of pyritic sulfur is mediated by Fe(III){sub aq}. The isotopic composition of dissolved sulfide, combined with the sulfur and oxygen isotopic composition of sulfate in RAPS effluents, proves BSR and details its dual isotope systematics. The occurrence and isotopic composition of solid phase iron sulfides indicate the removal of reduced sulfur within the RAPS, with significant amounts of elemental sulfur indicating reoxidation steps. However, only 0 to 9% of solid phase iron occurs as Fe sulfides, with approximately 70% of the removed iron occurs as Fe(III) (hydr)oxides. Some of the (hydr)oxide is supplied to the wetland as solids and is simply filtered by the wetland substrate, playing no role in alkalinity generation or proton removal. However, the majority of iron is supplied as dissolved Fe(II), indicating that acid generating oxidation and hydrolysis reactions dominate iron removal. The overall contribution of BSR to the sulfur geochemistry in the RAPS is limited and sulfate retention is dominated by sulfate precipitation, comparable to aerobic treatment systems, and show that the proton acidity resulting from iron oxidation and hydrolysis must be subsequently neutralised by calcite dissolution and/or BSR deeper in the RAPS sediments. BSR is not as important as previously thought for metal removal in RAPS. The results have practical consequences for the design, treatment performance and long

Volcanic Plume Impact on the Atmosphere and Climate: O- and S-Isotope Insight into Sulfate Aerosol Formation

Directory of Open Access Journals (Sweden)

Erwan Martin

2018-05-01

Full Text Available The impact of volcanic eruptions on the climate has been studied over the last decades and the role played by sulfate aerosols appears to be major. S-bearing volcanic gases are oxidized in the atmosphere into sulfate aerosols that disturb the radiative balance on earth at regional to global scales. This paper discusses the use of the oxygen and sulfur multi-isotope systematics on volcanic sulfates to understand their formation and fate in more or less diluted volcanic plumes. The study of volcanic aerosols collected from air sampling and ash deposits at different distances from the volcanic systems (from volcanic vents to the Earth poles is discussed. It appears possible to distinguish between the different S-bearing oxidation pathways to generate volcanic sulfate aerosols whether the oxidation occurs in magmatic, tropospheric, or stratospheric conditions. This multi-isotopic approach represents an additional constraint on atmospheric and climatic models and it shows how sulfates from volcanic deposits could represent a large and under-exploited archive that, over time, have recorded atmospheric conditions on human to geological timescales.

Sulfur metabolism in phototrophic sulfur bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Dahl, Christiane

2008-01-01

Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB......). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms...... in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative...

Isotopes in everyday life

International Nuclear Information System (INIS)

Seligman, H.; Gillen, V.A.

1990-12-01

Isotopes represent a tool which can do certain jobs better, easier, quicker, more simply and cheaper than competitive methods. Some measurements could not be done at all without the use of isotopes as there are no alternative methods available. A short review of these tools of science in their different fields is given: food and agriculture, human health applications, industry, hydrology, geology, geochemistry, geophysics and dating, environment, basic scientific research

Role of stable isotope mass spectroscopy in hydrological sciences

International Nuclear Information System (INIS)

Keesari, Tirumalesh

2017-01-01

Isotope Ratio Mass Spectrometry (IRMS) is a specialized technique used to provide information about a given sample about its geographic, chemical, physical and biological origin. The ability to determine the source of water molecule stems from the relative isotopic abundances of its constituent elements, viz., hydrogen and oxygen or sometimes through its dissolved elements such as carbon, nitrogen and sulphur etc. Since the isotope ratios of carbon, hydrogen, oxygen, sulfur, and nitrogen can become locally enriched or depleted through a variety of kinetic and thermodynamic factors, measurement of the isotope ratios can be used to unravel the processes and differentiate water samples which otherwise exhibit similar chemical signatures. For brevity, this article focuses mainly on measurement of water isotopes, common notation for expressing isotope data and standards, theory of isotope hydrology, field applications and advances

A SIMS Study of Sulfur Isotopes of Accessory Pyrites Associated with Barites from Methane Cold Seeps in the Gulf of Mexico

Science.gov (United States)

Morelli, E. C.; Aharon, P.

2017-12-01

Bacteria and archaea associated with seeps can fix methane from sublimating gas hydrates through coupled bacterial sulfate reduction/ anaerobic methane oxidation (BSR/AMO) and prevent outgassing to the atmosphere. The occurrence of such microbial processes has been established on the basis of the sulfur isotope compositions of microbial byproducts (pyrites; FeS2) that reflect the degree of fractionation between SO4 and FeS2 via the production of the H2S intermediate phase. BSR/AMO coupling has been discerned in accessory sulfides associated with carbonates from gas hydrate sites. Whether BSR/AMO coupling is also active in barites, another ubiquitous product of gas hydrate sublimation, has so far been overlooked. Here we present results of a new sulfur isotope study of accessory sulfides in barites associated with gas hydrates at the threshold of stability occurring on the Gulf of Mexico slope. Using a fractionation factor of 1.009 and a seawater δ34SSO4 value of 20.3‰ and assuming a Rayleigh distillation closed system model for marine sulfide precipitation, pyrites from barite gas seeps are predicted to exhibit a range of δ34S values (about -1‰ to 20‰ CDT) as the pool of sulfate is continuously depleted. Actual δ34S values could fall outside of the predicted range because the system in question is likely only partially closed and kinetic fractionations are likely. δ34S of accessory pyrites from three Garden Banks Lease Block 382 (510 - 640m water depth) and one Mississippi Canyon Lease Block 929 (590m) barite samples have been determined using an ims-1290 Secondary Ion Mass Spectrometer (SIMS). Two Garden Banks samples and one Mississippi Canyon sample reveal a spread of values from 5.30 ± 0.04 to 25.90 ± 0.09 (‰ CDT), which follow the predicted trend for gas seeps and indicate the source of fractionation is likely from the coupled BSR/AMO process. One Garden Banks sample yields a wide spread of values from -26.2 ± 0.05 to 20.5 ± 0.4 (‰ CDT). The

Determination Of Oxygen Isotope Ratio (18O-/16O) and Sulfur (34S-/32S) Value Of BaSO4 Din 5033 For Internal Standard

International Nuclear Information System (INIS)

Evarista Ristin, P.I.; Sidauruk, Paston; Wibagoyo; Djiono; Satrio

2000-01-01

It has been done an experiment to determine of oxygen( 18 O-/ 16 O) and Sulfur ( 34 S-/ 32 S) ) isotop value of BaSO 4 DIN 5033 (merck) for internal standard. The used technique for preparation of CO 2 gas to measure oxygen isotop ratio ratio (stated as deltaδ 18 O) is based on Rafter on Rafte method using graphite for reduction of BaSO 4 . Where the used technique for preparation of SO 2 gas to measure isotope sulphur ratio (started as δ 34 S) is based on Robinson - Kasakabe method using Cupro oxide to oxidize Ag 2 S. The result of this experiment is 11,48±0,41 0/00 and 5,00 plus minus ±0,33 o/oo for deltaδ 18 O and δ 34 S value respectively. Based on this experiment. BaSO 4 DIN 5033 can be used as internal standard because is values both oxygen and sulphur lie in the middle of range of its variation in nature. The result of interlab comparison shows that the value of this experiment is nearly similar to the value obtained from laboratorium of Pinstech-Pakistan. To acquire the result, it is necessary to carry out more interlab comparison

Textural, compositional, and sulfur isotope variations of sulfide minerals in the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Implications for Ore Formation

Science.gov (United States)

Kelley, K.D.; Leach, D.L.; Johnson, C.A.; Clark, J.L.; Fayek, M.; Slack, J.F.; Anderson, V.M.; Ayuso, R.A.; Ridley, W.I.

2004-01-01

The Red Dog Zn-Pb deposits are hosted in organic-rich mudstone and shale of the Mississippian Kuna Formation. A complex mineralization history is defined by four sphalerite types or stages: (1) early brown sphalerite, (2) yellow-brown sphalerite, (3) red-brown sphalerite, and (4) late tan sphalerite. Stages 2 and 3 constitute the main ore-forming event and are volumetrically the most important. Sulfides in stages 1 and 2 were deposited with barite, whereas stage 3 largely replaces barite. Distinct chemical differences exist among the different stages of sphalerite. From early brown sphalerite to later yellow-brown sphalerite and red-brown sphalerite, Fe and Co content generally increase and Mn and Tl content generally decrease. Early brown sphalerite contains no more than 1.9 wt percent Fe and 63 ppm Co, with high Mn (up to 37 ppm) and Tl (126 ppm), whereas yellow-brown sphalerite and red-brown sphalerite contain high Fe (up to 7.3 wt %) and Co (up to 382 ppm), and low Mn (ion microprobe sulfur isotope analyses show a progression from extremely low ??34S values for stage 1 (as low as -37.20???) to much higher values for yellow-brown sphalerite (mean of 3.3???; n = 30) and red-brown sphalerite (mean of 3.4; n = 20). Late tan sphalerite is isotopically light (-16.4 to -27.2???). The textural, chem ical, and isotopic data indicate the following paragenesis: (1) deposition of early brown sphalerite with abundant barite, minor pyrite, and trace galena immediately beneath the sea floor in unconsolidated mud; (2) deposition of yellow-brown sphalerite during subsea-floor hydrothermal recrystallization and coarsening of preexisting barite; (3) open-space deposition of barite, red-brown sphalerite and other sulfides in veins and coeval replacement of barite; and (4) postore sulfide deposition, including the formation of late tan sphalerite breccias. Stage 1 mineralization took place in a low-temperature environment where fluids rich in Ba mixed with pore water or water

Disentangling Diagenesis From the Rock Record: An Example From the Permo-Triassic Wordie Creek Formation, East Greenland

Science.gov (United States)

Roberts, J.; Turchyn, A. V.; Wignall, P. B.; Newton, R. J.; Vane, C. H.

2018-01-01

The measurement of isotope ratios in sedimentary rocks deposited over geological time can provide key insights to past environmental change over important intervals in the past. However, it is important to be aware that secondary alteration can overprint the original isotopic records. We demonstrate this principle using high-resolution carbon, sulfur, and oxygen isotope measurements in organic carbon, pyrite, and carbonate minerals (δ13Corg, δ34Spyr, δ34SCAS, δ13Ccarb, and δ18Ocarb) and kerogen analyses (HI and OI) from the Wordie Creek Formation, East Greenland. These sediments were initially deposited across the Permo-Triassic transition, but as we will show, the carbonate record has been altered by interaction with meteoric water significantly after initial deposition. Comparison of the better preserved organic carbon and pyrite records with a proximal Permo-Triassic sequence reveals significant pyrite-sulfur isotope variability across the Permo-Triassic transition. This regional heterogeneity argues against basin-wide euxinia and instead suggests localized changes in sulfur fractionation in response to variations in organic carbon flux. This hypothesis can be used to explain seemingly inconsistent regional trends in other sulfur isotopes across the Permo-Triassic transition.

Research on isotope geology. Assessment of heat production potential of granitic rocks and development of geothermal exploration techniques using radioactive/stable isotopes and fission track 2

Energy Technology Data Exchange (ETDEWEB)

Shin, Seong Cheon; Chi, Se Jung [Korea Inst. of Geology Mining and Materials, Taejon (Korea, Republic of)

1995-12-01

Radioelements and heat production rates of granitic rocks and stable isotopes of groundwaters were analyzed to investigate the geothermal potential of Wolchulsan granite complex in the southern Yeongam area. Wolchulsan granite complex is composed mainly by Cretaceous pink alkali-feldspar granite and partly Jurassic biotite granite. The main target for the geothermal exploration is the alkali-feldspar granite that is known in general to be favorable geothermal reservoir(e.g., Shap granite in UK). To develop exploration techniques for geothermal anomalies, all geochemical data were compared to those from the Jeonju granite complex. Heat production rates(HPR) of the alkali-feldspar granite is 1.8 - 10.6 {mu}Wm{sup -3}. High radio-thermal anomalies were revealed from the central western and northern parts of the granite body. These are relatively higher than the Caledonian hot dry granites in the UK. The integrated assessment of Wolchulsan granite complex suggests potential of the Cretaceous alkali-feldspar granite as a geothermal targets. Groundwater geochemistry of the Yeongam area reflects simple evaporation process and higher oxidation environment. Stable isotope data of groundwaters are plotted on or close to the Meteoric Water Line(MWL). These isotopic data indicate a significant meteoric water dominance and do not show oxygen isotope fractionation between groundwater and wall rocks. In despite of high HPR values of the Yeongam alkali-feldspar granite, groundwater samples do not show the same geochemical properties as a thermal water in the Jeonju area. This reason can be well explained by the comparison with geological settings of the Jeonju area. The Yeongam alkali-feldspar granite does not possess any adjacent heat source rocks despite its high radio-thermal HPR. While the Jeonju granite batholith has later heat source intrusive and suitable deep fracture system for water circulation with sedimentary cap rocks. (Abstract Truncated)

Radiogenic age and isotopic studies

International Nuclear Information System (INIS)

1992-01-01

This is one of an annual collection of reports presenting data from the Geochronology Section of the Continental Geoscience Division of the Geological Survey of Canada (GSC). The main purpose of this collection is to make geochronological and other radiogenic isotope data produced by the section available promptly to the geological community. Reports make full presentation of the data, relate these to field settings and make comparatively short interpretations. Other geochronological and isotope data produced in the laboratory but published in outside journals or separate GSC publications are summarized at the end of this report. Report 5 contains 24 papers from most regions of Canada, but particularly from British Columbia. The Geochronology Laboratory has, over the years, provided substantial U-Pb dating for the Cordilleran Division of the Geological Survey of Canada in Vancouver, and the results of a number of these studies are presented this year. A compilation of K-Ar ages is given. (figs., tabs., refs.)

Stable isotope sales: Mound Laboratory customer and shipment summaries, FY-1975

International Nuclear Information System (INIS)

Eck, C.F.

1976-01-01

A listing is given of Mound Laboratory's sales of stable isotopes of noble gases, carbon, oxygen, nitrogen, and sulfur for Fiscal Year 1975. Purchasers are listed alphabetically and are divided into domestic and foreign groups. A cross reference index by location is included for domestic customers. Cross reference listings by isotope purchased are included for all customers

Stable isotope sales: Mound Facility customer and shipment summaries, FY 1981

International Nuclear Information System (INIS)

Ruwe, A.H. Jr.

1982-01-01

A listing is given of Mound Facility's sales of stable isotopes of noble gases, carbon, oxygen, nitrogen, chlorine, and sulfur for Fiscal Year 1981. Purchasers are listed alphabetically and are divided into domestic and foreign groups. A cross-reference index by location is included for domestic customers. Cross-reference listings by isotope purchased are included for all customers

Stable isotope sales; Mound Facility customer and shipment summaries, FY 1977

International Nuclear Information System (INIS)

Ruwe, A.H. Jr.

1978-01-01

A listing is given of Mound Facility's sales of stable isotopes of noble gases, carbon, oxygen, nitrogen, chlorine, and sulfur for Fiscal Year 1977. Purchasers are listed alphabeticaly and are divided into domestic and foreign groups. A cross-reference index by location is included for domestic customers. Cross-reference listings by isotope purchased are included for all customers

Sulfur isotope separation by anion exchange chromatography: 34 S isotope enrichment

International Nuclear Information System (INIS)

Bendassolli, Jose Albertino; Trivelin, Paulo Cesar O.; Carneiro Junior, Francisco

1995-01-01

The 34 S isotope separation was carried out by isotopic exchange reactions between sulphurous acid in solution and bisulphite anions adsorbed on an ammonium quaternary (Dowex 1 x 8 and Dowex 2 x 8, 100-200 mesh) anion exchange resin packed in columns. Each resin column had 130 cm length and 2.2 cm diameter. The columns were connected in series during displacement of bisulphite bands. For the experiments, a band of bisulphite was fixed to the anion resin, initially in the hydroxyl ion form, and subsequently eluted with 0.2 0.3, 0.4 and 0.6 mol L -1 HCL solution. The hydrochloric acid solution was kept under a nitrogen atmosphere at 245 KPa of pressure, in order to prevent the evolution of gases and also the oxidation of the bisulphite. The experiments showed that the best results were obtained with the elution of bisulphite with 0.2 mol.L -1 HCL, with the Dowex 1 x 8 resin. Enrichments in 34 S of 17.33 atoms% were obtained using Dowex 1 x 8 resin, 0.2 mol.L -1 HCL solution and band displacement of 50 m. Replacing the depleted portion of the band with natural bisulphite, for each 10 m of band displacement, produced 6.79 mmol of sulphurous acid enriched with approximately 17% of 34 S, after 14 m of band dislocation. (author). 7 refs., 1 fig., 2 tabs

Carbon and oxygen isotope analysis of leaf biomass reveals contrasting photosynthetic responses to elevated CO2 near geologic vents in Yellowstone National Park

Directory of Open Access Journals (Sweden)

D. G. Williams

2009-01-01

Full Text Available In this study we explore the use of natural CO2 emissions in Yellowstone National Park (YNP in Wyoming, USA to study responses of natural vegetation to elevated CO2 levels. Radiocarbon (14C analysis of leaf biomass from a conifer (Pinus contortus; lodgepole pine and an invasive, non-native herb (Linaria dalmatica; Dalmation toadflax was used to trace the inputs of vent CO2 and quantify assimilation-weighted CO2 concentrations experienced by individual plants near vents and in comparable locations with no geologic CO2 exposure. The carbon and oxygen isotopic composition and nitrogen percent of leaf biomass from the same plants was used to investigate photosynthetic responses of these plants to naturally elevated atmospheric CO2 concentrations. The coupled shifts in carbon and oxygen isotope values suggest that dalmation toadflax responded to elevated CO2 exposure by increasing stomatal conductance with no change in photosynthetic capacity and lodgepole pine apparently responded by decreasing stomatal conductance and photosynthetic capacity. Lodgepole pine saplings exposed to elevated levels of CO2 likewise had reduced leaf nitrogen concentrations compared to plants with no enhanced CO2 exposure, further suggesting widespread and dominant conifer down-regulated photosynthetic capacity under elevated CO2 levels near geologic vents.

Use of the ion microprobe in geological dating

International Nuclear Information System (INIS)

Compston, W.; Williams, I.S.; Black, L.P.

1983-01-01

SHRIMP, the Sensitive High Resolution Ion Microprobe with computerised control and data acquisition system, has recently been commissioned. It is used within the Research School of Earth Sciences, Australian National University, for the isotopic analysis of geological samples. Principles of operation and geological applications are outlined. One example described is the application to Pb-U dating of zircon

Variations of sulfur isotope ratios in a single lichen thallus: A potential historical archive for sulfur pollution

Energy Technology Data Exchange (ETDEWEB)

Yun, Misuk, E-mail: yun@cc.umanitoba.c [Department of Earth Sciences and Environmental Science Program, Memorial University, St. John' s, NL, A1B 3X5 (Canada); Wadleigh, Moire A. [Department of Earth Sciences and Environmental Science Program, Memorial University, St. John' s, NL, A1B 3X5 (Canada); Mayer, Bernhard [Department of Geoscience, University of Calgary, 2500 University Dr. NW, Calgary, AB, T2N 1N4 (Canada)

2010-12-15

Utilizing the analytical capability to measure S isotope ratios of small quantities of S in biological material without any chemical pretreatment, the variation of {delta}{sup 34}S within a lichen thallus was investigated using old and young segments of fruticose lichen thalli (Alectoria sarmentosa) from an oil refinery area in Come-By-Chance and two coastal areas, Newfoundland, Canada. Old segments of lichen samples from the oil refinery area showed significantly higher {delta}{sup 34}S values (1.0-2.5 per mille) than their corresponding young segments. Lichen samples from two coastal areas showed no noticeable differences in {delta}{sup 34}S values between old and young segments. These results demonstrate that lichen thalli record temporal changes in the isotopic composition of atmospheric S and hence constitute a historical archive of atmospheric S pollution. - Lichen thalli record temporal changes in the isotopic composition of atmospheric S and hence constitute a suitable historical archive for biomonitoring.

Variations of sulfur isotope ratios in a single lichen thallus: A potential historical archive for sulfur pollution

International Nuclear Information System (INIS)

Yun, Misuk; Wadleigh, Moire A.; Mayer, Bernhard

2010-01-01

Utilizing the analytical capability to measure S isotope ratios of small quantities of S in biological material without any chemical pretreatment, the variation of δ 34 S within a lichen thallus was investigated using old and young segments of fruticose lichen thalli (Alectoria sarmentosa) from an oil refinery area in Come-By-Chance and two coastal areas, Newfoundland, Canada. Old segments of lichen samples from the oil refinery area showed significantly higher δ 34 S values (1.0-2.5 per mille ) than their corresponding young segments. Lichen samples from two coastal areas showed no noticeable differences in δ 34 S values between old and young segments. These results demonstrate that lichen thalli record temporal changes in the isotopic composition of atmospheric S and hence constitute a historical archive of atmospheric S pollution. - Lichen thalli record temporal changes in the isotopic composition of atmospheric S and hence constitute a suitable historical archive for biomonitoring.

Late Pleistocene to Holocene environmental changes as recorded in the sulfur geochemistry of coastal plain sediments, southwestern Taiwan

Science.gov (United States)

Chen, Y.-G.; Liu, J.C.-L.; Shieh, Y.-N.; Liu, T.-K.

2004-01-01

A core, drilled at San-liao-wan in the southwestern coastal plain of Taiwan, has been analyzed for total sulfur contents, isotopic values, as well as ratios of pyritic sulfur to organic carbon. Our results demonstrate a close relationship between late Pleistocene sea-level change and the proxies generated in this study. The inorganic sulfur contents indicate that at our study site, the Holocene transgression started at ???11 ka and remained under seawater for thousands of years until the late Holocene, corresponding to a depth of 20 m in the study core. The uppermost 20 m of core shows relatively high total organic carbon (TOC) and ??34S of inorganic sulfur, suggesting a transitional environment such as muddy lagoon or marsh, before the site turned into a modern coastal plain. In the lower part of the core, at depths of 110-145 m (corresponding ages of ???12-30 ka), low sulfur contents are recorded, probably indicating fluvial sediments deposited during the oceanic isotope stage (OIS) 2, a sea-level lowstand. The lower part of the core, roughly within OIS 3, records at least two transgressions, although the transgressional signals may be somewhat obscured by subsequent weathering. The reworked origin of organic matter reported in previous studies is confirmed by our organic sulfur data; however, the marine organic source was periodically dominant. The modern high sulfate concentrations in pore water have no correlation to the other sulfur species in the sediments, probably indicating that the sulfate migrated into the site subsequent to early diagenesis. ?? 2003 Elsevier Ltd. All rights reserved.

Sulfur utilization by rice and Crotalaria juncea from sulfate - 34S applied to the soil

Directory of Open Access Journals (Sweden)

Trivelin Paulo Cesar Ocheuze

2002-01-01

Full Text Available In tropical soils with intensive agriculture an increasing sulfur deficiency has been verified in several crops. The low available S in these soils is caused by the continuous use of concentrated NPK fertilizers. The objective of this work was to evaluate the utilization by rice (Oriza sativa L. and crotalaria juncea (Crotalaria juncea L. of sulfur applied to the soil, under greenhouse conditions. Pots with 3 kg of an Argisol (Paleudalf were used to test the isotopic technique with the stable isotope 34S, adding a solution of sodium sulfate labeled with 34S (14.30 ± 0.05 atom % of 34S to the soil (70 mg SO4-S per kg-1 of soil 18 days after sowing both species. The shoots of the crotalaria and rice were harvested, respectively on the 72nd and 122nd days after S fertilization. The concentration and the amount of sulfur in the crotalaria were higher than in rice, due to the higher legume requirement for this nutrient. The sulfur requirement and the short time interval between fertilization and harvest of the crotalaria resulted in a small amount of native SO4-S mineralized in the soil and a small quantity of 34SO4 immobilized by soil microorganisms. Thus, the percentage of sulfur in the crotalaria derived from the fertilizer (Sdff was higher than in the rice (%Sdff crotalaria = 91.3 ± 3.5%; %Sdff rice = 66.3 ± 0.8%. The expressive values of %Sdff indicate a low rate of mineralization of SO4-S probably as a consequence of the low available sulfur content in the soil.

Application of environmental isotope tracing technology to geothermal geochemistry

International Nuclear Information System (INIS)

Shang Yingnan

2006-01-01

This paper reviews the recent application and development of environmental isotope tracing technology to geothermal geochemistry in the following aspects: gas isotopes (He, C) tracing of warm springs; H, O isotope tracing on the origin and cause of geothermal water, environmental isotope dating of geothermal water, and the advantage of excess parameter of deuterium (d) in geothermal research. The author also suggests that isotope method should combine with other geological methods to expand its advantage. (authors)

Influence of earthworms on the sulfur turnover in the soil.

Science.gov (United States)

Grethe, S; Schrader, S; Giesemann, A; Larink, O; Weigel, H J

1996-08-01

Abstract The effects of earthworm activity on the concentration and isotopic composition of total sulfur in soils was investigated using batch experiments. Two ecologically different lumbricid species, the anecic Lumbricus terrestris and the endogeic Aporrectodea caliginosa, were used. The earthworms were fed birch leaves, beech leaves, cattle manure or mixed plant litter. All food sources differed isotopically (δ(34)S) from the soil (Parabraunerde). As a reference, one experiment was carried out without additional food. The experimental results show, that both earthworm species influence the total S-content and the δ(34)S-values in the soil by digestion of the different food sources. The differences in the total S-content of the earthworm tissues and in the S-isotopic composition of the casts can be attributed to the ecological differences between the earthworm species.

Stable carbon isotope response to oceanic anoxic events

International Nuclear Information System (INIS)

Hu Xiumian; Wang Chengshan; Li Xianghui

2001-01-01

Based on discussion of isotope compositions and fractionation of marine carbonate and organic carbon, the author studies the relationship between oceanic anoxic events and changes in the carbon isotope fractionation of both carbonate and organic matter. During the oceanic anoxic events, a great number of organisms were rapidly buried, which caused a kind of anoxic conditions by their decomposition consuming dissolved oxygen. Since 12 C-rich organism preserved, atmosphere-ocean system will enrich relatively of 13 C. As a result, simultaneous marine carbonate will record the positive excursion of carbon isotope. There is a distinctive δ 13 C excursion during oceanic anoxic events in the world throughout the geological time. In the Cenomanian-Turonian anoxic event. this positive excursion arrived at ∼0.2% of marine carbonate and at ∼0.4% of organic matter, respectively. Variations in the carbon isotopic compositions of marine carbonate and organic carbon record the changes in the fraction of organic carbon buried throughout the geological time and may provide clues to the changes in rates of weathering and burial of organic carbon. This will provide a possibility of interpreting not only the changes in the global carbon cycle throughout the geological time, but also that in atmospheric p CO 2

Iron and zinc partitioning between coexisting stannite and sphalerite: a possible indicator of temperature and sulfur fugacity

Science.gov (United States)

Shimizu, M.; Shikazono, N.

1985-10-01

Stannite and sphalerite coexisting with iron sulfides (pyrite and/or pyrrhotite) from Japanese ore deposits associated with tin mineralization were analyzed. Based on the iron and zinc partitioning between stannite and sphalerite, the formation temperature and sulfur fugacity for this mineral assemblage were estimated. A good correlation between stannite-sphalerite temperatures and filling temperatures of fluid inclusions and sulfur isotope temperatures was obtained. This good correlation suggests that the stannite-sphalerite pair is a useful indicator of temperature and sulfur fugacity. It is deduced that the formation temperatures are not different for skarn-type, polymetallic vein-type and Sn-W vein-type deposits, whereas the sulfur fugacities are different; sulfur fugacities increase from the skarn-type through the Sn-W vein-type to the polymetallic vein-type deposits.

The application of isotopic dating methods for prospection and exploration of nuclear raw material

International Nuclear Information System (INIS)

Komlev, L.V.; Anderson, E.B.

1977-01-01

Among the geological and geochemical methods for prospecting and searching the nuclear raw material, the isotope-dating methods determine the most important search criterion - the time of the ore-forming. The elaboration and use of these methods in uranium-ore regions reveal a series of geochemical epochs of uranium and thorium accumulation connected naturally with the history of geological evolution of the earth crust. The isotope-dating methods enable with confidence to establish the stages of tectono-magmatic activity resulting in the redistribution and the local concentration of uranium. The wide use of isotopic methods is a necessary condition for reasonable trends of the modern geological exploration [ru

Obtaining of culture of feengus-pathogene of pine root sponge-with double label (phosphorus-32 and sulfur-35)

Energy Technology Data Exchange (ETDEWEB)

Kobets, E V

1979-01-01

The culture of Fomitopsis annosa (Fr) Karst. is shown to be labelled with phosphorus and sulfur in the period of its development in the nutrient medium, which contains /sup 23/P and /sup 35/S radioactive isotopes. The labelled fungus culture retains the label in the process of its growing in the agar must medium, the correlation of sulfur-35 and phosphorus-32 activities being approximately stable.

Fractionation of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt aerosol: a new tool to investigate non-sea salt sulfate production in the marine boundary layer

Science.gov (United States)

Harris, E.; Sinha, B.; Hoppe, P.; Foley, S.; Borrmann, S.

2012-05-01

The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g). However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate - which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl aerosol, as well as the pH dependency of fractionation. Oxidation of SO2 by NaOCl aerosol was extremely efficient, with a reactive uptake coefficient of ≈0.5, and produced sulfate that was enriched in 32S with αOCl = 0.9882±0.0036 at 19 °C. Oxidation on sea salt aerosol was much less efficient than on NaOCl aerosol, suggesting alkalinity was already exhausted on the short timescale of the experiments. Measurements at pH = 2.1 and 7.2 were used to calculate fractionation factors for each step from SO2(g) → multiple steps → SOOCl2-. Oxidation on sea salt aerosol resulted in a lower fractionation factor than expected for oxidation of SO32- by O3 (αseasalt = 1.0124±0.0017 at 19 °C). Comparison of the lower fractionation during oxidation on sea salt aerosol to the fractionation factor for high pH oxidation shows HOCl contributed 29% of S(IV) oxidation on sea salt in the short experimental timescale, highlighting the potential importance of hypohalous acids in the marine environment. The sulfur isotope fractionation factors measured in this study allow differentiation between the alkalinity-limited pathways - oxidation by O3 and by Cl catalysis (α34 = 1.0163±0.0018 at 19 °C in pure water or 1.0199±0.0024 at pH = 7.2) - which favour the heavy isotope, and the alkalinity non

Fractionation of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt aerosol: a new tool to investigate non-sea salt sulfate production in the marine boundary layer

Directory of Open Access Journals (Sweden)

S. Borrmann

2012-05-01

Full Text Available The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g. However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate – which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl aerosol, as well as the pH dependency of fractionation. Oxidation of SO2 by NaOCl aerosol was extremely efficient, with a reactive uptake coefficient of ≈0.5, and produced sulfate that was enriched in 32S with αOCl = 0.9882±0.0036 at 19 °C. Oxidation on sea salt aerosol was much less efficient than on NaOCl aerosol, suggesting alkalinity was already exhausted on the short timescale of the experiments. Measurements at pH = 2.1 and 7.2 were used to calculate fractionation factors for each step from SO2(g → multiple steps → SOOCl2−. Oxidation on sea salt aerosol resulted in a lower fractionation factor than expected for oxidation of SO32− by O3 (αseasalt = 1.0124±0.0017 at 19 °C. Comparison of the lower fractionation during oxidation on sea salt aerosol to the fractionation factor for high pH oxidation shows HOCl contributed 29% of S(IV oxidation on sea salt in the short experimental timescale, highlighting the potential importance of hypohalous acids in the marine environment. The sulfur isotope fractionation factors measured in this study allow differentiation between the alkalinity-limited pathways – oxidation by O3 and by Cl catalysis (α34 = 1.0163±0.0018 at 19 °C in pure water or 1.0199±0.0024 at pH = 7.2 – which favour the heavy isotope, and

A combined chemical, isotopic and microstructural study of pyrite from roll-front uranium deposits, Lake Eyre Basin, South Australia

Science.gov (United States)

Ingham, Edwina S.; Cook, Nigel J.; Cliff, John; Ciobanu, Cristiana L.; Huddleston, Adam

2014-01-01

The common sulfide mineral pyrite is abundant throughout sedimentary uranium systems at Pepegoona, Pepegoona West and Pannikan, Lake Eyre Basin, South Australia. Combined chemical, isotopic and microstructural analysis of pyrite indicates variation in fluid composition, sulfur source and precipitation conditions during a protracted mineralization event. The results show the significant role played by pyrite as a metal scavenger and monitor of fluid changes in low-temperature hydrothermal systems. In-situ micrometer-scale sulfur isotope analyses of pyrite demonstrated broad-scale isotopic heterogeneity (δ34S = -43.9 to +32.4‰VCDT), indicative of complex, multi-faceted pyrite evolution, and sulfur derived from more than a single source. Preserved textures support this assertion and indicate a genetic model involving more than one phase of pyrite formation. Authigenic pyrite underwent prolonged evolution and recrystallization, evidenced by a genetic relationship between archetypal framboidal aggregates and pyrite euhedra. Secondary hydrothermal pyrite commonly displays hyper-enrichment of several trace elements (Mn, Co, Ni, As, Se, Mo, Sb, W and Tl) in ore-bearing horizons. Hydrothermal fluids of magmatic and meteoric origins supplied metals to the system but the geochemical signature of pyrite suggests a dominantly granitic source and also the influence of mafic rock types. Irregular variation in δ34S, coupled with oscillatory trace element zonation in secondary pyrite, is interpreted in terms of continuous variations in fluid composition and cycles of diagenetic recrystallization. A late-stage oxidizing fluid may have mobilized selenium from pre-existing pyrite. Subsequent restoration of reduced conditions within the aquifer caused ongoing pyrite re-crystallization and precipitation of selenium as native selenium. These results provide the first qualitative constraints on the formation mechanisms of the uranium deposits at Beverley North. Insights into

Isotopic tracers of sources, wells and of CO2 reactivity in geological reservoirs

International Nuclear Information System (INIS)

Assayag, N.

2006-12-01

The aim of this research works consisted in studying the behaviour of the carbonate system (dissolved inorganic carbon: DIC) following a CO 2 injection (artificial or natural), in geological reservoirs. One part of the study consisted in improving an analytical protocol for the measurement of δ 13 C DIC and DIC, using a continuous flow mass spectrometer. As a first study, we have focused our attention on the Pavin Lake (Massif Central, France). Owing to its limnologic characteristics (meromictic lake) and a deep volcanic CO 2 contribution, it can be viewed as a natural analogue of reservoir storing important quantities of CO 2 in the bottom part. Isotopic measurements (δ 18 O, δ 13 C DIC) allowed to better constrain the dynamics of the lake (stratification, seasonal variations), the magnitudes of biological activities (photosynthesis, organic matter decay, methane oxidation, methano-genesis), carbon sources (magmatic, methano-genetic), and the hydrological budgets (sub-lacustrine inputs). The second study was conducted on the Lamont-Doherty test well site (NY, USA). It includes an instrumental borehole which cuts through most of the section of the Palisades sill and into the Newark Basin sediments. Single well push-pull tests were performed: a test solution containing conservative tracers and a reactive tracer (CO 2 ) was injected at a permeable depth interval located in basaltic and meta sedimentary rocks. After an incubation period, the test solution/groundwater mixture was extracted from the hydraulically isolated zone. Isotopic measurements (δ 18 O, δ 13 C DIC) confronted to chemical data (major elements) allowed to investigate the extent of in-situ CO 2 -water-rock interactions: essentially calcite dissolution and at a lesser extend silicate dissolution...and for one of the test, CO 2 degassing. (author)

Separation and enrichment of isotopes using laser photochemistry - fundamentals and prospectives

International Nuclear Information System (INIS)

Guesten, H.

1978-01-01

Basic knowledge is summed up on isotope separation by laser photochemistry. The principal prerequisites are explained of the application of atomic and molecular spectroscopy for this purpose. Practical examples are given of isotope separation of uranium, nitrogen, chlorine, carbon, sulfur, and molybdenum showing the application of two basic techniques, i.e., of gradual atom photoionization or gradual molecule photodissociation and of selective photochemical reactions. (L.K.)

The need for New In Situ Measurements to Understand the Climate, Geology and Evolution of Venus.

Science.gov (United States)

Grinspoon, D. H.

2017-12-01

Many measurements needed to address outstanding questions about current processes and evolution of Venus can only be made from in situ platforms such as entry probes, balloons or landers. Among these are precise determination of the value and altitude dependence of the deuterium-to-hydrogen ratio, an important tracer of water history which, while clearly greatly elevated compared to the terrestrial ratio, is still unknown within a large range of uncertainty and appears, based on Venus Express results, to display an enigmatic altitude dependence. Rare gas abundances and isotopes provide clues to volatile sources and histories of outgassing and exospheric escape. Modern mass spectrometry at Venus would yield abundances of the eight stable xenon isotopes, bulk abundances of krypton, and isotopes of neon. Altitude profiles of sulfur-containing chemical species would illuminate global geochemical cycles, including cloud formation, outgassing rates and surface-atmosphere interactions. The altitude profile of wind speeds and radiation fluxes, interpreted in light of the Venus Express and Akatsuki data, would enrich understanding of the global circulation and climate dynamics of Venus. Descent and surface images of carefully chosen locations would lend ground truth to interpretations of the near-global Magellan data sets and provide context for global remote sensing data obtained by future orbiter missions. Landed instruments would provide refinement and calibration for chemical abundance measurements by historical missions as well as direct mineralogical measurements of Venusian surface and subsurface rocks. In concert with atmospheric measurements these would greatly constrain geologic history as well as the nature of surface-atmosphere interactions. Such a suite of measurements will deepen our understanding of the origin and evolution of Venus in the context of Solar System and extrasolar terrestrial planets, determine the level and style of current geological activity

Experimental investigation of sulphur isotope partitioning during outgassing of hydrogen sulphide from diluted aqueous solutions and seawater.

Science.gov (United States)

Baune, Claudia; Bottcher, Michael E

2010-12-01

The diffusion of hydrogen sulphide across the sediment-water interface and subsequent liberation to the atmosphere may occur in iron-deficient coastal marine environments with enhanced microbial activity in surface sediments and corresponding accumulation of dissolved H2S in near-surface pore waters. The involvement of analogue processes in periods of global mass extinctions during Earth's history (e.g. at the Permian-Triassic boundary) is currently in discussion [L.R. Kump, A. Pavlov, and M. Arthur,Massive Release of Hydrogen Sulfide to the Surface Ocean and Atmosphere During Intervals of Oceanic Anoxia, Geology 33, 397 (2005)]. The outgassing of H₂S is associated with a fractionation of the stable sulphur isotopes, which has so far only been investigated experimentally at selected acidic and neutral pH values, and no experiments with seawater had been carried out. In this communication, we report on sulphur isotope fractionation that takes place during the experimental degassing of H₂S from aqueous solution by an inert gas (N₂) at 21 °C. Experiments were conducted in the pH range between 2.6 and 10.8, corresponding to the dominance fields of dissolved hydrogen sulphide (H₂S(aq)), bisulphide (HS-(aq)), and mixtures of both sulphide species. Overall isotope enrichment factors between -1.6 and +3.0‰ were observed, with the residual dissolved sulphide being enriched or depleted in ³⁴S compared to the liberated H₂S at low and high pH values, respectively. The difference in the low and high pH isotope fractionation effects can be explained by isotope exchange between H₂S(aq) and HS-(aq) [B. Fry, H. Gest, and J.M. Hayes, Sulfur Isotope Effects Associated with Protonation of HS- and Volatilization of H₂S, Chem. Geol. (Isot. Geosci. Sec.) 58, 253 (1986); R. Geßler and K. von Gehlen, Investigation of Sulfur Isotope Fractionation Between H2S Gas and Aqueous Solutions, Fresenius J. Anal. Chem. 324, 130 (1986)] followed by the subsequent transfer of H�

Estimation of microbial respiration rates in groundwater by geochemical modeling constrained with stable isotopes

International Nuclear Information System (INIS)

Murphy, E.M.

1998-01-01

Changes in geochemistry and stable isotopes along a well-established groundwater flow path were used to estimate in situ microbial respiration rates in the Middendorf aquifer in the southeastern United States. Respiration rates were determined for individual terminal electron acceptors including O 2 , MnO 2 , Fe 3+ , and SO 4 2- . The extent of biotic reactions were constrained by the fractionation of stable isotopes of carbon and sulfur. Sulfur isotopes and the presence of sulfur-oxidizing microorganisms indicated that sulfate is produced through the oxidation of reduced sulfur species in the aquifer and not by the dissolution of gypsum, as previously reported. The respiration rates varied along the flow path as the groundwater transitioned between primarily oxic to anoxic conditions. Iron-reducing microorganisms were the largest contributors to the oxidation of organic matter along the portion of the groundwater flow path investigated in this study. The transition zone between oxic and anoxic groundwater contained a wide range of terminal electron acceptors and showed the greatest diversity and numbers of culturable microorganisms and the highest respiration rates. A comparison of respiration rates measured from core samples and pumped groundwater suggests that variability in respiration rates may often reflect the measurement scales, both in the sample volume and the time-frame over which the respiration measurement is averaged. Chemical heterogeneity may create a wide range of respiration rates when the scale of the observation is below the scale of the heterogeneity

Accurate isotope ratio mass spectrometry. Some problems and possibilities

International Nuclear Information System (INIS)

Bievre, P. de

1978-01-01

The review includes reference to 190 papers, mainly published during the last 10 years. It covers the following: important factors in accurate isotope ratio measurements (precision and accuracy of isotope ratio measurements -exemplified by determinations of 235 U/ 238 U and of other elements including 239 Pu/ 240 Pu; isotope fractionation -exemplified by curves for Rb, U); applications (atomic weights); the Oklo natural nuclear reactor (discovered by UF 6 mass spectrometry at Pierrelatte); nuclear and other constants; isotope ratio measurements in nuclear geology and isotope cosmology - accurate age determination; isotope ratio measurements on very small samples - archaeometry; isotope dilution; miscellaneous applications; and future prospects. (U.K.)

Thermal Regeneration of Sulfuric Acid Hydrates after Irradiation

Science.gov (United States)

Loeffler, Mark J.; Hudson, Reggie L.

2012-01-01

In an attempt to more completely understand the surface chemistry of the jovian icy satellites, we have investigated the effect of heating on two irradiated crystalline sulfuric acid hydrates, H2SO4 4H2O and H2SO4 H2O. At temperatures relevant to Europa and the warmer jovian satellites, post-irradiation heating recrystallized the amorphized samples and increased the intensities of the remaining hydrate's infrared absorptions. This thermal regeneration of the original hydrates was nearly 100% efficient, indicating that over geological times, thermally-induced phase transitions enhanced by temperature fluctuations will reform a large fraction of crystalline hydrated sulfuric acid that is destroyed by radiation processing. The work described is the first demonstration of the competition between radiation-induced amorphization and thermally-induced recrystallization in icy ionic solids relevant to the outer Solar System.

Sulphur-induced offsets in MC-ICP-MS silicon-isotope measurements

NARCIS (Netherlands)

van den Boorn, S.; Vroon, P.Z.; van Bergen, M.J.

2010-01-01

Sample preparation methods for MC-ICP-MS silicon-isotope measurements often involve a cation-exchange purification step. A previous study has argued that this would suffice for geological materials, as the occasional enrichment of anionic species would not compromise silicon-isotope analysis. Here

Graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

Science.gov (United States)

Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuiliang; Li, Xiaolin

2014-06-17

Rechargeable lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter less than 50 nm..

Significance of Isotopically Labile Organic Hydrogen in Thermal Maturation of Organic Matter

Energy Technology Data Exchange (ETDEWEB)

Arndt Schimmelmann; Maria Mastalerz

2010-03-30

Isotopically labile organic hydrogen in fossil fuels occupies chemical positions that participate in isotopic exchange and in chemical reactions during thermal maturation from kerogen to bitumen, oil and gas. Carbon-bound organic hydrogen is isotopically far less exchangeable than hydrogen bound to nitrogen, oxygen, or sulfur. We explore why organic hydrogen isotope ratios express a relationship with organic nitrogen isotope ratios in kerogen at low to moderate maturity. We develop and apply new techniques to utilize organic D/H ratios in organic matter fractions and on a molecular level as tools for exploration for fossil fuels and for paleoenvironmental research. The scope of our samples includes naturally and artificially matured substrates, such as coal, shale, oil and gas.

"Let's take back our roots through Science". The Sicilian Sulfur: a mineralogical treasure to rediscover.

Science.gov (United States)

Parisi, Bianca

2015-04-01

The name of sulfur is synonymous of Sicily! Sicilian Sulfur minerals and evaporitic deposits are well-known because they are connected with an important evolution stage of the old mediterranean area. In this Island, in the southern part of Italy, a geological formation of Messinian age, called "gessoso solfifera", outcrops. These rocks are widespread in the south and south-west Sicily, and, there, salt mines and "zolfare", sulfur mines, were located. The formation is characterized by large amounts of gypsum, potassium salts, sodium chlorates and other deposits. Most of the main mineralogical museum collections all over the world have at least a sample of one of these minerals that are usually characterized by a high aesthetic quality. When I proposed a lesson on the origin of sulfur in evaporitic rocks, I realized that an important part of the hystory of our region was in danger to be forgotten by younger generation. The exploitation of this mineral resource in the past is strictly linked to the troubled social and cultural transformation of Sicily during the last century. Thus, this is a particularly suitable topic for a multidisciplinary approach. In cooperation with the Mineralogical Museum (SteBiCeF Department, University of Palermo), a learning project was proposed to a group of 4th year high school students. It has been carrying on in order to develop the knowledge of the geological and chemical features of evaporitic deposits and to promote scientific abilities together with a better understanding of social-environmental issues. Project aims and activities include: ➢ Solubility and saturation experiments to reconstruct a simplified model of minerals deposition ➢ Working in groups: collection of data about old geological outcrops and current evaporating basins where rocks are forming in the world as well as information on sicilian mines from literature and historical documents (video, interviews, pictures, newspapers and others) ➢ a guided tour of the

Sources of carbon and sulfur nutrition for consumers in three meromictic lakes of New York State

International Nuclear Information System (INIS)

Fry, B.

1986-01-01

The trophic importance of bacterioplankton as a source of carbon and sulfur nutrition for consumers in meromictic lakes was tested using stable carbon (delta 13 C) and sulfur (delta 34 S) isotopic measurements. Studies in three lakes near Syracuse, New York, showed that most consumers ultimately derive their C and S nutrition from a mixture of terrestrial detritus, phytoplankton, and littoral vegetation, rather than from bacterioplankton. Food webs in these meromictic lakes are thus similar to those in other lakes that lack dense populations of bacterioplankton

Unraveling multiple phases of sulfur cycling during the alteration of ancient ultramafic oceanic lithosphere

Science.gov (United States)

Schwarzenbach, Esther M.; Gill, Benjamin C.; Johnston, David T.

2018-02-01

Ultramafic-hosted hydrothermal systems - characterized by ongoing serpentinization reactions - exert an important influence on the global sulfur cycle. Extensive water-rock interaction causes elemental exchange between seawater and the oceanic lithosphere, effectively removing sulfate from seawater through both abiogenic and biogenic processes. Here, we use bulk rock multiple sulfur isotope signatures (32S, 33S, 34S) and in situ sulfide analyses together with petrographic observations to track the sulfur cycling processes and the hydrothermal evolution of ancient peridotite-hosted hydrothermal systems. We investigate serpentinized peridotites from the Northern Apennine ophiolite in Italy and the Santa Elena ophiolite in Costa Rica and compare those with the Iberian Margin (Ocean Drilling Program (ODP) Leg 149 and 173) and the 15°20‧N Fracture Zone along the Mid-Atlantic Ridge (ODP Leg 209). In situ measurements of sulfides in the Northern Apennine serpentinites preserve a large range in δ34Ssulfide of -33.8 to +13.3‰ with significant heterogeneities within single sulfide grains and depending on mineralogy. Detailed mineralogical investigation and comparison with bulk rock Δ33Ssulfide and in situ δ34Ssulfide data implies a thermal evolution of the system from high temperatures (∼350 °C) that allowed thermochemical sulfate reduction and input of hydrothermal sulfide to lower temperatures (rock associated with detachment faulting along a mid-ocean ridge spreading center. The Santa Elena peridotites preserve distinct signatures for fluid circulation at high temperatures with both closed system thermochemical sulfate reduction and input of mafic-derived sulfur. In addition, the peridotites provide strong evidence that low Ca2+ concentrations in peridotite-hosted systems can limit sulfate removal during anhydrite precipitation at temperatures above 150 °C. This may play a central role for the availability of sulfate to microbial communities within these

Correlations Between Surficial Sulfur and a REE Crustal Assimilation Signature in Martian Shergottites

Science.gov (United States)

Jones, J. H.; Franz, H. B.

2015-01-01

Compared to terrestrial basalts, the Martian shergottite meteorites have an extraordinary range of Sr and Nd isotopic signatures. In addition, the S isotopic compositions of many shergottites show evidence of interaction with the Martian surface/ atmosphere through mass-independent isotopic fractionations (MIF, positive, non-zero delta(exp 33)S) that must have originated in the Martian atmosphere, yet ultimately were incorporated into igneous sulfides (AVS - acid-volatile sulfur). These positive delta(exp 33)S signatures are thought to be governed by solar UV photochemical processes. And to the extent that S is bound to Mars and not lost to space from the upper atmosphere, a positive delta(exp 33)S reservoir must be mass balanced by a complementary negative reservoir.

Electrochemically controlled iron isotope fractionation

Science.gov (United States)

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

2010-02-01

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

Scale of human mobility in the southern Andes (Argentina and Chile): A new framework based on strontium isotopes.

Science.gov (United States)

Barberena, Ramiro; Durán, Víctor A; Novellino, Paula; Winocur, Diego; Benítez, Anahí; Tessone, Augusto; Quiroga, María N; Marsh, Erik J; Gasco, Alejandra; Cortegoso, Valeria; Lucero, Gustavo; Llano, Carina; Knudson, Kelly J

2017-10-01

The goal of this article is to assess the scale of human paleomobility and ecological complementarity between the lowlands and highlands in the southern Andes during the last 2,300 years. By providing isotope results for human bone and teeth samples, we assess a hypothesis of "high residential mobility" suggested on the basis of oxygen isotopes from human remains. We develop an isotopic assessment of human mobility in a mountain landscape combining strontium and oxygen isotopes. We analyze bone and teeth samples as an approach to life-history changes in spatial residence. Human samples from the main geological units and periods within the last two millennia are selected. We present a framework for the analysis of bioavailable strontium based on the combination of the geological data with isotope results for rodent samples. The 87 Sr/ 86 Sr values from human samples indicate residential stability within geological regions along life history. When comparing strontium and oxygen values for the same human samples, we record a divergent pattern: while δ 18 O values for samples from distant regions overlap widely, there are important differences in 87 Sr/ 86 Sr values. Despite the large socio-economic changes recorded, 87 Sr/ 86 Sr values indicate a persisting scenario of low systematic mobility between the different geological regions. Our results suggest that strontium isotope values provide the most germane means to track patterns of human occupation of distinct regions in complex geological landscapes, offering a much higher spatial resolution than oxygen isotopes in the southern Andes. © 2017 Wiley Periodicals, Inc.

Radiogenic age and isotopic studies

International Nuclear Information System (INIS)

1991-01-01

This is one of an annual collection of reports presenting data from the Geochronology Section of the Continental Geoscience Division of the Geological Survey of Canada (GSC). The main purpose of this collection is to make geochronological and other radiogenic isotope data produced by the section available promptly to the geological community. Reports make full presentation of the data, relate these to field settings and make comparatively short interpretations. Other geochronological and isotope data produced in the laboratory but published in outside journals or separate GSC publications are summarized at the end of this report. Reports in this issue give U-Pb zircon ages for rocks in Newfoundland, Yukon Territory, Manitoba, Ontario, and the Northwest Territories; present a compilation of K-Ar ages; and discuss Precambrian activity in New Brunswick, the geochronology of rock from the Northwest Territories, and reconnaissance Nd studies of rocks from the Northwest Territories. (figs., tabs., refs.)

l modeling of r—diogeni™ isotopes in twoE™omponent mixing

Indian Academy of Sciences (India)

The mixing other by a mathematical operation, such as summa- equation for the isotopic ratio is as follows (e.g., Faure ..... physical sciences (New York: McGraw Hill) 336 p. ... Faure G 1986 Principles of isotope geology (New York: John.

Stable-isotope geochemistry of the Pierina high-sulfidation Au-Ag deposit, Peru: Influence of hydrodynamics on SO42--H2S sulfur isotopic exchange in magmatic-steam and steam-heated environments

Science.gov (United States)

Fifarek, R.H.; Rye, R.O.

2005-01-01

The Pierina high-sulfidation Au-Ag deposit formed 14.5 my ago in rhyolite ash flow tuffs that overlie porphyritic andesite and dacite lavas and are adjacent to a crosscutting and interfingering dacite flow dome complex. The distribution of alteration zones indicates that fluid flow in the lavas was largely confined to structures but was dispersed laterally in the tuffs because of a high primary and alteration-induced permeability. The lithologically controlled hydrodynamics created unusual fluid, temperature, and pH conditions that led to complete SO42--H2S isotopic equilibration during the formation of some magmatic-steam and steam-heated alunite, a phenomenon not previously recognized in similar deposits. Isotopic data for early magmatic hydrothermal and main-stage alunite (??34S=8.5??? to 31.7???; ??18 OSO4=4.9??? to 16.5???; ??18 OOH=2.2??? to 14.4???; ??D=-97??? to -39???), sulfides (??34 S=-3.0??? to 4.3???), sulfur (??34S=-1.0??? to 1.1???), and clay minerals (??18O=4.3??? to 12.5???; ??D=-126??? to -81???) are typical of high-sulfidation epithermal deposits. The data imply the following genetic elements for Pierina alteration-mineralization: (1) fluid and vapor exsolution from an I-type magma, (2) wallrock buffering and cooling of slowing rising vapors to generate a reduced (H2S/SO4???6) highly acidic condensate that mixed with meteoric water but retained a magmatic ??34S???S signature of ???1???, (3) SO2 disproportionation to HSO4- and H2S between 320 and 180 ??C, and (4) progressive neutralization of laterally migrating acid fluids to form a vuggy quartz???alunite-quartz??clay???intermediate argillic???propylitic alteration zoning. Magmatic-steam alunite has higher ??34S (8.5??? to 23.2???) and generally lower ??18OSO4 (1.0 to 11.5???), ??18OOH (-3.4 to 5.9???), and ??D (-93 to -77???) values than predicted on the basis of data from similar occurrences. These data and supporting fluid-inclusion gas chemistry imply that the rate of vapor ascent for this

Stable and strontium isotopic records of molluscan shells, lower jurassic, Cuenca Neuquina, southwestern Mendoza, Argentina

International Nuclear Information System (INIS)

Cagnoni, M.C.; Valencio, S.A.; Ramos, A.M; Riccardi, A.C; Panarello, H.O

2001-01-01

The strontium, carbon and oxygen isotopic signal of the past oceans is accurately recorded by authigenic marine minerals such as carbonates, sulfates and phosphates. The variation of these isotope ratios through the geological time is used as a tool in correlating and dating marine sedimentary rocks. Many works have been done concerning to the changes in carbon, oxygen and strontium isotope ratios of different marine successions in the world. These allow the construction of curves of secular variations of the isotope signals with geological time (Jones et al., 1994a, 1994b; Veizer et al., 1999; Jacobsen and Kaufman, 1999). This work presents strontium, carbon and oxygen isotope ratios of Early Jurassic biogenic marine carbonates of Cuenca Neuquina in southwestern Mendoza (au)

Stable isotopes back-track the origin of alabaster from the 'Ulrich Epitaph', Güstrow, Germany

Science.gov (United States)

Böttcher, Michael E.; Fuchs, Arnold; Gehre, Matthias; Krempler, Michael; Cooper, Anthony H.

2017-04-01

Natural calcium sulphate minerals (like gypsum, in the variety of 'alabaster') have been used for a long time for art and ornamental works despite its high solubility in aqueous solution due to its easy way of recovery and handling. To identify different European source provenances, geochemical and stable isotope forensic methods have been applied, thereby defining historical pathways of trade. A detailed geochemical characterization of both alabaster samples from the monument and potential sources is a pre-requisite for a backtracking material sources. Several tracers have been tested in the past identifiying the coupled sulfur and oxygen isotope composition of the sulfate molecule in the evaporite minerals to be highly characteristic. In the present study, we analyzed the stable sulfur and oxygen isotope composition of raw alabaster from the famous Ulrich Epithaph in Güstrow, Northeastern Germany, and compared the results with new measurements from one of the major European contributors of alabaster in the 16th century, the Cellaston quarry, Derbyshire (England) and literature data for further potential Spanish and Frensh source quarries (Kloppmann et a., 2014; Archaeometry, 56). We found that the stable sulfur and oxygen isotope signatures of alabaster from the Ulrich Epitaph indicate the origin from the Upper Triassic (Keuper) evaporites of the English Cellaston quarry and are not related to other potential alabaster sources. This further illustrates the alabaster trade way between England and Germany in the late 16th century.

Multi-element isotope dilution analyses using ICP-MS

International Nuclear Information System (INIS)

Volpe, A.M.

1996-01-01

Presently, 37 elements ranging from light (Li,B) through transition metals, noble, rare earth and heavy elements, to actinides and transuranics (Pu, Am, Cm) are measured by isotope dilution at Lawrence Livermore National Laboratory. Projects range from geological and hydrological to biological. The research goal is to measure accurately many elements present in diverse matrices at trace (ppb) levels using isotope dilution methods. Major advantages of isotope dilution methods are accuracy, elimination of ion intensity calibration, and quantitation for samples that require chemical separation. Accuracy depends on tracer isotope calibration, tracer-sample isotopic equilibration, and appropriate background, isobaric and mass bias corrections. Propagation of isotope ratio error due to improper tracer isotope addition is a major concern with multi-element analyses when abundances vary widely. 11 refs., 3 figs

Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

Science.gov (United States)

Migeon, Valérie; Bourdon, Bernard; Pili, Eric; Fitoussi, Caroline

2018-06-01

As an attempt to prevent illicit trafficking of nuclear materials, it is critical to identify the origin and transformation of uranium materials from the nuclear fuel cycle based on chemical and isotope tracers. The potential of molybdenum (Mo) isotopes as tracers is considered in this study. We focused on leaching, the first industrial process used to release uranium from ores, which is also known to extract Mo depending on chemical conditions. Batch experiments were performed in the laboratory with pH ranging from 0.3 to 5.5 in sulfuric acid. In order to span a large range in uranium and molybdenum yields, oxidizers such as nitric acid, hydrogen peroxide and manganese dioxide were also added. An enrichment in heavy Mo isotopes is produced in the solution during leaching of a granitic uranium ore, when Mo recovery is not quantitative. At least two Mo reservoirs were identified in the ore: ∼40% as Mo oxides soluble in water or sulfuric acid, and ∼40% of Mo hosted in sulfides soluble in nitric acid or hydrogen peroxide. At pH > 1.8, adsorption and/or precipitation processes induce a decrease in Mo yields with time correlated with large Mo isotope fractionations. Quantitative models were used to evaluate the relative importance of the processes involved in Mo isotope fractionation: dissolution, adsorption, desorption, precipitation, polymerization and depolymerization. Model best fits are obtained when combining the effects of dissolution/precipitation, and adsorption/desorption onto secondary minerals. These processes are inferred to produce an equilibrium isotope fractionation, with an enrichment in heavy Mo isotopes in the liquid phase and in light isotopes in the solid phase. Quantification of Mo isotope fractionation resulting from uranium leaching is thus a promising tool to trace the origin and transformation of nuclear materials. Our observations of Mo leaching are also consistent with observations of natural Mo isotope fractionation taking place during

Age and isotope evidence for the evolution of continental crust

International Nuclear Information System (INIS)

Moorbath, S.

1978-01-01

Irreversible chemical differentiation of the mantle's essentially infinite reservoir for at least the past 3800 Ma has produced new continental, sialic crust during several relatively short (ca. 100-300 Ma) episodes which were widely separated in time and may have been of global extent. During each episode (termed 'accretion-differentiation superevent'), juvenile sial underwent profound igneous, metamorphic and geochemical differentiation, resulting in thick (ca. 25-40 km), stable, compositionally gradational, largely indestructible, continental crust exhibiting close grouping of isotopic ages of rock formation, as well as mantle-type initial Sr and Pb isotopic ratios for all major constituents. Isotopic evidence suggests that within most accretion-differentiation superevents - and especially during the earlier ones - continental growth predominated over reworking of older sialic crust. Reworking of older sialic crust can occur in several types of geological environment and appears to have become more prevalent with the passage of geological time. It is usually clearly distinguishable from continental growth, by application of appropriate age and isotope data. (author)

Sulfur Geochemistry of a Lacustrine Record from Taiwan Reveals Enhanced Marine Aerosol Input during the Early Holocene.

Science.gov (United States)

Ding, Xiaodong; Li, Dawei; Zheng, Liwei; Bao, Hongyan; Chen, Huei-Fen; Kao, Shuh-Ji

2016-12-12

Lacustrine record of marine aerosol input has rarely been documented. Here, we present the sulfur geochemistry during the last deglaciation and early Holocene of a sediment core retrieved from the Dongyuan Lake in southern Taiwan. An unusually high sulfur peak accompanying pyrite presence is observed at 10.5 ka BP. Such high sulfur content in lacustrine record is unusual. The δ 34 S of sulfur varied from +9.5 to + 17.1‰ with two significant positive shifts at 10.5 and 9.4 ka BP. The sources of sulfur and potential processes involving the sulfur isotope variation including bacterial sulfate reduction, volcanic emissions, in-catchment sulfide oxidation and marine aerosol input are discussed. Enhanced marine aerosol input is the most likely explanation for such sulfur peaks and δ 34 S shifts. The positive δ 34 S shifts appeared concurrently with the maximum landslide events over Taiwan resulted from enhanced typhoon activities. The synchronicity among records suggests that increased typhoon activities promoted sea spray, and consequently enhanced the marine aerosol input with 34 S-enriched sulfate. Our sulfur geochemistry data revealed sea spray history and marine influence onto terrestrial environment at coastal regions. Wider coverage of spatial-temporal lacustrine sulfur geochemistry record is needed to validate the applicability of sulfur proxy in paleoenvironmental research.

Resetting of Mg isotopes between calcite and dolomite during burial metamorphism: Outlook of Mg isotopes as geothermometer and seawater proxy

Science.gov (United States)

Hu, Zhongya; Hu, Wenxuan; Wang, Xiaomin; Lu, Yizhou; Wang, Lichao; Liao, Zhiwei; Li, Weiqiang

2017-07-01

Magnesium isotopes are an emerging tool to study the geological processes recorded in carbonates. Calcite, due to its ubiquitous occurrence and the large Mg isotope fractionation associated with the mineral, has attracted great interests in applications of Mg isotope geochemistry. However, the fidelity of Mg isotopes in geological records of carbonate minerals (e.g., calcite and dolomite) against burial metamorphism remains poorly constrained. Here we report our investigation on the Mg isotope systematics of a dolomitized Middle Triassic Geshan carbonate section in eastern China. Magnesium isotope analysis was complemented by analyses of Sr-C-O isotopic compositions, major and trace element concentrations, and petrographic and mineralogical features. Multiple lines of evidence consistently indicated that post-depositional diagenesis of carbonate minerals occurred to the carbonate rocks. Magnesium isotope compositions of the carbonate rocks closely follow a mixing trend between a high δ26Mg dolomite end member and a low δ26Mg calcite end member, irrespective of sample positions in the section and calcite/dolomite ratio in the samples. By fitting the measured Mg isotope data using a two-end member mixing model, an inter-mineral Δ26Mgdolomite-calcite fractionation of 0.72‰ was obtained. Based on the experimentally derived Mg isotope fractionation factors for dolomite and calcite, a temperature of 150-190 °C was calculated to correspond to the 0.72‰ Δ26Mgdolomite-calcite fractionation. Such temperature range matches with the burial-thermal history of the local strata, making a successful case of Mg isotope geothermometry. Our results indicate that both calcite and dolomite had been re-equilibrated during burial metamorphism, and based on isotope mass balance of Mg, the system was buffered by dolomite in the section. Therefore, burial metamorphism may reset Mg isotope signature of calcite, and Mg isotope compositions in calcite should be dealt with caution in

Hafnium isotope ratios of nine GSJ reference samples

International Nuclear Information System (INIS)

Hanyu, Takeshi; Nakai, Shun'ichi; Tatsuta, Riichiro

2005-01-01

176 Hf/ 177 Hf ratios of nine geochemical reference rocks from the Geological Survey of Japan, together with BIR-1 and BCR-2, were determined using multi-collector inductively coupled plasma mass spectrometry. Our data for BIR-1, BCR-2 and JB-1 are in agreement with those previously reported, demonstrating the appropriateness of the chemical procedure and isotopic measurement employed in this study. The reference rocks have a wide range of 176 Hf/ 177 Hf covering the field defined by various volcanic rocks, such as mid-ocean ridge basalts, ocean island basalts, and subduction related volcanic rocks. They are therefore suitable as rock standards for Hf isotope measurement of geological samples. (author)

Recent development in isotope ratio mass spectrometry

International Nuclear Information System (INIS)

Platzner, I.

1992-01-01

Within the limited of this review the following topics will be briefly discussed: a) Accuracy, precision, internal relative standard deviation (RISD) and external relative standard deviation (RESD) of isotope ratio measurements. With advanced instrumentation and use of standard reference materials, high accuracy and RESD = 0.002% (or better) may be achieved; b) The advantages of modern automatic isotope ratio mass spectrometer are briefly described. Computer controlled operation and data acquisition, and multiple ion collection are the recent important improvement; c) The isotopic fractionation during the course of isotope ratio measurement is considered as a major source of errors in thermal ionization of metallic elements. The phenomenon in strontium, neodymium, uranium, lead and calcium and methods to correct the measured data are discussed; d) Applications of isotope ratio mass spectrometry in atomic weight determinations, the isotope dilution technique, isotope geology, and isotope effects in biological systems are described together with specific applications in various research and technology area. (author)

Evaluation of nutrient and energy sources of the deepest known serpentinite-hosted ecosystem using stable carbon, nitrogen, and sulfur isotopes.

Science.gov (United States)

Onishi, Yuji; Yamanaka, Toshiro; Okumura, Tomoyo; Kawagucci, Shinsuke; Watanabe, Hiromi Kayama; Ohara, Yasuhiko

2018-01-01

The Shinkai Seep Field (SSF) in the southern Mariana forearc discovered in 2010 is the deepest (~5,700 m in depth) known serpentinite-hosted ecosystem dominated by a vesicomyid clam, Calyptogena (Abyssogena) mariana. The pioneering study presumed that the animal communities are primary sustained by reducing fluid originated from the serpentinization of mantle peridotite. For understanding the nutrient and energy sources for the SSF community, this study conducted four expeditions to the SSF and collected additional animal samples such as polychaetes and crustaceans as well as sediments, fragments of chimneys developing on fissures of serpentinized peridotite, seeping fluid on the chimneys, and pore water within the chimneys. Geochemical analyses of seeping fluids on the chimneys and pore water of the chimneys revealed significantly high pH (~10) that suggest subseafloor serpentinization controlling fluid chemistry. Stable isotope systematics (carbon, nitrogen, and sulfur) among animals, inorganic molecules, and environmental organic matter suggest that the SSF animal community mostly relies on the chemosynthetic production while some organisms appear to partly benefit from photosynthetic production despite the great depth of SSF.

Isotope hydrogeochemistry in exploration for buried and blind mineralization

International Nuclear Information System (INIS)

Andrew, A.S.; Carr, G.R.; Giblin, A.M.; Whitford, D.J.

2000-01-01

Buried and blind deposits, with no direct geological or geochemical manifestation at the surface, are becoming increasingly important targets in Australia. One of the key exploration challenges relates to assessing and ranking targets established from geophysical and other remotely sensed surveys. Sub-surface geology is reflected in the geochemistry of groundwaters (Giblin, 1996) and hydrogeochemical methods provide a particularly powerful technique in areas of poor surface exposure, deep weathering and where transported overburden obscures the underlying geology (Giblin, 1997). In such areas several hundred samples are used to define locally prospective areas although how these relate to a specific mineralization style may be difficult to determine. The question of proximity to an orebody is fundamental to mineral exploration and isotopic (S, Pb, Sr) methods are uniquely capable of contributing to an answer. The isotopic composition of ores and waters that interact with ores carries important information about the elemental source; S and Pb are direct ore indicators allowing straight-forward interpretation of possible ore associations. The isotopic methods also provide unequivocal evidence for mixing. The isotopic compositions of S, Pb and Sr in rocks are unaffected by weathering and in natural waters are unaffected by precipitation, evaporation or dilution. Isotopic methods provide information that is complementary to that obtainable from major and trace element abundances. The application of integrated isotopic studies to conventional hydrogeochemical interpretations was tested in several areas (Fig. 1); Menninnie Dam (Pb, Zn; Eyre Peninsula SA), Abra (Ag, Pb; Bangemall Basin WA), Benambra (Cu, Zn, Pb: Lachlan Fold Belt Vic), Goonumbla (Cu, Au; Lachlan Fold Belt NSW) and Kanmantoo (Cu, Pb, Zn, Au; Kanmantoo Fold Belt SA). These were chosen to include different deposit types, tectonic regimes, climatic and topographic environments and groundwater chemistry

Laboratory-grown coccoliths exhibit no vital effect in clumped isotope (Δ47) composition on a range of geologically relevant temperatures

Science.gov (United States)

Katz, Amandine; Bonifacie, Magali; Hermoso, Michaël; Cartigny, Pierre; Calmels, Damien

2017-07-01

The carbonate clumped isotope (or Δ47) thermometer relies on the temperature dependence of the abundance of 13C18O16O22- ion groups within the mineral lattice. This proxy shows tremendous promise to reconstruct past sea surface temperatures (SSTs), but requires calibration of the relationship between Δ47 and calcification temperatures. Specifically, it is important to determine whether biologically-driven fractionation (the so-called "vital effect") overprints Δ47 values, as reported in some biominerals such as the foraminifera and the coccoliths for the carbon and oxygen isotope systems. Despite their abundance in the pelagic environment, coccolithophores have not been comprehensively investigated to test the reliability of coccolith Δ47-inferred temperatures. In this study, we cultured three geologically-relevant coccolith species (Emiliania huxleyi, Coccolithus pelagicus, and Calcidiscus leptoporus) at controlled temperatures between 7 and 25 ± 0.2 °C. Other variables such as pCO2, pH, alkalinity, nutrient concentrations and salinity were kept constant at mean present-day oceanic conditions. Although cultured coccoliths exhibit substantial species-specific oxygen and carbon isotope vital effects, we found that their Δ47 composition follows a statistically indistinguishable relationship with 1/T2 for all three species, indicating a lack of interspecific vital effects in coccoliths. Further, the Δ47 composition of coccolith calcite is identical to inorganic calcite precipitated at the same temperature, indicating an overall absence of clumped isotope vital effect in coccolith biominerals. From a paleoceanographic perspective, this study indicates that the Δ47 values of sedimentary coccoliths - even from highly diverse/mixed assemblages - can be analyzed to reconstruct SSTs with confidence, as such temperature estimates are not biased by taxonomic content or changing interspecies vital effects through time.

Z.W.O. Laboratory for Isotopic Geology

International Nuclear Information System (INIS)

1979-01-01

Summaries of the 14 most important research projects performed during the reporting year are presented. These are mainly concerned with isotope dating using Rb-Sr, K-Ar and U-Pb systems. Publications on this work are listed. Activities in mineralogy and mineral separation, X-ray analysis, chemistry, mass spectrometry, alpha spectrometry and fission-track dating are outlined. Information is also included on the laboratory personnel, speeches and papers, foreign trips and fieldwork, colloguia and receptions, foreign vistors and finance. (C.F.)

Geologic environmental study

International Nuclear Information System (INIS)

Kim, Chun Soo; Bae, Dae Seok; Kim, Kyung Su; Park, Byung Yoon; Koh, Young Kown; Chun, Kwan Sik; Kim, Jhin Wung

2000-05-01

The geoscience research works are focused on the production of geologic basic data accompanying with the technical development of geology and hydrogeologic characterization. The lithology of the Korean peninsula consists of a complex structure of 29 rock types from Archean to Quaternary. The wide distribution of Mesozoic plutonic rock is an important consideration as a potential host rock allowing flexibility of siting. The recent tectonic activities are limited to localized particular area, which can be avoided by excluding in the early stage of siting. Three rock types such as plutonic rocks, crystalline gneisses and massive volcanic rocks were suggested as the preferred host rocks for the further study on HLW disposal system. This report contains grouping of regional faults, and on the distributional characteristics of faults and fractures(zones) in terms of lithological domain and tectonical provinces. The regional groundwater regime can be grouped into 3 regimes by tectonic setting and four groundwater regions based on an altitute. Groundwaters can be grouped by their chemistry and host rocks. The origin of groundwater was proposed by isotope ( 1 8O, 2 H, 1 3C, 3 4S, 8 7Sr, 1 5N) studies and the residence time of groundwater was inferred from their tritium contents. Based on the geochemical and isotope characteristics, the geochemical evolutions of each types of groundwater were simulated using SOLVEQ/CHILLER and PHREEQC programs

Nové poznatky ze studia mineralogie, fluidních inkluzí a izotopů síry v rudách skarnového ložiska v Obřím dole

Czech Academy of Sciences Publication Activity Database

Pašava, J.; Veselovský, F.; Dobeš, P.; Haluzová, Eva; Ackerman, Lukáš; Tásler, R.

2016-01-01

Roč. 49, č. 1 (2016), s. 47-52 ISSN 0514-8057 R&D Projects: GA ČR GA13-15390S Institutional support: RVO:67985831 Keywords : Obří důl skarn-type deposit * mineralogy * fluid inclusions * sulfur isotopes Subject RIV: DB - Geology ; Mineralogy

Could a secular increase in organic burial explain the rise of oxygen? Insights from a geological carbon cycle model constrained by the carbon isotope record

Science.gov (United States)

Krissansen-Totton, J.; Kipp, M.; Catling, D. C.

2017-12-01

The stable isotopes of carbon in marine sedimentary rock provide a window into the evolution of the Earth system. Conventionally, a relatively constant carbon isotope ratio in marine sedimentary rocks has been interpreted as implying constant organic carbon burial relative to total carbon burial. Because organic carbon burial corresponds to net oxygen production from photosynthesis, it follows that secular changes in the oxygen source flux cannot explain the dramatic rise of oxygen over Earth history. Instead, secular declines in oxygen sink fluxes are often invoked as causes for the rise of oxygen. However, constant fractional organic burial is difficult to reconcile with tentative evidence for low phosphate concentrations in the Archean ocean, which would imply lower marine productivity and—all else being equal—less organic carbon burial than today. The conventional interpretation of the carbon isotope record rests on the untested assumption that the isotopic ratio of carbon inputs into the ocean reflect mantle isotopic values throughout Earth history. In practice, differing rates of carbonate and organic weathering will allow for changes in isotopic inputs, as suggested by [1] and [2]. However, these inputs can not vary freely because large changes in isotopic inputs would induce secular trends in carbon reservoirs, which are not observed in the isotope record. We apply a geological carbon cycle model to all Earth history, tracking carbon isotopes in crustal, mantle, and ocean reservoirs. Our model is constrained by the carbon isotope record such that we can determine the extent to which large changes in organic burial are permitted. We find both constant organic burial and 3-5 fold increases in organic burial since 4.0 Ga can be reconciled with the carbon isotope record. Changes in the oxygen source flux thus need to be reconsidered as a possible contributor to Earth's oxygenation. [1] L. A. Derry, Organic carbon cycling and the lithosphere, in Treatise on

Z.W.O. Laboratory for isotope geology

International Nuclear Information System (INIS)

1980-01-01

Accounts of a number of research projects, performed in the reporting year, are presented. Many of these involved isotope dating methods using the Rb-Sr, K-Ar and U-Pb systems. This is followed by a survey of associated publications. General details regarding staff, finance, conference, visits, vistors, etc. are given and a brief account of the activities is presented under the following subject areas - mineralogy and mineral separation, X-ray analysis, chemistry, mass spectrometry, electronics and computing, alpha spectrometry and fission track dating. (C.F.)

Development of analytical techniques for determining rare earth elements in geological materials

International Nuclear Information System (INIS)

Moraes, Noemia M.P. de; Kakazu, M.H.; Iyer, S.S.

1987-01-01

This work presents a comparative study between instrumental neutron activation analysis, inductively coupled plasma emission spectrometry and mass spectrometric isotope dilution techniques. Some advantages and disadvantages of the techniques are presented, depending on the type of the analysis required. Emphasis in give upon mass spectrometric isotope dilution, and some procedures for the development of this technique are presented. This methodology is being established by the nuclear and isotopic geology group of the IPEN. (author) [pt

Radiogenic age and isotopic studies

International Nuclear Information System (INIS)

Parrish, R.R.

1990-01-01

This is one of an annual collection of reports presenting data from the Geochronology Section of the Continental Geoscience Division of the Geological Survey of Canada (GSC). The main purpose of this collection is to make geochronological and other radiogenic isotope data produced by the section available promptly to the geological community. Reports make full presentation of the data, relate these to field settings and make comparatively short interpretations. Other geochronological and isotope data produced in the laboratory but published in outside journals or separate GSC publications are summarized at the end of this report. Reports in this issue cover methods for Rb-Sr and Sm-Nd isotopic analyses; 40 Ar- 39 Ar ages for the New Quebec Crater and for basaltic rocks; U-Pb ages for a differentiated mafic sill in the Ogilvie Mountains, plutonic rocks in the Contwoyto-Nose Lakes are, zircons from the Anton Complex, the Clinton-Colden gabbro-anorthosite intrusion, the Himag plutonic suite, the Campbell granite, the Central Gneiss Belt, Silurian granites, a metarhyolite, plagiogranite and gabbro, and the Wage shear zone; Rb-Sr ages for granitic rocks; K-Ar and Rb-Sr geochronology of granites; a compilation of K-Ar ages; ages of archean and proterozoic mylonites and pre-Misi granitoid domes; and reconnaissance geochronology of Baffin Island

Biologically produced sulfur

NARCIS (Netherlands)

Kleinjan, W.E.; Keizer, de A.; Janssen, A.J.H.

2003-01-01

Sulfur compound oxidizing bacteria produce sulfur as an intermediate in the oxidation of hydrogen sulfide to sulfate. Sulfur produced by these microorganisms can be stored in sulfur globules, located either inside or outside the cell. Excreted sulfur globules are colloidal particles which are

Paleoproterozoic high-sulfidation mineralization in the Tapajós gold province, Amazonian Craton, Brazil: geology, mineralogy, alunite argon age, and stable-isotope constraints

Science.gov (United States)

Juliani, Caetano; Rye, Robert O.; Nunes, Carmen M.D.; Snee, Lawrence W.; Correa, Rafael H.; Monteiro, Lena V.S.; Bettencourt, Jorge S.; Neumann, Rainer; Neto, Arnaldo A.

2005-01-01

The Brazilian Tapajós gold province contains the first evidence of high-sulfidation gold mineralization in the Amazonian Craton. The mineralization appears to be in large nested calderas. The Tapajós–Parima (or Ventuari–Tapajós) geological province consists of a metamorphic, igneous, and sedimentary sequence formed during a 2.10 to 1.87 Ga ocean−continent orogeny. The high-sulfidation mineralization with magmatic-hydrothermal alunite is related to hydrothermal breccias hosted in a rhyolitic volcanic ring complex that contains granitic stocks ranging in age from 1.89 to 1.87 Ga. Cone-shaped hydrothermal breccias, which flare upward, contain vuggy silica and have an overlying brecciated cap of massive silica; the deposits are located in the uppermost part of a ring-structure volcanic cone. Drill cores of one of the hydrothermal breccias contain alunite, natroalunite, pyrophyllite, andalusite, quartz, rutile, diaspore, woodhouseite–svanbergite, kaolinite, and pyrite along with inclusions of enargite–luzonite, chalcopyrite, bornite, and covellite. The siliceous core of this alteration center is surrounded by advanced argillic and argillic alteration zones that grade outward into large areas of propylitically altered rocks with sericitic alteration assemblages at depth. Several occurrences and generations of alunite are observed. Alunite is disseminated in the advanced argillic haloes that envelop massive and vuggy silica or that underlie the brecciated silica cap. Coarse-grained alunite also occurs in branching veins and locally is partly replaced by a later generation of fine-grained alunite. Silicified hydrothermal breccias associated with the alunite contain an estimated reserve of 30 tonnes of gold in rock that grades up to 4.5 g t−1 Au. Seven alunite samples gave 40Ar/39Ar ages of 1.869 to 1.846 Ga, with various degrees of apparent minor Ar loss. Stable isotopic data require a magmatic-hydrothermal origin for the alunite, typical for high

Studies in the determination of lead isotope ratios by inductively coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Date, A.R.; Yuk Ying Cheung

1987-01-01

The application of ICP-MS to the determination of lead isotope ratios in geological materials is described. Data presented for a series of lead mineral concentrates are compared with reference values obtained by conventional solid source thermal ionisation mass spectrometry. The simultaneous determination of lead isotope ratios and trace elements is carried out in a rapid analysis mode. The application of an electrothermal vaporisation technique for small solution aliquots is described. Lead isotope ratio data for the United States Geological Survey standard reference silicate rock BCR-1, obtained without separation of lead from the matrix, are compared with previously published values obtained after separation. (author)

Effect of sulfur content in a sulfur-activated carbon composite on the electrochemical properties of a lithium/sulfur battery

Energy Technology Data Exchange (ETDEWEB)

Park, Jin-Woo; Kim, Changhyeon; Ryu, Ho-Suk; Cho, Gyu-Bong; Cho, Kwon-Koo; Kim, Ki-Won [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Ahn, Jou-Hyeon [Department of Chemical & Biological Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Wang, Guoxiu [School of Chemistry and Forensic Science, University of Technology Sydney, Sydney, NSW 2007 (Australia); Ahn, Jae-Pyeung [Advanced Analysis Center, Research Planning & Coordination Division, KIST, Seoul (Korea, Republic of); Ahn, Hyo-Jun, E-mail: ahj@gnu.ac.kr [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of)

2015-09-15

Highlights: • The content of sulfur in activated carbon was controlled by solution process. • The sulfur electrode with low sulfur content shows the best performance. • The Li/S battery has capacity of 1360 mAh/g at 1 C and 702 mAh/g at 10 C. - Abstract: The content of sulfur in sulfur/activated carbon composite is controlled from 32.37 wt.% to 55.33 wt.% by a one-step solution-based process. When the sulfur content is limited to 41.21 wt.%, it can be loaded into the pores of an activated carbon matrix in a highly dispersed state. On the contrary, when the sulfur content is 55.33 wt.%, crystalline sulfur can be detected on the surface of the activated carbon matrix. The best electrochemical performance can be obtained for a sulfur electrode with the lowest sulfur content. The sulfur/activated carbon composite with 32.37 wt.% sulfur afforded the highest first discharge capacity of 1360 mAh g{sup −1} at 1 C rate and a large reversible capacity of 702 mAh g{sup −1} at 10 C (16.75 A/g)

Ultra-high-precision Nd-isotope measurements of geological materials by MC-ICPMS

DEFF Research Database (Denmark)

Saji, Nikitha Susan; Wielandt, Daniel Kim Peel; Paton, Chad

2016-01-01

We report novel techniques allowing the measurement of Nd-isotope ratios with unprecedented accuracy and precision by multi-collector inductively coupled plasma mass spectrometry. Using the new protocol, we have measured the Nd-isotopic composition of rock and synthetic Nd standards as well as th...

Isotope composition and volume of Earth´s early oceans

DEFF Research Database (Denmark)

Pope, Emily Catherine; Bird, Dennis K.; Rosing, Minik Thorleif

2012-01-01

Oxygen and hydrogen isotope compositions of Earth´s seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hyd...... in Earth´s oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH4 and CO2 concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth.......Oxygen and hydrogen isotope compositions of Earth´s seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs......, but hydrogen´s was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as Î...

Water isotope systematics: Improving our palaeoclimate interpretations

Science.gov (United States)

Jones, M. D.; Dee, S.; Anderson, L.; Baker, A.; Bowen, G.; Noone, D.

2016-01-01

The stable isotopes of oxygen and hydrogen, measured in a variety of archives, are widely used proxies in Quaternary Science. Understanding the processes that control δ18O change have long been a focus of research (e.g. Shackleton and Opdyke, 1973; Talbot, 1990 ; Leng, 2006). Both the dynamics of water isotope cycling and the appropriate interpretation of geological water-isotope proxy time series remain subjects of active research and debate. It is clear that achieving a complete understanding of the isotope systematics for any given archive type, and ideally each individual archive, is vital if these palaeo-data are to be used to their full potential, including comparison with climate model experiments of the past. Combining information from modern monitoring and process studies, climate models, and proxy data is crucial for improving our statistical constraints on reconstructions of past climate variability.As climate models increasingly incorporate stable water isotope physics, this common language should aid quantitative comparisons between proxy data and climate model output. Water-isotope palaeoclimate data provide crucial metrics for validating GCMs, whereas GCMs provide a tool for exploring the climate variability dominating signals in the proxy data. Several of the studies in this set of papers highlight how collaborations between palaeoclimate experimentalists and modelers may serve to expand the usefulness of palaeoclimate data for climate prediction in future work.This collection of papers follows the session on Water Isotope Systematics held at the 2013 AGU Fall Meeting in San Francisco. Papers in that session, the breadth of which are represented here, discussed such issues as; understanding sub-GNIP scale (Global Network for Isotopes in Precipitation, (IAEA/WMO, 2006)) variability in isotopes in precipitation from different regions, detailed examination of the transfer of isotope signals from precipitation to geological archives, and the

Calcium Isotope Analysis by Mass Spectrometry

Science.gov (United States)

Boulyga, S.; Richter, S.

2010-12-01

The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. This presentation discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. Additionally, the availability of Ca isotope reference materials will be discussed.

In vivo synthesized 34S enriched amino acid standards for species specific isotope dilution of proteins

DEFF Research Database (Denmark)

Hermann, Gerrit; Moller, Laura Hyrup; Gammelgaard, Bente

2016-01-01

(ICP-MS) combined to anion exchange showed that very high concentrated spike material could be produced with [small mu ]mol amounts of proteinogenic sulfur containing amino acids per g cell dry weight. An enrichment of 34S to 96.3 +/- 0.4% (n = 3) and 98.5 +/- 0.4% (n = 3) for cysteic acid...... with the concept of species specific isotope dilution analysis (IDA). The method relies on the determination of the two sulfur containing amino acids, cysteine and methionine by sulfur speciation analysis and is hence applicable to any protein containing sulfur. In vivo synthesis using 34S as sulfur source...... and methionine sulfone, respectively, was assessed. The established IDA method was validated for the absolute quantification of commercially available lysozyme and ceruloplasmin standards including the calculation of a total combined uncertainty budget....

Stable Isotope Group progress report for the period July 1989-June 1990

Energy Technology Data Exchange (ETDEWEB)

Lyon, G L [Nuclear Sciences Group, DSIR Physical Sciences, Lower Hutt (New Zealand)

1991-07-01

The work of the stable isotope and geochronology laboratories in 1989-90 continued to emphasise geochemical and geological applications of mass spectrometry. Research included studies in mass spectrometer instrumentation, atmospheric science, isotope hydrology, geology and biology. A new sulphur isotope reference solid was prepared for international distribution. Geochronological research has included work on the dating and petrogenesis of Taupo Volcanic Zone eruptives, Coromandel Peninsula volcanics, Canterbury-Marlborough plutonics and volcanics, the Subantarctic Islands, West Coast granitoids and the schists and greywackes of New Zealand. Oxygen isotopes continue to be valuable in the study of geothermal systems and of a fossil geothermal system in Fiordland rocks. Geothermal studies have included work in El Salvador as well as a major new study of the Rotorua geothermal system. Atmospheric studies have concentrated on the applications of isotope ratios especially 13C/12C in the trace gases CH4 and CO. Groundwater research on the role of the unsaturated zone continued, and studies of the 14C and 13C content of deep groundwaters of Poverty Bay and Marlborough were carried out. Isotope variations in groundwater near faults are being monitored to look for earthquake precursors. (author). 45 refs., 1 fig.

Stable Isotope Group progress report for the period July 1989-June 1990

International Nuclear Information System (INIS)

Lyon, G.L.

1991-01-01

The work of the stable isotope and geochronology laboratories in 1989-90 continued to emphasise geochemical and geological applications of mass spectrometry. Research included studies in mass spectrometer instrumentation, atmospheric science, isotope hydrology, geology and biology. A new sulphur isotope reference solid was prepared for international distribution. Geochronological research has included work on the dating and petrogenesis of Taupo Volcanic Zone eruptives, Coromandel Peninsula volcanics, Canterbury-Marlborough plutonics and volcanics, the Subantarctic Islands, West Coast granitoids and the schists and greywackes of New Zealand. Oxygen isotopes continue to be valuable in the study of geothermal systems and of a fossil geothermal system in Fiordland rocks. Geothermal studies have included work in El Salvador as well as a major new study of the Rotorua geothermal system. Atmospheric studies have concentrated on the applications of isotope ratios especially 13C/12C in the trace gases CH4 and CO. Groundwater research on the role of the unsaturated zone continued, and studies of the 14C and 13C content of deep groundwaters of Poverty Bay and Marlborough were carried out. Isotope variations in groundwater near faults are being monitored to look for earthquake precursors. (author). 45 refs., 1 fig

Sulfur-Kβ /sub emission studies on sulfur-bearing heterocycles

International Nuclear Information System (INIS)

Phillips, D.R.; Andermann, G.G.; Fujiwara, F.

1986-01-01

Sulfur-K/β /sub x-ray fluorescence spectroscopy (XFS) has been used to study the electronic structure and bonding in sulfur-bearing heterocycles. XFS not only has the capability of experimentally measuring valence electron energies in molecular species, but can also provide intensity data which can help define the nature of the molecular orbitals defined by the electrons. This report discusses the feasibility of using XFS as an analytical tool for the determination of total and specific sulfur heterocycle content in samples. A variety of compounds were studied. These include thiophene, thiophene derivatives, tetranydrothiophene, several more complex saturated and unsaturated sulfur heterocycles, and heterocycles containing both sulfur and nitrogen. The sulfur-K/β /sub spectra were obtained using a double crystal spectrometer which provided an instrumental resolution of about 0.7 eV

Geologic environmental study

Energy Technology Data Exchange (ETDEWEB)

Kim, Chun Soo; Bae, Dae Seok; Kim, Kyung Su; Park, Byung Yoon; Koh, Young Kown; Chun, Kwan Sik; Kim, Jhin Wung

2000-05-01

The geoscience research works are focused on the production of geologic basic data accompanying with the technical development of geology and hydrogeologic characterization. The lithology of the Korean peninsula consists of a complex structure of 29 rock types from Archean to Quaternary. The wide distribution of Mesozoic plutonic rock is an important consideration as a potential host rock allowing flexibility of siting. The recent tectonic activities are limited to localized particular area, which can be avoided by excluding in the early stage of siting. Three rock types such as plutonic rocks, crystalline gneisses and massive volcanic rocks were suggested as the preferred host rocks for the further study on HLW disposal system. This report contains grouping of regional faults, and on the distributional characteristics of faults and fractures(zones) in terms of lithological domain and tectonical provinces. The regional groundwater regime can be grouped into 3 regimes by tectonic setting and four groundwater regions based on an altitute. Groundwaters can be grouped by their chemistry and host rocks. The origin of groundwater was proposed by isotope ({sup 1}8O, {sup 2}H, {sup 1}3C, {sup 3}4S, {sup 8}7Sr, {sup 1}5N) studies and the residence time of groundwater was inferred from their tritium contents. Based on the geochemical and isotope characteristics, the geochemical evolutions of each types of groundwater were simulated using SOLVEQ/CHILLER and PHREEQC programs.

Evolution of the magmatic-hydrothermal acid-sulfate system at Summitville, Colorado: Integration of geological, stable-isotope, and fluid-inclusion evidence

Science.gov (United States)

Bethke, P.M.; Rye, R.O.; Stoffregen, R.E.; Vikre, P.G.

2005-01-01

The Summitville Au-Ag-Cu deposit is a classic volcanic dome-hosted high-sulfidation deposit. It occurs in the Quartz Latite of South Mountain, a composite volcanic dome that was emplaced along the coincident margins of the Platoro and Summitville calderas at 22.5??0.5 Ma, penecontemporaneous with alteration and mineralization. A penecontemporaneous quartz monzonite porphyry intrusion underlies the district and is cut and overlain by pyrite-quartz stockwork veins with traces of chalcopyrite and molybdenite. Alteration and mineralization proceeded through three hypogene stages and a supergene stage, punctuated by at least three periods of hydrothermal brecciation. Intense acid leaching along fractures in the quartz latite produced irregular pipes and lenticular pods of vuggy silica enclosed sequentially by alteration zones of quartz-alunite, quartz-kaolinite, and clay. The acid-sulfate-altered rocks host subsequent covellite+enargite/luzonite+chalcopyrite mineralization accompanied by kaolinite, and later barite-base-metal veins, some containing high Au values and kaolinite. The presence of both liquid- and vapor-rich fluid inclusions indicates the episodic presence of a low-density fluid at all levels of the system. In the mineralized zone, liquid-rich fluid inclusions in healed fractures in quartz phenocrysts and in quartz associated with mineralization homogenize to temperatures between 160 and 390 ??C (90% between 190 and 310 ??C), consistent with the range (200-250 ??C) estimated from the fractionation of sulfur isotopes between coexisting alunite and pyrite. A deep alunite-pyrite pair yielded a sulfur-isotope temperature of 390 ??C, marking a transition from hydrostatic to lithostatic pressure at a depth of about 1.5 km. Two salinity populations dominate the liquid-rich fluid inclusions. One has salinities between 0 and 5 wt.% NaCl equivalent; the other has salinities of up to 43 wt.% NaCl equivalent. The occurrence of high-salinity fluid inclusions in vein

Geological, geochemical and isotopic characteristics of the Archaean Kaap Valley pluton, Barberton mountain land, South Africa

International Nuclear Information System (INIS)

Robb, L.J.; Barton, J.M. Jr.; Kable, E.J.D.; Wallace, R.C.

1984-01-01

The Kaap Valley pluton consists predominantly of a homogeneous weakly foliated, hornblende-bearing tonalite. It is among the oldest granitoid bodies yet recognized in the environs of the Barberton greenstone belt, yielding 207 Pb/ 206 Pb mineral ages of about 3300 Ma and a Rb-Sr whole rock isochron age of about 3500 Ma. The Kaap Valley pluton is distinctive in many respects. Whereas all other gneiss plutons in the area are characterized by a trondhjemitic bulk composition with mafic mineralogies dominated by biotite, the Kaap Valley pluton is tonalitic in bulk composition with hornblende (plus minus minor biotite) as its major mafic phase. In this paper, the results of a detailed geological, geochemical and Pb-isotopic study of the Kaap Valley pluton are presented. Questions relating to the origin of the body are considered, with an emphasis on the formation of a tonalitic magma which is more mafic than those typically encountered in the region. Although exposure does not permit a detailed structural study of the gneiss pluton consideration is given to its mode of emplacement

Iron isotopic systematics of oceanic basalts

Science.gov (United States)

Teng, Fang-Zhen; Dauphas, Nicolas; Huang, Shichun; Marty, Bernard

2013-04-01

The iron isotopic compositions of 93 well-characterized basalts from geochemically and geologically diverse mid-ocean ridge segments, oceanic islands and back arc basins were measured. Forty-three MORBs have homogeneous Fe isotopic composition, with δ56Fe ranging from +0.07‰ to +0.14‰ and an average of +0.105 ± 0.006‰ (2SD/√n, n = 43, MSWD = 1.9). Three back arc basin basalts have similar δ56Fe to MORBs. By contrast, OIBs are slightly heterogeneous with δ56Fe ranging from +0.05‰ to +0.14‰ in samples from Koolau and Loihi, Hawaii, and from +0.09‰ to +0.18‰ in samples from the Society Islands and Cook-Austral chain, French Polynesia. Overall, oceanic basalts are isotopically heavier than mantle peridotite and pyroxenite xenoliths, reflecting Fe isotope fractionation during partial melting of the mantle. Iron isotopic variations in OIBs mainly reflect Fe isotope fractionation during fractional crystallization of olivine and pyroxene, enhanced by source heterogeneity in Koolau samples.

Geological interpretation of Eastern Cuba Laterites from an airborne magnetic and radioactive isotope survey

Energy Technology Data Exchange (ETDEWEB)

Batista, J.A; Blanco, J [Departamento de Geologia, Instituto Superior Minero Metalurgico de Moa, (Cuba); Perez-Flores, M.A [Centro de Investigacion Cientifica y Educacion Superior de Ensenada, Baja California (Mexico)

2008-04-15

In eastern Cuba area several geophysical techniques have been applied to distinguish the main geological characteristics of the laterites which are of economical importance for the extraction of iron, nickel and chrome. The geophysical measurements include an aeromagnetic survey and thorium (eTh), potassium (K) and uranium (eU) isotope measurements. The results of gamma spectrometer measurements make a distinction between laterite reservoirs. The application of the magnetic and isotope methods allowed the determination of the distribution and development of the laterite crust, as well as the determination of hydrothermal alterations affecting the laterites, which is very useful for mining exploration and exploitation. Such alterations indicate the presence of silicates, which have negative effects on the metallurgic process. It is known that laterite crust has a high content of eU and eTh. [Spanish] Se han utilizado varias tecnicas geofisicas en la region oriental de Cuba para distinguir las principales caracteristicas geologicas de las lateritas, que poseen importancia economica para la extraccion de hierro, niquel y cobalto. Las mediciones geofisicas incluyen un estudio aeromagnetico y mediciones de isotopos de torio (eTh), potasio (K) y uranio (eU). Los resultados de las mediciones espectrometricas establecen diferencias entre los yacimientos de lateritas. De la aplicacion del metodo magnetico e isotopico se determino la distribucion y desarrollo de las cortezas lateriticas, asi como la ubicacion de alteraciones hidrotermales que afectan a las lateritas, lo cual es muy util durante la exploracion y explotacion minera. Esas alteraciones indican la presencia de silicatos, que tienen un efecto negativo en el proceso metalurgico. Se conoce que las cortezas lateriticas tienen altos contenidos de eU y eTh. De los contenidos de eU y eTh se infiere que las lateritas de la region de Moa se formaron antes que las de Mayari. De estas mediciones fue posible inferir el

Graphene-wrapped sulfur nanospheres with ultra-high sulfur loading for high energy density lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Ya; Guo, Jinxin; Zhang, Jun, E-mail: zhangjun@zjnu.cn; Su, Qingmei; Du, Gaohui, E-mail: gaohuidu@zjnu.edu.cn

2015-01-01

Graphical abstract: - Highlights: • A graphene-wrapped sulfur nanospheres composite with 91 wt% S is prepared. • It shows highly improved electrochemical performance as cathode for Li–S cell. • The PVP coating and conductive graphene minimize polysulfides dissolution. • The flexible coatings with void space accommodate the volume expansion of sulfur. - Abstract: Lithium–sulfur (Li–S) battery with high theoretical energy density is one of the most promising energy storage systems for electric vehicles and intermittent renewable energy. However, due to the poor conductivity of the active material, considerable weight of the electrode is occupied by the conductive additives. Here we report a graphene-wrapped sulfur nanospheres composite (S-nanosphere@G) with sulfur content up to 91 wt% as the high energy density cathode material for Li–S battery. The sulfur nanospheres with diameter of 400–500 nm are synthesized through a solution-based approach with the existence of polyvinylpyrrolidone (PVP). Then the sulfur nanospheres are uniformly wrapped by conductive graphene sheets through the electrostatic interaction between graphene oxide and PVP, followed by reducing of graphene oxide with hydrazine. The design of graphene wrapped sulfur nanoarchitecture provides flexible conductive graphene coating with void space to accommodate the volume expansion of sulfur and to minimize polysulfide dissolution. As a result, the S-nanosphere@G nanocomposite with 91 wt% sulfur shows a reversible initial capacity of 970 mA h g{sup −1} and an average columbic efficiency > 96% over 100 cycles at a rate of 0.2 C. Taking the total mass of electrode into account, the S-nanosphere@G composite is a promising cathode material for high energy density Li–S batteries.

Multiple-heteroatom-containing sulfur compounds in a high sulfur coal

International Nuclear Information System (INIS)

Winans, R.E.; Neill, P.H.

1990-01-01

Flash vacuum pyrolysis of a high sulfur coal has been combined with high resolution mass spectrometry yielding information on aromatic sulfur compounds containing an additional heteroatom. Sulfur emission from coal utilization is a critical problem and in order to devise efficient methods for removing organic sulfur, it is important to know what types of molecules contain sulfur. A high sulfur Illinois No. 6 bituminous coal (Argonne Premium Coal Sample No. 3) was pyrolyzed on a platinum grid using a quartz probe inserted into a modified all glass heated inlet system and the products characterized by high resolution mass spectrometry (HRMS). A significant number of products were observed which contained both sulfur and an additional heteroatom. In some cases two additional heteroatoms were observed. These results are compared to those found in coal extracts and liquefaction products

Evaporite-hosted native sulfur in Trans-Pecos Texas: Relation to late-phase basin and range deformation

International Nuclear Information System (INIS)

Hentz, T.F.; Henry, C.D.

1989-01-01

Major deposits of biogenic native sulfur are associated with narrow, northeast-trending grabens and normal faults that disrupt the gently tilted, east-dipping Upper Permian evaporite succession of the western Delaware Basin in Trans-Pecos Texas. Orebodies are restricted to geologic traps in the fractured and dissolution-modified downfaulted blocks of the grabens. Other parallel, regionally distributed grabens and normal faults are commonly the sites of noncommercial sulfur deposits and genetically related secondary-replacement (diagenetic) limestone bodies. The sulfur-bearing structures probably formed during the later of two episodes of Basin and Range extension that have not previously been differentiated in Texas but are well defined elsewhere in the western United States. In Texas several lines of evidence collectively support the existence of late-phase, northwest-directed extension that was initiated in the middle Miocene

Isotopic dilution methods to determine the gross transformation rates of nitrogen, phosphorus, and sulfur in soil: a review of the theory, methodologies, and limitations

International Nuclear Information System (INIS)

Di, H. J.; Cameron, K. C.; McLaren, R. G.

2000-01-01

The rates at which nutrients are released to, and removed from, the mineral nutrient pool are important in regulating the nutrient supply to plants. These nutrient transformation rates need to be taken into account when developing nutrient management strategies for economical and sustainable production. A method that is gaining popularity for determining the gross transformation rates of nutrients in the soil is the isotopic dilution technique. The technique involves labelling a soil mineral nutrient pool, e.g. NH 4 + , NO 3 - , PO 4 3- , or SO 4 2- , and monitoring the changes with time of the size of the labelled nutrient pool and the excess tracer abundance (atom %, if stable isotope tracer is used) or specific activity (if radioisotope is used) in the nutrient pool. Because of the complexity of the concepts and procedures involved, the method has sometimes been used incorrectly, and results misinterpreted. This paper discusses the isotopic dilution technique, including the theoretical background, the methodologies to determine the gross flux rates of nitrogen, phosphorus, and sulfur, and the limitations of the technique. The assumptions, conceptual models, experimental procedures, and compounding factors are discussed. Possible effects on the results by factors such as the uniformity of tracer distribution in the soil, changes in soil moisture content, substrate concentration, and aeration status, and duration of the experiment are also discussed. The influx and out-flux transformation rates derived from this technique are often contributed by several processes simultaneously, and thus cannot always be attributed to a particular nutrient transformation process. Despite the various constraints or possible compounding factors, the technique is a valuable tool that can provide important quantitative information on nutrient dynamics in the soil-plant system. Copyright (2000) CSIRO Publishing

Insight into the loading temperature of sulfur on sulfur/carbon cathode in lithium-sulfur batteries

International Nuclear Information System (INIS)

Ye, Huan; Yin, Ya-Xia; Guo, Yu-Guo

2015-01-01

Highlights: • A cost-effective chemical activation method to prepare porous carbon nanospheres. • Carbon nanospheres with bimodal microporous structure show high specific area and large micropore volume. • The S/C composite cathodes with in-situformed S−C bond exhibit high sulfur activity with a reversible capacity of 1000 mA h g −1 . • S−C bond enables well confinement on sulfur and polysulfides. - Abstract: Lithium–sulfur batteries are highly desired because of their characteristics such as high energy density. However, the applications of Li-S batteries are limited because they exist dissolution of polysulfides into electrolytes. This study reports the preparation of sulfur cathodes by using bimodal microporous (0.5 nm and 0.8 nm to 2.0 nm) carbon spheres with high specific area (1992 m 2 g −1 ) and large micropore volume (1.2 g cm −1 ), as well as the encapsulation of polysulfides via formation of carbon–sulfur bonds in a sealed vacuum glass tube at high temperature. Given that sulfur and polysulfides are well confined by the S−C bond, the shuttle effect is effectively suppressed. The prepared S/C cathodes with a sulfur loading of up to 75% demonstrate high sulfur activity with reversible capacity of 1000 mA h g −1 at the current density of 0.1 A g −1 and good cycling stability (667 mA h g −1 after 100 cycles).

Role of Sulfur in the Formation of Magmatic-Hydrothermal Copper-Gold Deposits

Science.gov (United States)

Seo, J.; Guillong, M.; Heinrich, C.

2009-05-01

recent laboratory experiments [4], indicating that sulfur is the key component determining the efficiency of ore formation in porphyry-style and epithermal systems. [1] Heinrich et al. (1999) Geology [2] Guillong et al. (2008) J.Anal. At. Spectrom. [3] Seo et al. (2009) Earth Planet. Sci. Lett. in review. [4] Pokrovski et al. (2008) Earth Planet. Sci. Lett.

Improved method for minimizing sulfur loss in analysis of particulate organic sulfur.

Science.gov (United States)

Park, Ki-Tae; Lee, Kitack; Shin, Kyoungsoon; Jeong, Hae Jin; Kim, Kwang Young

2014-02-04

The global sulfur cycle depends primarily on the metabolism of marine microorganisms, which release sulfur gas into the atmosphere and thus affect the redistribution of sulfur globally as well as the earth's climate system. To better quantify sulfur release from the ocean, analysis of the production and distribution of organic sulfur in the ocean is necessary. This report describes a wet-based method for accurate analysis of particulate organic sulfur (POS) in the marine environment. The proposed method overcomes the considerable loss of sulfur (up to 80%) that occurs during analysis using conventional methods involving drying. Use of the wet-based POS extraction procedure in conjunction with a sensitive sulfur analyzer enabled accurate measurements of cellular POS. Data obtained using this method will enable accurate assessment of how rapidly sulfur can transfer among pools. Such information will improve understanding of the role of POS in the oceanic sulfur cycle.

Preparation and use of nitrogen (2) oxide of special purity for production of oxygen and nitrogen isotopes

International Nuclear Information System (INIS)

Polevoj, A.S.

1989-01-01

Problems related with production of oxygen and nitrogen isotopes by means of low-temperature rectification of nitrogen (2) oxide are analyzed. Special attention, in particular, is payed to the techniques of synthesis and high purification of initial NO, utilization of waste flows formed during isotope separation. Ways to affect the initial isotope composition of nitrogen oxide and the rate of its homogeneous-isotope exchange, which provide for possibility of simultaneous production of oxygen and nitrogen isotopes by means of NO rectification, are considered. Description of a new technique for high purification of nitrogen oxide, prepared at decomposition of nitric acid by sulfurous anhydride, suggested by the author is presented

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

Science.gov (United States)

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

2016-01-01

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

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

Science.gov (United States)

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

2016-01-01

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

Stable isotope sales: Mound Laboratory customer and shipment summaries, FY 1976 and FY 1976A

International Nuclear Information System (INIS)

Ruwe, A.H. Jr.

1977-01-01

A listing is given of Mound Laboratory's sales of stable isotopes of noble gases, carbon, oxygen, nitrogen, chlorine, and sulfur for fiscal years 1976 and 1976A (the period July 1, 1975 through September 30, 1976). Purchasers are listed alphabetically and are divided into domestic and foreign groups. A cross-reference index by location is included for domestic customers. Cross-reference listings by isotope purchased are included for all customers

Isotopic analysis of boron by thermal ionization mass spectrometry

International Nuclear Information System (INIS)

Kakazu, M.H.; Sarkis, J.E.S.; Souza, I.M.S.

1991-07-01

This paper presents a methodology for isotopic analysis of boron by thermal ionization mass spectrometry technique through the ion intensity measurement of Na 2 BO + 2 in H 3 BO 3 , B o and B 4 C. The samples were loaded on single tantalum filaments by different methods. In the case of H 3 BO 3 , the method of neutralization with NaOH was used. For B 4 C the alcaline fusion with Na 2 CO 3 and for B o dissolution with 1:1 nitric sulfuric acid mixture followed by neutralization with NaOH was used. The isotopic ratio measurements were obtained by the use of s Faraday cup detector with external precision of ±0,4% and accuracy of ±0,1%, relative to H 3 BO 3 isotopic standard NBS 951. The effects of isotopic fractionation was studied in function of the time during the analyses and the different chemical forms of deposition. (author)

Isotope studies to determine dry deposition of sulfate to deciduous and coniferous trees: Final draft

International Nuclear Information System (INIS)

Garten, C.T. Jr.

1988-01-01

Experiments have been conducted at two locations near Oak Ridge, Tennessee, with radioactive 35 S (87 day half-life) to examine the cycling behavior of sulfur in yellow poplar (Liriodendron tulipifera), red maple (Acer rubrum), and loblolly pine (Pinus taeda) trees. Some findings pertain to methods development for estimating dry deposition of sulfur to forest canopies and the magnitude of sulfur emissions from natural sources (Task II). We will determine through field studies, the internal cycling, storage, and biogenic emission of sulfur, as traced by 35 SO 4 2- , in environments impacted by atmospheric sulfate deposition; and will determine through isotope dilution studies, the contribution of foliar leaching and dry deposition to net throughfall (NTF) sulfate concentrations beneath deciduous and coniferous trees in such environments. 3 refs., 2 figs., 1 tab

Applications of stable isotope analysis in foodstuffs surveillance and environmental research

International Nuclear Information System (INIS)

Pichlmayer, F.; Blochberger, F.

1991-12-01

The instrumental coupling of Elemental Analysis and Mass Spectrometry, constituting a convenient tool for isotope ratio measurements of the bioelements in solid or liquid samples is now well established. Advantages of this technique compared with the so far usual wet chemistry sample preparation are: speed of analysis, easy operation and minor sample consumption. The performance of the system is described and some applications are given. Detection of foodstuffs adulterations is mainly based on the natural carbon isotope differences between C 3 - and C 4 -plants. In the field of environmental research the existing small isotopic variations of carbon, nitrogen and sulfur in nature, which depend on substance origin and history, are used as intrinsic signature of the considered sample. Examples of source appointment or exclusion by help of this natural isotopic tracer method are dealt with. (authors)

Sulfur-Containing Agrochemicals.

Science.gov (United States)

Devendar, Ponnam; Yang, Guang-Fu

2017-10-09

Modern agricultural chemistry has to support farmers by providing innovative agrochemicals. In this context, the introduction of sulfur atoms into an active ingredient is still an important tool in modulating the properties of new crop-protection compounds. More than 30% of today's agrochemicals contain at least one sulfur atom, mainly in fungicides, herbicides and insecticides. A number of recently developed sulfur-containing agrochemical candidates represent a novel class of chemical compounds with new modes of action, so we intend to highlight the emerging interest in commercially active sulfur-containing compounds. This chapter gives a comprehensive overview of selected leading sulfur-containing pesticidal chemical families namely: sulfonylureas, sulfonamides, sulfur-containing heterocyclics, thioureas, sulfides, sulfones, sulfoxides and sulfoximines. Also, the most suitable large-scale synthetic methods of the recently launched or provisionally approved sulfur-containing agrochemicals from respective chemical families have been highlighted.

Proceedings of the 39. Brazilian congress on geology. v. 6

International Nuclear Information System (INIS)

1996-01-01

The book presents the 39. Brazilian Congress on Geology works, occurred in Salvador, Bahia, during the period of September 1 to 6, 1996. The meeting main subject - geology and society - reflects the current change epoch. The symposiums revealed the more important actions about geosciences applications to the society in the country. The round tables, structured for the polemical subject debates that involve the geosciences and the mineral sector crisis aspects, were achieved by several invited participants completely embraced with the subject. During the congress activities development there were some courses, technical excursions and external actions in Salvador, aiming to show the geosciences role to the social welfare. This volume focuses papers about geology and metallogenesis from high degree metamorphic terrain and isotope applications in geology

Isotopic abundance in atom trap trace analysis

Science.gov (United States)

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 Stanford-U.S. Geological Survey SHRIMP ion microprobe--a tool for micro-scale chemical and isotopic analysis

Science.gov (United States)

Bacon, Charles R.; Grove, Marty; Vazquez, Jorge A.; Coble, Matthew A.

2012-01-01

Answers to many questions in Earth science require chemical analysis of minute volumes of minerals, volcanic glass, or biological materials. Secondary Ion Mass Spectrometry (SIMS) is an extremely sensitive analytical method in which a 5–30 micrometer diameter "primary" beam of charged particles (ions) is focused on a region of a solid specimen to sputter secondary ions from 1–5 nanograms of the sample under high vacuum. The elemental abundances and isotopic ratios of these secondary ions are determined with a mass spectrometer. These results can be used for geochronology to determine the age of a region within a crystal thousands to billions of years old or to precisely measure trace abundances of chemical elements at concentrations as low as parts per billion. A partnership of the U.S. Geological Survey and the Stanford University School of Earth Sciences operates a large SIMS instrument, the Sensitive High-Resolution Ion Microprobe with Reverse Geometry (SHRIMP–RG) on the Stanford campus.

Geology and development: proceedings of the 40. Brazilian congress on geology; EXPOGEO 98 - Brazilian exposition of Geology. Abstracts

International Nuclear Information System (INIS)

1998-01-01

The proceedings of the 40. Brazilian Congress on Geology register relevant papers on the nuclear and energy areas. The papers devoted to the nuclear area covers the following subjects: geochronology; stratigraphy; geochemistry; age estimation; isotope dating; litogeochemistry; mineralization; uranium deposits; crystallization; environmental impacts related to the uranium mines and the non nuclear mining industries; petrogenesis; paleoclimatology; natural radioactivity; spectrometry; and the uranium extraction. The articles on the energy area are referent to the petroleum, coal and natural gas exploration; environmental impacts related to the oil spilling; and the history and the perspectives of the petroleum exploration in Brazil

USE OF SLACK-WATER ENVIRONMENTS BY COHO SALMON JUVENILES IN A COASTAL OREGON STREAM AS INDICATED BY 34S STABLE ISOTOPE ANALYSIS

Science.gov (United States)

Stable isotopes of sulfur are rarely used in studies of elemental cycling, trophic position or use of marine-derived nutrients by salmonids. The main reason for this probably is the reluctance on the part of isotope labs to expose their instruments to SO2 (because of its corrosi...

Stable isotope sales: Mound Laboratory customer and shipment summaries, FY 1976 and FY 1976A

Energy Technology Data Exchange (ETDEWEB)

Ruwe, A.H. Jr. (comp.)

1977-06-06

A listing is given of Mound Laboratory's sales of stable isotopes of noble gases, carbon, oxygen, nitrogen, chlorine, and sulfur for fiscal years 1976 and 1976A (the period July 1, 1975 through September 30, 1976). Purchasers are listed alphabetically and are divided into domestic and foreign groups. A cross-reference index by location is included for domestic customers. Cross-reference listings by isotope purchased are included for all customers.

Determination of uranium, thorium and radium isotope ratio

International Nuclear Information System (INIS)

Sokolova, Z.A.

1983-01-01

The problems connected with the study of isotope composition of natural radioactive elements in natural objects are considered. It is pointed out that for minerals, ores and rocks the following ratios are usually determined: 234 U/ 238 U, 230 Th/ 238 U, 226 Ra/ 238 U, 228 Th/ 230 Th, 228 Th/ 232 Th and lead isotopes; for natural waters, besides the enumerated - 226 Ra/ 228 Ra. General content of uranium and thorium in the course of isotope investigations is determined from separate samples, most frequently by the X-ray spectral method, radium content - by usual radiochemical method, uranium and radium content in waters -respectively by calorimetric and emanation methods. Radiochemical preparation of geologic powder and aqueous samples for isotope analysis is described in detail. The technique of measuring and calculating isotope ratios (α-spectrometry for determining isotope composition of uranium and thorium and emanation method for determining 226 Ra/ 228 Ra) is presented

Isotope effects associated with the anaerobic oxidation of sulfide by the purple photosynthetic bacterium, Chromatium vinosum

International Nuclear Information System (INIS)

Fry, B.; Gest, H.; Hayes, J.M.

1984-01-01

Small inverse isotope effects of 1-3 per thousand were consistently observed for the oxidation of sulfide to elemental sulfur during anaerobic photometabolism by Chromatium vinosum. The inverse fractionation can be accounted for by an equilibrium isotope effect between H 2 S and HS - , and may indicate that C. vinosum (and other photosynthetic bacteria) utilizes H 2 S rather than HS - as the substrate during sulfide oxidation. (Auth.)

Nature and origin of the nonsulfide zinc deposits in the Sierra Mojada District, Coahuila, Mexico: constraints from regional geology, petrography, and isotope analyses

Science.gov (United States)

Kyle, J. Richard; Ahn, Hyein; Gilg, H. Albert

2018-02-01

The Sierra Mojada District comprises multiple types of near-surface mineral concentrations ranging from polymetallic sulfide zones, "nonsulfide Zn" (NSZ) deposits, and a silver-rich Pb carbonate deposit hosted by lower Cretaceous carbonate strata. Hypogene concentrations of Fe-Zn-Pb-Cu-Ag sulfides and sulfosalts are locally preserved and are associated with hydrothermal dolomite and silica. Alteration mineralogy and sulfur isotope data suggest primary Zn-Pb-Ag mineralization from circa 200 °C hydrothermal fluids. The NSZ deposits dominantly consist of smithsonite and hemimorphite associated with local Mn-Fe oxides. The Red Zinc Zone consists of strata-bound zones dominantly of hemimorphite that fills pores in residual and resedimented Fe oxides. The White Zinc Zone shows local dissolution features, including internal sediments interbanded with and cemented by smithsonite. Similar Pb isotopic compositions of smithsonite, hemimorphite, and cerussite to Sierra Mojada galena document that the NSZ deposits originated from polymetallic carbonate-replacement sulfide deposits, with flow of metal-bearing groundwater being controlled by local topography and structural features in this extensional terrane. Oxygen isotope values for Sierra Mojada smithsonite are relatively constant (δ18OVSMOW = 20.9 to 23.3‰) but are unusually low compared to other supergene smithsonites. Using δ18OVSMOW (- 8‰) of modern groundwater at nearby Cuatrociénegas, smithsonite formational temperatures are calculated to have been between 26 to 35 °C. Smithsonite precipitation was favored by near-neutral conditions typical of carbonate terranes, whereas hemimorphite precipitated by reaction with wallrock silica and locally, or episodically, more acidic conditions resulting from sulfide oxidation. Transition to, and stabilization of, the modern desert climate over the past 9000 years from the Late Pleistocene wetter, cooler climate of northern Mexico resulted in episodic drawdown of the water

Catalyst for the reduction of sulfur dioxide to elemental sulfur

Science.gov (United States)

Jin, Y.; Yu, Q.; Chang, S.G.

1996-02-27

The inventive catalysts allow for the reduction of sulfur dioxide to elemental sulfur in smokestack scrubber environments. The catalysts have a very high sulfur yield of over 90% and space velocity of 10,000 h{sup {minus}1}. They also have the capacity to convert waste gases generated during the initial conversion into elemental sulfur. The catalysts have inexpensive components, and are inexpensive to produce. The net impact of the invention is to make this technology practically available to industrial applications. 21 figs.

Isotopes in the earth sciences

Energy Technology Data Exchange (ETDEWEB)

Bowen, Robert

1988-01-01

This book examines significant aspects of isotope applications in geology and geochemistry commencing with basic matters, such as atomic structure, stable nuclides and their fractionation, as well as the various decay modes of unstable nuclides. Modern mass spectrometry techniques including electrostatic tandem accelerators are followed by a review of radioisotope dating technology. The relatively new method using the rare earth elements samarium and neodymium are covered. Other geochronometers, applicable to both rocks and minerals not dateable otherwise, are included. A review is given of isotopes in the atmosphere, hydrosphere and lithosphere of the Earth. Those of oxygen and hydrogen together with the cosmogenic radionuclides tritium and radiocarbon are discussed in relation to the biosphere. The role of isotopes of carbon, nitrogen and sulphur is described and extended to fossil fuels and rocks as well as meteorites. Related themes such as Phanerozoic oceans, oceanic palaeothermometry, snow and ice stratigraphy and geothermal waters are covered. The field of isotopic palaeoecology is discussed. Radioactive wastes, their accumulation, dangers and disposal are investigated with especial reference to their environmental impacts.

Stable isotopic composition of East African lake waters

International Nuclear Information System (INIS)

Odada, E.O.

2001-01-01

The investigation of stable isotopic composition of East African lake waters was conducted by scientists from the Department of Geology, University of Nairobi, as part of the International Decade for the East African Lakes (IDEAL) project and in close collaboration with the scientists from Large Lakes Observatory of the University of Minnesota and the Isotope Hydrology Laboratory of the IAEA in Vienna. The Research Contract was part of the IAEA Co-ordinated Research Programme on Isotope Techniques in Lake Dynamics Investigations, and was sponsored by the Agency. Water and grab sediment samples were obtained from East African Lakes during the month of January and February 1994 and July/August 1995. Water samples were analysed for oxygen and deuterium isotopic composition at the IAEA Laboratories in Vienna, Austria. In this final paper we report the results of the study of oxygen and deuterium isotopic composition from the East African lake waters. (author)

Isotope geochemistry of sulfur in forest soils and in new groundwater below forest soils

International Nuclear Information System (INIS)

Mayer, B.

1993-04-01

The isotope geochemistry of sulphur in aerobic forest soils and new groundwater below forest soils was investigated for the purpose of investigating the transport and transformation behaviour of sulfate in the water-unsaturated zone. The effects of hydrodynamic and biogeochemical processes on the development of seepage water sulfate isotopes between depositions and groundwater were investigated by means of laboratory experiments, profile studies, lysimeter experiments, and field studies in order to determine the sulphur conversion processes. Dissolved sulphur from precipitates, seepage water, creek water and groundwater, as well as sulphur extracted from soil samples, were precipitated in the form of BaSO 4 or AgS 2 , decomposed thermally into SO 2 or CO 2 , and the 34 S/ 32 S and 18 O/ 16 O isotope ratios were determined by mass spectrometry. (orig.) [de

Traverse across the Nelspruit batholith and the geology of the excursion route between Sabie and Witbank

International Nuclear Information System (INIS)

Robb, L.J.; Anhaeusser, C.R.

1981-01-01

A geologic survey was done on the traverse across the Nelspruit batholith and the geology of the excursion route between Sabie and Witbank. Rubidium isotopes, strontium 86 and strontium 87 were used to determine the rock age. The petrogenetic aspects relating to the Nelspruit batholith were also studied

The Application of Stable Isotopes for Assessing the Hydrological, Sulfur, and Iron Balances of Acidic Mining Lake ML 111 (Lusatia, Germany) as a Basis for Biotechnological Remediation

International Nuclear Information System (INIS)

Knoeller, K.; Strauch, G.

2002-01-01

Stable isotope (δ 18 O-H 2 O, δ 2 H-H 2 O δ 34 S-SO 4 2- ) and hydrochemical data (SO 4 2- , Fe-concentrations) have been used to estimate the annual groundwater inflow and outflow of mining lake ML 111 and to calculate the total amount of dissolved sulfate and iron that is carried into the lake by groundwater. The hydrological balance suggests an annual groundwater inflow of 23 700 m 3 and an annual groundwater outflow of 15 700 m 3 . The calculation of the sulfur and iron balances yielded an annual sulfate input of 37 800 kg and an annual iron input of 7000 kg with the groundwater inflow. Furthermore it was shown that significant fluxes of these elements go into the lake sediments which results in continuous release of acidity in the lake water

Noble Gas Isotope Evidence for Mantle Volatiles in the Cu-Mo Porphyry and Main Stage Polymetallic Veins at Butte, Montana

Science.gov (United States)

Hofstra, A. H.; Rusk, B. G.; Manning, A. H.; Hunt, A. G.; Landis, G. P.

2017-12-01

Recent studies suggest that volatiles released from mafic intrusions may be important sources of heat, sulfur, and metals in porphyry Cu-Mo-Au and epithermal Au-Ag deposits associated with intermediate to silicic stocks. The huge Cu-Mo porphyry and Main Stage polymetallic vein deposits at Butte are well suited to test this hypothesis because there is no geologic or isotopic evidence of basaltic intrusions in the mine or drill holes. The Butte porphyry-vein system is associated with quartz monzonite stocks and dikes within the southwest part of the Late Cretaceous Boulder batholith. The Boulder batholith was emplaced into Mesoproterozoic to Mesozoic sedimentary rocks and Late Cretaceous volcanic rocks. The Boulder batholith and Butte intrusions have Sri and eNd values indicative of crustal contamination. Eu and Ce anomalies in zircon from Butte intrusions provide evidence of oxidation due to magma degassing. To ascertain the source of volatiles in this system, 11 samples from the Cu-Mo porphyry and 16 from Main Stage veins were selected. The isotopic composition of Ar, Ne, and He extracted from fluid inclusions in quartz, magnetite, pyrite, chalcopyrite, sphalerite, galena, enargite, and covellite were determined. Helium isotopes exceed blank levels in all samples and Ne and Ar in some samples. On a 38Ar/36Ar vs. 40Ar/36Ar diagram, data plot near air. On a 20Ne/22Ne vs. 21Ne/22Ne diagram, data extend from air along the trajectories of OIB and MORB. On a 36Ar/4He vs. 3He/4He RA diagram, data extend from crust toward the air-mantle mixing line. The maximum 3He/4He RA values in the Cu-Mo porphyry (2.86) and Main Stage veins (3.46) are from pyrite and these values correspond to 36 and 43 % mantle helium. The Ne and He results show that fluid inclusions contain volatiles discharged from mantle magmas and that these volatiles were diluted by groundwater containing He derived from country rocks. Despite the lack of mafic intrusions in the Butte magmatic center, noble gas

Sulfur-binding in recent environments: II. Speciation of sulfur and iron and implications for the occurrence of organo-sulfur compounds

Science.gov (United States)

Hartgers, Walter A.; Lòpez, Jordi F.; Sinninghe Damsté, Jaap S.; Reiss, Christine; Maxwell, James R.; Grimalt, Joan O.

1997-11-01

Speciation of iron and sulfur species was determined for two recent sediments (La Trinitat and Lake Cisó) which were deposited in environments with a high biological productivity and sulfate-reducing activity. In sediments from calcite ponds of La Trinitat an excess of reactive iron species (iron monosulfides, iron hydroxides) results in a depletion of reactive sulfur which is accompanied by a virtual absence of organo-sulfur compounds, both in low (LMW) and high molecular-weight (HMW) fractions. Small amounts of phytanyl and highly branched isoprenoid (HBI) thiophenes in the extract demonstrate that these molecules exhibit a higher reactivity towards reduced sulfur species as compared to detrital iron. Euxinic sediments from Lake Cisó are characterised by an excess of reduced sulfur species which can rapidly trap reactive iron. High concentrations of H 2S results in the formation of organo-sulfur compounds which were encountered in both LMW and HMW fractions. The major part of the organic sulfur is bound to the carbohydrate portion of woody tissues, whose presence was revealed by a specific alkylthiophene distribution in the flash pyrolysate and by Li/EtNH 2 desulfurisation of the kerogen which resulted in the solubilisation of the sulfur-enriched hemicellulose fraction. Relatively high amounts of sulfurised C 25 HBI compounds in the sediment extract of Lake Cisó reflect the incorporation of sulfur into algal derived organic matter upon early diagenesis. The combined approach of the speciation of iron and sulfur species and the molecular analysis of sedimentary fractions demonstrates that abiotic sulfur binding to organic matter occurs at the earliest stages of diagenesis under specific depositional conditions (anoxic, stratified water column) in which an excess of reduced sulfur species relative to the amount of reactive iron is a controlling factor.

Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China

Energy Technology Data Exchange (ETDEWEB)

Xie Xianjun [MOE Key Laboratory of Biogeology and Environmental Geology and School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Ellis, Andre [Department of Geological Sciences, University of Texas at El Paso, TX 79968-0555 (United States); Wang Yanxin, E-mail: yx.wang@cug.edu.cn [MOE Key Laboratory of Biogeology and Environmental Geology and School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Xie Zuoming; Duan Mengyu; Su Chunli [MOE Key Laboratory of Biogeology and Environmental Geology and School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China)

2009-06-01

High arsenic groundwater in the Quaternary aquifers of Datong Basin, northern China contain As up to 1820 {mu}g/L and the high concentration plume is located in the slow flowing central parts of the basin. In this study we used hydrochemical data and sulfur isotope ratios of sulfate to better understand the conditions that are likely to control arsenic mobilization. Groundwater and spring samples were collected along two flow paths from the west and east margins of the basin and a third set along the basin flow path. Arsenic concentrations range from 68 to 670 {mu}g/L in the basin and from 3.1 to 44 {mu}g/L in the western and eastern margins. The margins have relatively oxidized waters with low contents of arsenic, relatively high proportions of As(V) among As species, and high contents of sulfate and uranium. By contrast, the central parts of the basin are reducing with high contents of arsenic in groundwater, commonly with high proportions of As(III) among As species, and low contents of sulfate and uranium. No statistical correlations were observed between arsenic and Eh, sulfate, Fe, Mn, Mo and U. While the mobility of sulfate, uranium and molybdenum is possibly controlled by the change in redox conditions as the groundwater flows towards central parts of the basin, the reducing conditions alone cannot account for the occurrence of high arsenic groundwater in the basin but it does explain the characteristics of arsenic speciation. With one exception, all the groundwaters with As(III) as the major As species have low Eh and those with As(V) have high Eh. Reductive dissolution of Fe-oxyhydroxides or reduction of As(V) are consistent with the observations, however no increase in dissolved Fe concentration was noted. Furthermore, water from the well with the highest arsenic was relatively oxidizing and contained mostly As(V). From previous work Fe-oxyhydroxides are speculated to exist as coatings rather than primary minerals. The wide range of {delta}{sup 34}S

Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China

International Nuclear Information System (INIS)

Xie Xianjun; Ellis, Andre; Wang Yanxin; Xie Zuoming; Duan Mengyu; Su Chunli

2009-01-01

High arsenic groundwater in the Quaternary aquifers of Datong Basin, northern China contain As up to 1820 μg/L and the high concentration plume is located in the slow flowing central parts of the basin. In this study we used hydrochemical data and sulfur isotope ratios of sulfate to better understand the conditions that are likely to control arsenic mobilization. Groundwater and spring samples were collected along two flow paths from the west and east margins of the basin and a third set along the basin flow path. Arsenic concentrations range from 68 to 670 μg/L in the basin and from 3.1 to 44 μg/L in the western and eastern margins. The margins have relatively oxidized waters with low contents of arsenic, relatively high proportions of As(V) among As species, and high contents of sulfate and uranium. By contrast, the central parts of the basin are reducing with high contents of arsenic in groundwater, commonly with high proportions of As(III) among As species, and low contents of sulfate and uranium. No statistical correlations were observed between arsenic and Eh, sulfate, Fe, Mn, Mo and U. While the mobility of sulfate, uranium and molybdenum is possibly controlled by the change in redox conditions as the groundwater flows towards central parts of the basin, the reducing conditions alone cannot account for the occurrence of high arsenic groundwater in the basin but it does explain the characteristics of arsenic speciation. With one exception, all the groundwaters with As(III) as the major As species have low Eh and those with As(V) have high Eh. Reductive dissolution of Fe-oxyhydroxides or reduction of As(V) are consistent with the observations, however no increase in dissolved Fe concentration was noted. Furthermore, water from the well with the highest arsenic was relatively oxidizing and contained mostly As(V). From previous work Fe-oxyhydroxides are speculated to exist as coatings rather than primary minerals. The wide range of δ 34 S [SO4] values (from

Eaglet property, southeastern British Columbia: Re-Os geochronology, sulphur isotopes, and thermobarometry

Czech Academy of Sciences Publication Activity Database

Hora, Z. D.; Stein, H.; Žák, Karel; Dobeš, P.

2018-01-01

Roč. 2017, č. 1 (2018), s. 157-166 ISSN 0381-243X Institutional support: RVO:67985831 Keywords : Eaglet deposit * MINFILE 093A 046 * fluorite * celestite * molybdenite * sulphur isotopes * Re-Os geochronology * fluid inclusion microthermobarometry Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology http://cmscontent.nrs.gov.bc.ca/geoscience/PublicationsCatalogue/Fieldwork/Documents/2017/P2018-1.pdf

Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

Science.gov (United States)

Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

2017-05-23

Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

Iridium, sulfur isotopes and rare earth elements in the Cretaceous-Tertiary boundary clay at Stevns Klint, Denmark

Science.gov (United States)

Schmitz, Birger; Andersson, Per; Dahl, Jeremy

1988-01-01

Microbial activity and redox-controlled precipitation have been of major importance in the process of metal accumulation in the strongly Ir-enriched Cretaceous-Tertiary (K-T) boundary clay, the Fish Clay, at Stevns Klint in Denmark. Two important findings support this view: 1) Kerogen, recovered by leaching the Fish Clay in HCl and HF, shows an Ir concentration of 1100 ppb; this represents about 50% of the Ir present in the bulk sample Fish Clay. Strong organometallic complexes is the most probable carrier phase for this fraction of Ir. Kerogen separated from the K-T boundary clay at Caravaca, Spain, similarly exhibits enhanced Ir concentrations. 2) Sulfur isotope analyses of metal-rich pyrite spherules, which occur in extreme abundance (about 10% by weight) in the basal Fish Clay, give a δ 34S value of -32%.. This very low value shows that sulfide formation by anaerobic bacteria was intensive in the Fish Clay during early diagenesis. Since the pyrite spherules are major carriers of elements such as Ni, Co, As, Sb and Zn, microbial activity may have played an important role for concentrating these elements. In the Fish Clay large amounts of rare earth elements have precipitated from sea water on fish scales. Analyses reveal that, compared with sea water, the Fish Clay is only about four times less enriched in sea-water derived lanthanides than in Ir. This shows that a sea-water origin is plausible for elements that are strongly enriched in the clay, but whose origin cannot be accounted for by a lithogenic precursor.

Sulfur isotope composition of orogenic spinel lherzolite massifs from Ariege (north-eastern pyrenees, France): An ion microprobe study

Energy Technology Data Exchange (ETDEWEB)

Chaussidon, M. (Centre de Recherches Petrographiques et Geochimiques, Vandoeuvre-les-Nancy (France)); Lorand, J. (Unite associee au CNRS, Paris (France))

1990-10-01

The orogenic spinel lherzolite massifs from Ariege, which represent tectonically emplaced fragments of the sub-continental upper mantle, are composed mainly of variously depleted peridotites. These rocks are crosscut by two generations of pyroxenites. The first is made up of layered pyroxenites, which are interpreted either as crystal segregates from Triassic continental tholeiites or as subducted parts of the oceanic crust re-injected within the upper mantle. The second consists of amphibole-rich dikes separated from Cretaceous alkali basalts. Forty sulfide grains, occurring either as inclusions within silicates or as interstitial grains, were investigated by ion microprobe for their sulfur isotopic compositions. Comparison between sulfide inclusions in silicates and interstitial sulfide grains strongly suggests that serpentinization and pyrenean metamorphism had no significant effect don the {delta}{sup 34}S values. Likewise, these values are broadly independent of the degree of partial melting. The negative {delta}{sup 34}S values of the massive peridotites could represent an ancient depletion event in the upper mantle. By contrast, the positive {delta}{sup 34}S values observed in the layered pryoxenites and the amphibole-rich dikes indicate that the two parent magmas had in common a mantle source variously enriched in {sup 34}S. Therefore, the present study reveals two extreme reservoirs characterized by different {delta}{sup 34}S values in the upper mantle. This range of variations can explain most {delta}{sup 34}S values found in MORB, continental tholeiites, and alkali basalts.

Isotopic study of Karst water

International Nuclear Information System (INIS)

Leskovsek-Sefman, H.

1985-01-01

Measurement of the isotopic composition of water formed part of an extended investigation of the water drainage system in the Slovenian Karst. These studies were planned to complement geological and speleological investigations which are already being performed in this area, with the knowledge of the mechanism of changes in the isotopic composition of water in the natural environment on some smaller locations, Planina cave near Postojna where the vertical percolation of meteoric water through the karstified carbonate ceiling was studied and the water catchment areas of some small rivers, Ljubljanica, Rizana and Idrijca. Mass spectrometric investigations of the isotopic composition of some elements ( 18 O, D, 13 C and T) in water and in dissolved carbonates, as well as the isotopic composition of 18 O and 13 C in cave carbonates were performed. The results allow to conclude that the waters in karst aquifers in spite of producing the homogenisation to a great extent, qualitative determination of the retention time and of the prevailing sources for some springs and surface and underground water flows is nevertheless possible. The isotopic composition of 18 O in water and of 18 O and 13 C in dissolved carbonates depends on climatic conditions and on denudation processes. The investigation of cave carbonates revealed that they have different isotopic compositions of 18 O and 13 C because of different locations and also different ages

Performance evaluation of nitrogen isotope ratio determination in marine and lacustrine sediments: An inter-laboratory comparison

NARCIS (Netherlands)

Bahlmann, E.; Bernasconi, S.M.; Bouillon, S.; Houtekamer, M.J.; Korntheuer, M.; Langenberg, F.; Mayr, C.; Metzke, M.; Middelburg, J.J.; Nagel, B.; Struck, U.; Voß, M.; Emeis, K.C.

2010-01-01

Nitrogen isotopes of organic matter are increasingly studied in marine biogeochemistry and geology, plant and animal ecology, and paleoceanography. Here, we present results of an inter-laboratory test on determination of nitrogen isotope ratios in marine and lacustrine sediments. Six different

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

Science.gov (United States)

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-06-06

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-12-26

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

Osmium isotopic tracing of atmospheric emissions from an aluminum smelter

Science.gov (United States)

Gogot, Julien; Poirier, André; Boullemant, Amiel

2015-09-01

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

Method of removing and recovering elemental sulfur from highly reducing gas streams containing sulfur gases

Science.gov (United States)

Gangwal, Santosh K.; Nikolopoulos, Apostolos A.; Dorchak, Thomas P.; Dorchak, Mary Anne

2005-11-08

A method is provided for removal of sulfur gases and recovery of elemental sulfur from sulfur gas containing supply streams, such as syngas or coal gas, by contacting the supply stream with a catalyst, that is either an activated carbon or an oxide based catalyst, and an oxidant, such as sulfur dioxide, in a reaction medium such as molten sulfur, to convert the sulfur gases in the supply stream to elemental sulfur, and recovering the elemental sulfur by separation from the reaction medium.

The life sulfuric: microbial ecology of sulfur cycling in marine sediments.

Science.gov (United States)

Wasmund, Kenneth; Mußmann, Marc; Loy, Alexander

2017-08-01

Almost the entire seafloor is covered with sediments that can be more than 10 000 m thick and represent a vast microbial ecosystem that is a major component of Earth's element and energy cycles. Notably, a significant proportion of microbial life in marine sediments can exploit energy conserved during transformations of sulfur compounds among different redox states. Sulfur cycling, which is primarily driven by sulfate reduction, is tightly interwoven with other important element cycles (carbon, nitrogen, iron, manganese) and therefore has profound implications for both cellular- and ecosystem-level processes. Sulfur-transforming microorganisms have evolved diverse genetic, metabolic, and in some cases, peculiar phenotypic features to fill an array of ecological niches in marine sediments. Here, we review recent and selected findings on the microbial guilds that are involved in the transformation of different sulfur compounds in marine sediments and emphasise how these are interlinked and have a major influence on ecology and biogeochemistry in the seafloor. Extraordinary discoveries have increased our knowledge on microbial sulfur cycling, mainly in sulfate-rich surface sediments, yet many questions remain regarding how sulfur redox processes may sustain the deep-subsurface biosphere and the impact of organic sulfur compounds on the marine sulfur cycle. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Sulfur Removal by Adding Iron During the Digestion Process of High-sulfur Bauxite

Science.gov (United States)

Zhanwei, Liu; Hengwei, Yan; Wenhui, Ma; Keqiang, Xie; Dunyong, Li; Licong, Zheng; Pengfei, Li

2018-04-01

This paper proposes a novel approach to sulfur removal by adding iron during the digestion process. Iron can react with high-valence sulfur (S2O3 2-, SO3 2-, SO4 2-) to generate S2- at digestion temperature, and then S2- enter red mud in the form of Na3FeS3 to be removed. As iron dosage increases, high-valence sulfur concentration decreases, but the concentration of S2- increases; sulfur digestion rate decreases while sulfur content in red mud markedly increases; the alumina digestion rate, conversely, remains fairly stable. So sulfur can be removed completely by adding iron in digestion process, which provide a theoretical basis for the effective removal of sulfur in alumina production process.

Nanostructured sulfur cathodes

KAUST Repository

Yang, Yuan

2013-01-01

Rechargeable Li/S batteries have attracted significant attention lately due to their high specific energy and low cost. They are promising candidates for applications, including portable electronics, electric vehicles and grid-level energy storage. However, poor cycle life and low power capability are major technical obstacles. Various nanostructured sulfur cathodes have been developed to address these issues, as they provide greater resistance to pulverization, faster reaction kinetics and better trapping of soluble polysulfides. In this review, recent developments on nanostructured sulfur cathodes and mechanisms behind their operation are presented and discussed. Moreover, progress on novel characterization of sulfur cathodes is also summarized, as it has deepened the understanding of sulfur cathodes and will guide further rational design of sulfur electrodes. © 2013 The Royal Society of Chemistry.

Ages and Growth of the Continental Crust from Radiogenic Isotopes

Science.gov (United States)

Patchett, P. J.; Samson, S. D.

2003-12-01

The development and application of radiogenic isotopes to dating of geologic events, and to questions of growth, evolution, and recycling processes in the continental crust are mature areas of scientific inquiry. By this we understand that many of the approaches used to date rocks and constrain the evolution of the continents are well established, even routine, and that the scope of data available on age and evolution of continents is very large. This is not to say that new approaches have not been developed in recent years, or that new approaches and/or insights cannot be developed in the future. However, the science of continental crustal evolution is definitely a domain where many of the problems are well defined, the power of the techniques used to solve them are well known, and the limitations of field and laboratory databases, as well as the preserved geologic record, are understood.From the very early days of crustal evolution studies, it was innovations and improvements in laboratory techniques that drove the pace of discovery (e.g., Holmes, 1911; Nier, 1939). This remained true through all the increments in capability reviewed in this chapter, up to the present day. Thus, continental crustal evolution is an area of Earth science where a species of very laboratory-oriented investigator, the "radiogenic isotope geologist" or "geochronologist," has made major advances, even breakthroughs, in understanding. This is true in spite of the fact that many of the individuals of the species may have lacked field expertise, or even more than a primitive level of geologic background. Because design and building of instruments like radiation detectors or mass spectrometers requires a knowledge of physics, many of the early practitioners of rock dating were physicists, like Alfred Nier (cited above). Since the 1970s, essentially all mass spectrometers have been constructed by specialized commercial firms, and the level of physics expertise among isotope geologists has

Validation of multi-element isotope dilution ICPMS for the analysis of basalts

Energy Technology Data Exchange (ETDEWEB)

Willbold, M.; Jochum, K.P.; Raczek, I.; Amini, M.A.; Stoll, B.; Hofmann, A.W. [Max-Planck-Institut fuer Chemie, Mainz (Germany)

2003-09-01

In this study we have validated a newly developed multi-element isotope dilution (ID) ICPMS method for the simultaneous analysis of up to 12 trace elements in geological samples. By evaluating the analytical uncertainty of individual components using certified reference materials we have quantified the overall analytical uncertainty of the multi-element ID ICPMS method at 1-2%. Individual components include sampling/weighing, purity of reagents, purity of spike solutions, calibration of spikes, determination of isotopic ratios, instrumental sources of error, correction of mass discrimination effect, values of constants, and operator bias. We have used the ID-determined trace elements for internal standardization to improve indirectly the analysis of 14 other (mainly mono-isotopic trace elements) by external calibration. The overall analytical uncertainty for those data is about 2-3%. In addition, we have analyzed USGS and MPI-DING geological reference materials (BHVO-1, BHVO-2, KL2-G, ML3B-G) to quantify the overall bias of the measurement procedure. Trace element analysis of geological reference materials yielded results that agree mostly within about 2-3% relative to the reference values. Since these results match the conclusions obtained by the investigation of the overall analytical uncertainty, we take this as a measure for the validity of multi-element ID ICPMS. (orig.)

Sulfur removal from low-sulfur gasoline and diesel fuel by metal-organic frameworks

Energy Technology Data Exchange (ETDEWEB)

Hagen, G.; Haemmerle, M.; Moos, R. [Functional Materials, University of Bayreuth, Bayreuth (Germany); Malkowsky, I.M.; Kiener, C. [BASF SE, Ludwigshafen (Germany); Achmann, S.

2010-02-15

Several materials in the class of metal-organic frameworks (MOF) were investigated to determine their sorption characteristics for sulfur compounds from fuels. The materials were tested using different model oils and common fuels such as low-sulfur gasoline or diesel fuel at room temperature and ambient pressure. Thiophene and tetrahydrothiophene (THT) were chosen as model substances. Total-sulfur concentrations in the model oils ranged from 30 mg/kg (S from thiophene) to 9 mg/kg (S from tetrahydrothiophene) as determined by elementary analysis. Initial sulfur contents of 8 mg/kg and 10 mg/kg were identified for low-sulfur gasoline and for diesel fuel, respectively, by analysis of the common liquid fuels. Most of the MOF materials examined were not suitable for use as sulfur adsorbers. However, a high efficiency for sulfur removal from fuels and model oils was noticed for a special copper-containing MOF (copper benzene-1,3,5-tricarboxylate, Cu-BTC-MOF). By use of this material, 78 wt % of the sulfur content was removed from thiophene containing model oils and an even higher decrease of up to 86 wt % was obtained for THT-based model oils. Moreover, the sulfur content of low-sulfur gasoline was reduced to 6.5 mg/kg, which represented a decrease of more than 22 %. The sulfur level in diesel fuel was reduced by an extent of 13 wt %. Time-resolved measurements demonstrated that the sulfur-sorption mainly occurs in the first 60 min after contact with the adsorbent, so that the total time span of the desulfurization process can be limited to 1 h. Therefore, this material seems to be highly suitable for sulfur reduction in commercial fuels in order to meet regulatory requirements and demands for automotive exhaust catalysis-systems or exhaust gas sensors. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate

Science.gov (United States)

Breit, G.N.; Simmons, E.C.; Goldhaber, M.B.

1985-01-01

A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87Sr 86Sr ratios by less than 0.00001 at 1.95?? of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87Sr 86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material. ?? 1985.

Determining total sulfur content in coal by MSC radiometric sulfur meter

Energy Technology Data Exchange (ETDEWEB)

Czerw, B; Sikora, T; Golebiowski, W

1976-01-01

The MSC radiometric sulfur meter is used to determine total sulfur content in brown and black coals. Sulfur content is determined by measuring intensity of radiation beam which has travelled through a coal sample with the optimum constant surface mass. Construction of the MSC, consisting of a measuring head and the electronic measuring system, is shown in a scheme. AM-241 (with activity of 50 mCi) is the source of radiation. Energy of 25.3 keV (tin disc) is selected as the optimum. The SSU-70 probe with NaJ/Tl crystal is the radiation detector. The black coal sample weighs 10 g and the brown coal sample weighs 18 g. Duration of sulfur determination is 10 min. Error of sulfur determination ranges from plus or minus 0.2% to 0.3%. The results of operational tests of MSC radiometric sulfur meters in black and brown coal mines are discussed. Accuracy of measurement is shown in 5 tables. (8 refs.)

Optically detected magnetic resonance of sulfur doped gallium phosphide

International Nuclear Information System (INIS)

Brower, K.L.

1990-01-01

The authors have recently extended our magnetic resonance capabilities to include optically detected magnetic resonance (ODMR) for purposes of studying defects in III-V compound semiconductors systems. Some of the systems of particular interest with regard to defect studies are samples implanted with particular isotopes. For example, this technique may allow one to observe the hyperfine structure of impurity donors in GaP. Other interesting material systems are the strained layer superlattices and their interfaces. GaP is one of the III-V compound semiconductors of particular interest for ODMR studies. In this paper the authors report the results of preliminary ODMR observations on as-grown sulfur doped GaP

What can Fe stable isotopes tell us about magmas?

DEFF Research Database (Denmark)

Stausberg, Niklas

the differentiation of magmas from the perspective of Fe stable isotopes, integrated with petrology, by studying igneous rocks and their constituent phases (minerals and glasses) from the Bushveld Complex, South Africa, Thingmuli, Iceland, Pantelleria, Italy, and the Bishop Tuff, USA. The findings are interpreted......The majority of the Earth’s crust is formed by magmas, and understanding their production and differentiation is important to interpret the geologic rock record. A powerful tool to investigate magmatic processes is the distribution of the stable isotopes of the major redox-sensitive element...... in magmas, Fe. Fe isotope compositions of magmatic rocks exhibit systematic differences, where the heaviest compositions are found in rhyolites and granites. Understanding of these systematics is complicated by a lack of constraints on Fe isotope fractionation among minerals and liquids under magmatic...

Stable Isotope Group 1984 progress report

International Nuclear Information System (INIS)

Lyon, G.L.

1985-04-01

The work of the group in 1984 is described and includes studies in isotope geology, isotope hydrology, geochronology, isotope biology and mass spectrometer instrumentation. Geothermal studies have decreased compared to other years, but major data summaries were made for Wairakei and Ngawha. The hydrology of Whakarewarewa and Rotorua is being elucidated using water isotopes. Models of the subsurface flows at Kawerau and Ngawha are being made to relate fluid to mineral isotope compositions. A study of the δ 13 C and δ 34 S compositions of New Zealand oils has been started. Groups of oils of related origin are being defined, and compositions will be compared with those of potential source rocks. A method was developed for isotope analysis of sulphur in rocks. The isotopic composition of water is being used to identify and characterise groundwater aquifers in the Wairarapa and at Poverty Bay. Stable carbon isotopes have been used to identify food sources for invertebrates, and to show biochemical pathways in lactation by cows. The geochronology group is involved in major studies in Antarctica, using U-Pb, Rb-Sr and K-Ar methods. Rocks from North Victoria Land, Marie Byrd Land and the USARP mountains are being compared with possible correlatives in New Zealand and Argentina. Strontium isotope data is being applied to the origin of magmas in several regions of New Zealand. The K-Ar data is being stored on computer files. Fission track measurements are being applied to unravel uplift histories in Westland and Taranaki

Testing Urey's carbonate-silicate cycle using the calcium isotopic composition of sedimentary carbonates

Science.gov (United States)

Blättler, Clara L.; Higgins, John A.

2017-12-01

Carbonate minerals constitute a major component of the sedimentary geological record and an archive of a fraction of the carbon and calcium cycled through the Earth's surface reservoirs for over three billion years. For calcium, carbonate minerals constitute the ultimate sink for almost all calcium liberated during continental and submarine weathering of silicate minerals. This study presents >500 stable isotope ratios of calcium in Precambrian carbonate sediments, both limestones and dolomites, in an attempt to characterize the isotope mass balance of the sedimentary carbonate reservoir through time. The mean of the dataset is indistinguishable from estimates of the calcium isotope ratio of bulk silicate Earth, consistent with the Urey cycle being the dominant mechanism exchanging calcium among surface reservoirs. The variability in bulk sediment calcium isotope ratios within each geological unit does not reflect changes in the global calcium cycle, but rather highlights the importance of local mineralogical and/or diagenetic effects in the carbonate record. This dataset demonstrates the potential for calcium isotope ratios to help assess these local effects, such as the former presence of aragonite, even in rocks with a history of neomorphism and recrystallization. Additionally, 29 calcium isotope measurements are presented from ODP (Ocean Drilling Program) Site 801 that contribute to the characterization of altered oceanic crust as an additional sink for calcium, and whose distinct isotopic signature places a limit on the importance of this subduction flux over Earth history.

Uranium-lead dating method at the Pará-Iso isotope geology laboratory, UFPA, Belém - Brazil

Directory of Open Access Journals (Sweden)

Robert S. Krymsky

2007-03-01

Full Text Available Analytical procedures for U-Pb isotope dilution analyses at the Pará-Iso isotope geology laboratory of the Federal University of Pará (UFPA are described in detail. The procedures are applied to zircon, titanite, rutile, apatite, columbite-tantalite and whole rock. Reagent preparation and chemical processing are done in clean-room conditions. Samples are dissolved using TeflonTM microcapsules in steel jacket TeflonTM Parr InstrumentTM bomb or TeflonTM screw cap containers. U and Pb are separated using anion exchange AG 1x8 resin columns. Typical blanks for mineral sample amounts of 0.01 to 1.0 mg are less than 1 pg U and 20-30 pg Pb. Isotope analysis of the U and Pb from the same filament are carried out using a Finnigan MAT 262 mass-spectrometer in static and dynamic modes. The current analytical level is demonstrated on analyses of international standard zircon 91500 with three different 235U-205Pb and 235U-208Pb isotope tracers and whole rock standards. Results of analyses of two zircon samples are also presented.Os procedimentos analíticos para análises U-Pb por diluição isotópica no Laboratório de Geologia Isotópica (Pará-Iso da Universidade Federal do Pará (UFPA são descritos detalhadamente. Esses procedimentos são aplicados para análises de zircão, titanita, rutilo, apatita, columbita-tantalita e rocha total. A purificação dos reagentes e os procedimentos químicos são feitos em salas limpas. As amostras são dissolvidas em microcápsulas de Teflon em bombas do tipo Parr InstrumentTM. U e Pb são separados em colunas com resina de troca iônica AG 1x8. Os brancos de procedimento para amostra típica(0,01-1 mg são menores que 1 pg de U e 20-30 pg de Pb. As análises isotópicas de Pb e de U são feitas em um único filamento de Re em um espectrômetro de massa Finnigan MAT 262 nos modos estático e dinâmico. O nível analítico atual é comprovado pelas análises do padrão internacional de zircão 91500, usando tr

Decoupling the Impacts of Heterotrophy and Autotrophy on Sulfuric Acid Speleogenesis

Science.gov (United States)

Jones, A. A.; Bennett, P.

2013-12-01

Within caves such as Movile Caves (Romania), the Frasassi Caves (Italy), and Lower Kane Cave (LKC, Wyoming, USA) the combination of abiotic autoxidation and microbiological oxidation of H2S produces SO42- and H+ that promotes limestone dissolution through sulfuric-acid speleogenesis (SAS). Microbial sulfide oxidation by sulfur-oxidizing bacteria (SOB) has been shown recently to be the dominant process leading to speleogenesis in these caves. However, due to the inherently large diversity of microbial communities within these environments, there are a variety of metabolic pathways that can impact limestone dissolution and carbon cycling to varying degrees. In order to investigate these variations we outfitted a continuous flow bioreactor with a Picarro Wavelength-Scanned Cavity Ring Down Spectrometer (WS-CRDS) that continuously monitored and logged 12CO2 and 13CO2 at ppmv sensitivity and isotope ratios at consumed resulting in lighter CO2 in the headspace. 16S rRNA sequences confirm that heterotrophic sulfur-reducing bacteria dominate the community within this reactor. When both acetate and CO2 were supplied the heterotrophic behavior appeared to dominate the system which resulted in a significant drop (15‰) in δ13C and a correlative drop in limestone dissolution rate. These results suggest that chemoautotrophy increases the rate of SAS and CO2 flux within the cave environment while heterotrophy leads to slower SAS or even calcite precipitation. Furthermore, changes in carbon substrate (CO2 vs. Acetate) or sulfur substrate concentrations caused an immediate microbial response that could be observed in all measured chemical variables.

Isotopic approach to the provenance study of artifacts

International Nuclear Information System (INIS)

Mabuchi, Hisao

1994-01-01

Isotopic abundance ratios, which are proved to be generally constant, are known to vary, for certain elements, from one place to another. Light elements, such as hydrogen, lithium, boron, carbon, nitrogen, oxygen and sulfur, show measurable variations of their isotope ratios due to isotopic fractionation which takes place during geochemical or biochemical processes. Isotope ratios of strontium and lead vary due to the decay of long-lived radioactive nuclides 87 Rb and 238 U- 235 U- 232 Th, respectively. Such isotopic anomalies can be applicable to provenance studies of archaeological objects. Thus, 13 C/ 12 C, 18 O/ 16 O, or 87 Sr/ 86 Sr were used to examine the authenticity of Greek marble statues. Also, lead isotope ratios have been used since mid-1960s extensively for provenance studies of glasses and bronzes of different civilizations. As an example, the author presents a series of his own works on lead isotope ratios applied to ancient Japanese bronzes, which are summarized as follows. 1) It was generally observed that lead isotope ratios reflect difference in culture to which bronzes belong. 2) Mirrors in the Western Han period (206 B.C. - A.D.8) are clearly distinguished by lead isotope ratios from those made after the mid-Eastern Han period (ca.A.D.150 - 300). 3) Korean mirrors and weapons excavated from the Yayoi sites contain lead of easily recognizable Mississippi Valley type. 4) Bronze objects made in Japan (imitative Han style mirrors, Dotaku, imitative weapons, arrowheads etc.) in the Yayoi and Kofun periods are classified by lead isotope ratios in the following order: the Korean mirror type to the Western Han mirror type in the Yayoi period and the mid- to post- Han mirror type in the Kofun period. 5) Indigenous Japanese lead seems to have been used after the mid-7th century. (J.P.N.)

Microbial ecology of soda lakes: investigating sulfur and nitrogen cycling at Mono Lake, CA, USA

Science.gov (United States)

Fairbanks, D.; Phillips, A. A.; Wells, M.; Bao, R.; Fullerton, K. M.; Stamps, B. W.; Speth, D. R.; Johnson, H.; Sessions, A. L.

2017-12-01

Soda lakes represent unique ecosystems characterized by extremes of pH, salinity and distinct geochemical cycling. Despite these extreme conditions, soda lakes are important repositories of biological adaptation and have a highly functional microbial system. We investigated the biogeochemical cycling of sulfur and nitrogen compounds in Mono Lake, California, located east of the Sierra Nevada mountains. Mono lake is characterized by hyperalkaline, hypersaline and high sulfate concentrations and can enter prolonged periods of meromixis due to freshwater inflow. Typically, the microbial sulfur cycle is highly active in soda lakes with both oxidation and reduction of sulfur compounds. However, the biological sulfur cycle is connected to many other main elemental cycles such as carbon, nitrogen and metals. Here we investigated the interaction between sulfur and nitrogen cycling in Mono lake using a combination of molecular, isotopic, and geochemical observations to explore the links between microbial phylogenetic composition and functionality. Metagenomic and 16S rRNA gene amplicon sequencing were determined at two locations and five depths in May 2017. 16S rRNA gene amplicon sequencing analysis revealed organisms capable of both sulfur and nitrogen cycling. The relative abundance and distribution of functional genes (dsrA, soxAB, nifH, etc) were also determined. These genetic markers indicate the potential in situ relevance of specific carbon, nitrogen, and sulfur pathways in the water column prior to the transition to meromictic stratification. However, genes for sulfide oxidation, denitrification, and ammonification were present. Genome binning guided by the most abundant dsrA sequences, GC content, and abundance with depth identified a Thioalkalivibrio paradoxus bin containing genes capable of sulfur oxidation, denitrification, and nitrate reduction. The presence of a large number of sulfur and nitrogen cycling genes associated with Thioalkalivibrio paradoxus

Introduction to chemistry and applications in nature of mass independent isotope effects special feature.

Science.gov (United States)

Thiemens, Mark H

2013-10-29

Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented.

The Etendeka lavas SWA/Namibia: geology, chemistry and spatial and temporal relationships

International Nuclear Information System (INIS)

Marsh, J.S.; Erlank, A.J.; Duncan, A.R.; Miller, R.McG.; Rex, D.C.

1981-01-01

The paper discusses a geologic survey on the Etendeka lavas in South West Africa/Namibia with special attention to the geology, chemistry and spatial and temporal relationships in the area. K/Ar age data indicate that the bulk of the Etendeka lavas are about 120 m.y. old. In the study use was also made of 87 Sr/ 86 Sr, 143 Nd/ 144 Nd, 206 Pb/ 204 Pb, 207 Pb/ 204 Pb and 208 Pb/ 204 Pb isotope ratios

Stable isotope ratio mass spectrometry in forensic science and food adulteration research

International Nuclear Information System (INIS)

Kumar, B.

2009-01-01

Stable Isotope Ratio Mass Spectrometry (SIRMS) is an established technique for the determination of origin of geological, biological, chemical and physio-chemical samples/materials. With the development of highly precise mass spectrometers, the stable isotope ratio determination of hydrogen, carbon, nitrogen and oxygen have gained considerable interest in the fields of forensic science and food authentication. Natural variations in the isotopic composition of lighter elements occur due to fractionation effects, resulting in the finger printing of specific isotope ratio values that are characteristic of the origin, purity, and manufacturing processes of the products and their constituents. Forensic science uses scientific and technical methods to investigate traceable evidence of criminal acts. Stable isotope ratio mass spectrometry has been applied to numerous aspects of the forensic science. The analysis of explosives such as ammonium nitrate, gun powder and tri-nitro-toluene (TNT), cases of murder, armed robbery, drug smuggling, terrorism, arson and hit and run traffic accidents are a few of them. The main types of geological evidences in such cases are mud, soil, rocks, sand, gravel, dust particles, biological materials, organic particles and anthropogenic components. Stable isotopes are used as tools to corroborate and confirm the evidential leads in the investigation of such crimes. The variation in natural abundances of carbon and nitrogen and their isotopic ratios δ 13 C and δ 15 N can identify links between items found at crime scene with those of suspect. The paper discusses the applications of SIRMS in the field of forensic science and food adulteration research

CHARACTERIZATION OF GEOLOGICAL MATERIALS USING ION AND PHOTON BEAMS

International Nuclear Information System (INIS)

TOROK, SZ.B.; JONES, K.W.; TUNIZ, C.

1998-01-01

Geological specimens are often complex materials that require different analytical methods for their characterization. The parameters of interest may include the chemical composition of major, minor and trace elements. The chemical compounds incorporated in the minerals, the crystal structure and isotopic composition need to be considered. Specimens may be highly heterogeneous thus necessitating analytical methods capable of measurements on small sample volumes with high spatial resolution and sensitivity. Much essential information on geological materials can be obtained by using ion or photon beams. In this chapter we describe the principal analytical techniques based on particle accelerators, showing some applications that are hardly possible with conventional methods. In particular, the following techniques will be discussed: (1) Synchrotron radiation (SR) induced X-ray emission (SRIXE) and particle-induced X-ray emission (PEE) and other ion beam techniques for trace element analysis. (2) Accelerator mass spectrometry (AMS) for ultra sensitive analysis of stable nuclides and long-lived radionuclides. In most of the cases also the possibilities of elemental and isotopic analysis with high resolution will be discussed

Geological factors of the isotopic distribution of carbon of organic matter in sedimentary rocks

International Nuclear Information System (INIS)

Maass, J.

1981-01-01

The isotope ratio of carbon of fossile organic matter can be regarded as a definite criterion of its genetic origin. As the biofacial character of organic matter, especially the chemical composition (H/C-ratio), decisively influences the mode and quantity of the potential hydrocarbon production, isotopic analysis is an essential method for the prognostic evaluation of sedimentary basins with regard to their oil and gas perspectives. The genetic relations to the parent substance continue in the bituminization and coalification products and make it possible to apply the isotopic analysis of carbon to prospection work for hydrocarbons. (author)

Rubidium-strontium and uranium-lead isotopic age studies

International Nuclear Information System (INIS)

Loveridge, W.D.

1981-01-01

The results of five Rb-Sr isotopic age studies predominantly on whole-rock samples, and six U-Pb studies on zircon monazite concentrates are presented. Descriptions of the geological problems and interpretations of the measured ages are included. Laboratory age determination methods and techniques are described or referenced

Genomic Insights into the Sulfur Metabolism of Phototrophic Green Sulfur Bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Bryant, Donald A.

2008-01-01

Green sulfur bacteria (GSB) utilize various combinations of sulfide, elemental sulfur, thiosulfate, ferrous iron, and hydrogen for anaerobic photoautotrophic growth. Genome sequence data is currently available for 12 strains of GSB. We present here a genome-based survey of the distribution...... and phylogenies of genes involved in oxidation of sulfur compounds in these strains. Sulfide:quinone reductase, encoded by sqr, is the only known sulfur-oxidizing enzyme found in all strains. All sulfide-utilizing strains contain the dissimilatory sulfite reductase dsrABCEFHLNMKJOPT genes, which appear...... to be involved in elemental sulfur utilization. All thiosulfate-utilizing strains have an identical sox gene cluster (soxJXYZAKBW). The soxCD genes found in certain other thiosulfate-utilizing organisms like Paracoccus pantotrophus are absent from GSB. Genes encoding flavocytochrome c (fccAB), adenosine-5...

Geochemical behavior of beryllium isotopes in the ocean

International Nuclear Information System (INIS)

Kusakabe, M.; Ku, T.L.; Cusimano, G.L.; Southon, J.R.; Measures, C.I.

1989-01-01

9 Be and 10 Be have been measured in a variety of geological samples: sea water, marine particulate, bottom sediment and river water. While the 10 Be/ 9 Be ratio in the Pacific deep water seems to be constant, ∼ 1 x 10 -7 , the deep water in the Atlantic Ocean has significantly lower and variable ratio (0.7 x 10 -7 or less), reflecting larger input of riverine 9 Be to the Atlantic Ocean. The study of Be isotopes in river water, sea water, and sediment pore water from the southern California borderland shows that coastal areas play an important role in the removal of Be isotopes from the ocean. The behavior of particulate Be isotopes in the ocean is also discussed

Capital cost: high and low sulfur coal plants-1200 MWe. [High sulfur coal

Energy Technology Data Exchange (ETDEWEB)

1977-01-01

This Commercial Electric Power Cost Study for 1200 MWe (Nominal) high and low sulfur coal plants consists of three volumes. The high sulfur coal plant is described in Volumes I and II, while Volume III describes the low sulfur coal plant. The design basis and cost estimate for the 1232 MWe high sulfur coal plant is presented in Volume I, and the drawings, equipment list and site description are contained in Volume II. The reference design includes a lime flue gas desulfurization system. A regenerative sulfur dioxide removal system using magnesium oxide is also presented as an alternate in Section 7 Volume II. The design basis, drawings and summary cost estimate for a 1243 MWe low sulfur coal plant are presented in Volume III. This information was developed by redesigning the high sulfur coal plant for burning low sulfur sub-bituminous coal. These coal plants utilize a mechanical draft (wet) cooling tower system for condenser heat removal. Costs of alternate cooling systems are provided in Report No. 7 in this series of studies of costs of commercial electrical power plants.

Characterization of desulfurization, denitrogenation and process sulfur transfer during hydropyrolysis of Chinese high sulfur coals

Energy Technology Data Exchange (ETDEWEB)

Sun Chenggong; Li Baoqing [Chinese Academy of Sciences, Taiyuan (China). State Key Lab. of Coal Conversion; Snape, C.E. [Strathclyde Univ., Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry

1997-12-31

The process desulphurization and denitrogenation of Chinese high sulfur coals and the characteristics of sulfur transformation during non-catalytic hydropyrolysis were investigated by a 10 g fixed-bed reactor and a small-scaled reactor with online spectrometry respectively. It was indicated that more than 70% of the total sulfur of the two high sulfur coals and almost all pyritic sulfur are removed as H{sub 2}S, leaving the char and tar products with much less sulfur distribution. The liability of sulfur transformation to tar products is closely related to the thiophenic structure forms rather than sulfidic forms. At the same time, the formation of trace amount of sulfur dioxide indicates the presence of inherent sulfur oxidation reactions inside coal frame structures even under H{sub 2} pressure. (orig.)

Isotopic Evidence for Microbial Activity in Crystalline Bedrock Fractures - a Case Study from Olkiluoto, SW Finland

Science.gov (United States)

Sahlstedt, E. K.; Karhu, J.; Pitkänen, P.

2015-12-01

Changes in the geochemical environment in crystalline bedrock fractures were investigated using the stable isotopes of C, O and S in fracture filling minerals as tracers. Of special interest were the possible changes which may occur in the subsurface at low temperatures. Especially, the influence of microbial activity was recognized as a catalyst for inducing changes in the geochemical environment. The study site is the Olkiluoto island located on the western coast of Finland, planned to host a geological repository for nuclear waste. Fracture surfaces were investigated to recognize the latest mineralizations at the site. These fillings were comprised of thin plates or small euhedral crystals of calcite and pyrite. The carbon and sulfur isotope compositions of calcite and pyrite were measured from bulk material by conventional IRMS, and in situ by secondary ion mass spectrometry. A notable feature of the late-stage fillings was high variabilities in the δ13C values of calcite and the δ34S values of pyrite, which ranged from -53.8 ‰ to +31.6 ‰ and from -50.4 ‰ to +77.7 ‰, respectively. Based on the isotopic compositions of the fillings, several features in the past hydrogeochemical environment could be recognized. The isotopic composition of the fracture fillings indicate an environment which was stratified with respect to depth. Characteristic features include bacterial sulfate reduction (BSR) occurring at depths 50 m. It appears that methanic conditions were replaced by sulfate reduction at depths >50 m likely due to infiltration of SO42--rich brackish waters. Sulfate reducing bacteria used mainly surface derived organic carbon as electron donors. Some indication of minor methanotrophic activity was recognized in anomalously low δ13C values of calcite, down to -53.8 ‰, at the depth range of 34-54 m. This methanotrophic activity may have been related to bacteria using CH4 as an electron donor in BSR.

How the oxygen isotope ratio of rain water influences the isotope ratio of chicken eggshell carbonate

Science.gov (United States)

Price, Gregory; Grimes, Stephen

2015-04-01

The stable oxygen isotope ratio of chicken eggshell carbonate was analysed from chicken eggs laid under free range, and organic farming regimes from across the UK. The eggshell carbonate oxygen isotope data shows a clear depletion in delta18O distribution from the southwest to the northeast. Although consistently offset by around 1 permil, the same isotopic distribution as that seen in eggshell carbonate is observed in the delta18O ratio of rainfall and groundwater from across the UK. This distribution is related to the Rayleigh distillation of rainfall driven by westerly winds across the UK landmass. The clear relationship observed between eggshell delta18O values and that of rainwater presumably reflects the nature of free range chickens which must be drinking locally derived rainwater and supplementing their diet and water intake with locally derived food. These results suggest that the oxygen isotope value of chicken eggshells can be used as a forensic tool to identify the locality that free range and organic eggs were laid within the UK. Furthermore, if suitable material is preserved in the archaeological and geological record then such a relationship can potentially be used to establish the oxygen isotope value of rainwater from which ancient and / or ancestral birds lived.

In-situ sulfuration synthesis of sandwiched spherical tin sulfide/sulfur-doped graphene composite with ultra-low sulfur content

Science.gov (United States)

Zhao, Bing; Yang, Yaqing; Wang, Zhixuan; Huang, Shoushuang; Wang, Yanyan; Wang, Shanshan; Chen, Zhiwen; Jiang, Yong

2018-02-01

SnS is widely studied as anode materials since of its superior structural stability and physicochemical property comparing with other Sn-based composites. Nevertheless, the inconvenience of phase morphology control and excessive consumption of sulfur sources during synthesis hinder the scalable application of SnS nanocomposites. Herein, we report a facile in-situ sulfuration strategy to synthesize sandwiched spherical SnS/sulfur-doped graphene (SnS/S-SG) composite. An ultra-low sulfur content with approximately stoichiometric ratio of Sn:S can effectively promote the sulfuration reaction of SnO2 to SnS and simultaneous sulfur-doping of graphene. The as-prepared SnS/S-SG composite shows a three-dimensional interconnected spherical structure as a whole, in which SnS nanoparticles are sandwiched between the multilayers of graphene sheets forming a hollow sphere. The sandwiched sphere structure and high S doping amount can improve the binding force between SnS and graphene, as well as the structural stability and electrical conductivity of the composite. Thus, a high reversibility of conversion reaction, promising specific capacity (772 mAh g-1 after 100 cycles at 0.1 C) and excellent rate performance (705 and 411 mAh g-1 at 1 C and 10 C, respectively) are exhibited in the SnS/S-SG electrode, which are much higher than that of the SnS/spherical graphene synthesized by traditional post-sulfuration method.

ADVANCED SULFUR CONTROL CONCEPTS

Energy Technology Data Exchange (ETDEWEB)

Apostolos A. Nikolopoulos; Santosh K. Gangwal; William J. McMichael; Jeffrey W. Portzer

2003-01-01

Conventional sulfur removal in integrated gasification combined cycle (IGCC) power plants involves numerous steps: COS (carbonyl sulfide) hydrolysis, amine scrubbing/regeneration, Claus process, and tail-gas treatment. Advanced sulfur removal in IGCC systems involves typically the use of zinc oxide-based sorbents. The sulfides sorbent is regenerated using dilute air to produce a dilute SO{sub 2} (sulfur dioxide) tail gas. Under previous contracts the highly effective first generation Direct Sulfur Recovery Process (DSRP) for catalytic reduction of this SO{sub 2} tail gas to elemental sulfur was developed. This process is currently undergoing field-testing. In this project, advanced concepts were evaluated to reduce the number of unit operations in sulfur removal and recovery. Substantial effort was directed towards developing sorbents that could be directly regenerated to elemental sulfur in an Advanced Hot Gas Process (AHGP). Development of this process has been described in detail in Appendices A-F. RTI began the development of the Single-step Sulfur Recovery Process (SSRP) to eliminate the use of sorbents and multiple reactors in sulfur removal and recovery. This process showed promising preliminary results and thus further process development of AHGP was abandoned in favor of SSRP. The SSRP is a direct Claus process that consists of injecting SO{sub 2} directly into the quenched coal gas from a coal gasifier, and reacting the H{sub 2}S-SO{sub 2} mixture over a selective catalyst to both remove and recover sulfur in a single step. The process is conducted at gasifier pressure and 125 to 160 C. The proposed commercial embodiment of the SSRP involves a liquid phase of molten sulfur with dispersed catalyst in a slurry bubble-column reactor (SBCR).

USGS42 and USGS43: Human-hair stable hydrogen and oxygen isotopic reference materials and analytical methods for forensic science and implications for published measurement results

Science.gov (United States)

Coplen, T.B.; Qi, H.

2012-01-01

Because there are no internationally distributed stable hydrogen and oxygen isotopic reference materials of human hair, the U.S. Geological Survey (USGS) has prepared two such materials, USGS42 and USGS43. These reference materials span values commonly encountered in human hair stable isotope analysis and are isotopically homogeneous at sample sizes larger than 0.2 mg. USGS42 and USGS43 human-hair isotopic reference materials are intended for calibration of δ(2)H and δ(18)O measurements of unknown human hair by quantifying (1) drift with time, (2) mass-dependent isotopic fractionation, and (3) isotope-ratio-scale contraction. While they are intended for measurements of the stable isotopes of hydrogen and oxygen, they also are suitable for measurements of the stable isotopes of carbon, nitrogen, and sulfur in human and mammalian hair. Preliminary isotopic compositions of the non-exchangeable fractions of these materials are USGS42(Tibetan hair)δ(2)H(VSMOW-SLAP) = -78.5 ± 2.3‰ (n = 62) and δ(18)O(VSMOW-SLAP) = +8.56 ± 0.10‰ (n = 18) USGS42(Indian hair)δ(2)H(VSMOW-SLAP) = -50.3 ± 2.8‰ (n = 64) and δ(18)O(VSMOW-SLAP) = +14.11 ± 0.10‰ (n = 18). Using recommended analytical protocols presented herein for δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) measurements, the least squares fit regression of 11 human hair reference materials is δ(2)H(VSMOW-SLAP) = 6.085δ(2)O(VSMOW-SLAP) - 136.0‰ with an R-square value of 0.95. The δ(2)H difference between the calibrated results of human hair in this investigation and a commonly accepted human-hair relationship is a remarkable 34‰. It is critical that readers pay attention to the δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) of isotopic reference materials in publications, and they need to adjust the δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) measurement results of human hair in previous publications, as needed, to ensure all results on are on the same scales.

The significance of elemental sulfur dissolution in liquid electrolyte lithium sulfur batteries

NARCIS (Netherlands)

Harks, Peter Paul R.M.L.; Robledo, Carla B.; Verhallen, Tomas W.; Notten, Peter H.L.; Mulder, Fokko M.

2017-01-01

It is shown that the dissolution of elemental sulfur into, and its diffusion through, the electrolyte allows cycling of lithium–sulfur batteries in which the sulfur is initially far removed and electrically insulated from the current collector. These findings help to understand why liquid

Isotope-abundance variations and atomic weights of selected elements: 2016 (IUPAC Technical Report)

Science.gov (United States)

Coplen, Tyler B.; Shrestha, Yesha

2016-01-01

There are 63 chemical elements that have two or more isotopes that are used to determine their standard atomic weights. The isotopic abundances and atomic weights of these elements can vary in normal materials due to physical and chemical fractionation processes (not due to radioactive decay). These variations are well known for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium), and the standard atomic weight of each of these elements is given by IUPAC as an interval with lower and upper bounds. Graphical plots of selected materials and compounds of each of these elements have been published previously. Herein and at the URL http://dx.doi.org/10.5066/F7GF0RN2, we provide isotopic abundances, isotope-delta values, and atomic weights for each of the upper and lower bounds of these materials and compounds.

Self-assembled peptides for coating of active sulfur nanoparticles in lithium–sulfur battery

International Nuclear Information System (INIS)

Jewel, Yead; Yoo, Kisoo; Liu, Jin; Dutta, Prashanta

2016-01-01

Development of lithium–sulfur (Li–S) battery is hindered by poor cyclability due to the loss of sulfur, although Li–S battery can provide high energy density. Coating of sulfur nanoparticles can help maintain active sulfur in the cathode of Li–S battery, and hence increase the cyclability. Among myriad of coating materials, synthetic peptides are very attractive because of their spontaneous self-assembly as well as electrical conductive characteristics. In this study, we explored the use of various synthetic peptides as a coating material for sulfur nanoparticles. Atomistic simulations were carried out to identify optimal peptide structure and density for coating sulfur nanoparticles. Three different peptide models, poly-proline, poly(leucine–lysine) and poly-histidine, are selected for this study based on their peptide–peptide and peptide-sulfur interactions. Simulation results show that both poly-proline and poly(leucine–lysine) can form self-assembled coating on sulfur nanoparticles (2–20 nm) in pyrrolidinone, a commonly used solvent for cathode slurry. We also studied the structural integrity of these synthetic peptides in organic [dioxolane (DOL) and dimethoxyethane (DME)] electrolyte used in Li–S battery. Both peptides show stable structures in organic electrolyte (DOL/DME) used in Li–S battery. Furthermore, the dissolution of sulfur molecules in organic electrolyte is investigated in the absence and presence of these peptide coatings. It was found that only poly(leucine–lysine)-based peptide can most effectively suppress the sulfur loss in electrolyte, suggesting its potential applications in Li–S battery as a coating material.Graphical abstract

Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liang, Chengdu; Dudney, Nancy J.; Howe, Jane Y.

2017-08-01

The invention is directed in a first aspect to a sulfur-carbon composite material comprising: (i) a bimodal porous carbon component containing therein a first mode of pores which are mesopores, and a second mode of pores which are micropores; and (ii) elemental sulfur contained in at least a portion of said micropores. The invention is also directed to the aforesaid sulfur-carbon composite as a layer on a current collector material; a lithium ion battery containing the sulfur-carbon composite in a cathode therein; as well as a method for preparing the sulfur-composite material.

Trace elements and isotope data of the Um Garayat gold deposit, Wadi Allaqi district, Egypt

Science.gov (United States)

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.

Sulfurized carbon: a class of cathode materials for high performance lithium/sulfur batteries

Directory of Open Access Journals (Sweden)

Sheng S. Zhang

2013-12-01

Full Text Available Liquid electrolyte lithium/sulfur (Li/S batteries cannot come into practical applications because of many problems such as low energy efficiency, short cycle life, and fast self-discharge. All these problems are related to the dissolution of lithium polysulfide, a series of sulfur reduction intermediates, in the liquid electrolyte, and resulting parasitic reactions with the Li anode. Covalently binding sulfur onto carbon surface is a solution to completely eliminate the dissolution of lithium polysulfide and make the Li/S battery viable for practical applications. This can be achieved by replacing elemental sulfur with sulfurized carbon as the cathode material. This article reviews the current efforts on this subject and discusses the syntheses, electrochemical properties, and prospects of the sulfurized carbon as a cathode material in the rechargeable Li/S batteries.

Isotope composition and volume of Earth's early oceans.

Science.gov (United States)

Pope, Emily C; Bird, Dennis K; Rosing, Minik T

2012-03-20

Oxygen and hydrogen isotope compositions of Earth's seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen's was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth's oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH(4) and CO(2) concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth.

Effect of different sulfur levels from various sources on brassica napus growth and soil sulfur fractions

International Nuclear Information System (INIS)

Khalid, R.; Khan, K.S.; Islam, M.; Yousaf, M.; Shabbir, G.

2012-01-01

A two year field study was conducted at two different locations in northern rain fed Punjab, Pakistan to assess the effect of different rates of sulfur application from various sources on soil sulfur fractions and growth of Brassica napus. The treatments included three sulfur sources i. e., single super phosphate, ammonium sulfate and gypsum each applied at five different rates (0, 10, 20, 30 and 40 kg S ha/sup -1/ ). Sulfur application had a significant positive effect on the growth and yield parameters of Brassica napus. Among the sulfur sources ammonium sulfate resulted in maximum increase in plant growth and yield parameters, followed by single super phosphate. Sulfur content and uptake by crop plants was significantly higher with ammonium sulfate application as compared to other two sulfur sources. Sulfur application also exerted a significant positive effect on different S fractions in the soils. On an average, 18.0% of the applied sulfur got incorporated into CaCl/sub 2/ extractable sulfur fraction, while 15.6% and 35.5% entered into adsorbed and organic sulfur fractions in the soils, respectively. The value cost ratio increased significantly by sulfur application up to 30 kg ha/sup -1/. Among sulfur sources, ammonium sulfate performed best giving the highest net return. (author)

Using multiple isotopes to understand the source of ingredients used in golden beverages

Science.gov (United States)

Wynn, J. G.

2011-12-01

Traditionally, beer contains 4 simple ingredients: water, barley, hops and yeast. Each of these ingredients used in the brewing process contributes some combination of a number of "traditional" stable isotopes (i.e., isotopes of H, C, O, N and S) to the final product. As an educational exercise in an "Analytical Techniques in Geology" course, a group of students analyzed the isotopic composition of the gas, liquid and solid phases of a variety of beer samples collected from throughout the world (including other beverages). The hydrogen and oxygen isotopic composition of the water followed closely the isotopic composition of local meteoric water at the source of the brewery, although there is a systematic offset from the global meteoric water line that may be due to the effects of CO2-H2O equilibration. The carbon isotopic composition of the CO2 reflected that of the solid residue (the source of carbon used as a fermentation substrate), but may potentially be modified by addition of gas-phase CO2 from an inorganic source. The carbon isotopic composition of the solid residue similarly tracks that of the fermentation substrate, and may indicate some alcohol fermented from added sugars in some cases. The nitrogen isotopic composition of the solid residue was relatively constant, and may track the source of nitrogen in the barley, hops and yeast. Each of the analytical methods used is a relatively standard technique used in geological applications, making this a "fun" exercise for those involved, and gives the students hands-on experience with a variety of analytes from a non-traditional sample material.

Sulfur nanocrystals anchored graphene composite with highly improved electrochemical performance for lithium-sulfur batteries

Science.gov (United States)

Zhang, Jun; Dong, Zimin; Wang, Xiuli; Zhao, Xuyang; Tu, Jiangping; Su, Qingmei; Du, Gaohui

2014-12-01

Two kinds of graphene-sulfur composites with 50 wt% of sulfur are prepared using hydrothermal method and thermal mixing, respectively. Transmission Electron Microscopy (TEM) and Energy Dispersive X-ray Spectra mapping show that sulfur nanocrystals with size of ∼5 nm dispersed on graphene sheets homogeneously for the sample prepared by hydrothermal method (NanoS@G). While for the thermal mixed graphene-sulfur composite (S-G mixture), sulfur shows larger and uneven size (50-200 nm). X-ray Photoelectron Spectra (XPS) reveals the strong chemical bonding between the sulfur nanocrystals and graphene. Comparing with the S-G mixture, the NanoS@G composite shows highly improved electrochemical performance as cathode for lithium-sulfur (Li-S) battery. The NanoS@G composite delivers an initial capacity of 1400 mAh g-1 with the sulfur utilization of 83.7% at a current density of 335 mA g-1. The capacity keeps above 720 mAh g-1 over 100 cycles. The strong adherence of the sulfur nanocrystals on graphene immobilizes sulfur and polysulfides species and suppressed the "shuttle effect", resulting higher coulombic efficiency and better capacity retention. Electrochemical impedance also suggests that the strong bonding enabled rapid electronic/ionic transport and improved electrochemical kinetics, therefore good rate capability is obtained. These results demonstrate that the NanoS@G composite is a very promising candidate for high-performance Li-S batteries.

The impact of the Cretaceous-Paleogene (K-Pg) mass extinction event on the global sulfur cycle: Evidence from Seymour Island, Antarctica

Science.gov (United States)

Witts, James D.; Newton, Robert J.; Mills, Benjamin J. W.; Wignall, Paul B.; Bottrell, Simon H.; Hall, Joanna L. O.; Francis, Jane E.; Alistair Crame, J.

2018-06-01

The Cretaceous-Paleogene (K-Pg) mass extinction event 66 million years ago led to large changes to the global carbon cycle, primarily via a decrease in primary or export productivity of the oceans. However, the effects of this event and longer-term environmental changes during the Late Cretaceous on the global sulfur cycle are not well understood. We report new carbonate associated sulfate (CAS) sulfur isotope data derived from marine macrofossil shell material from a highly expanded high latitude Maastrichtian to Danian (69-65.5 Ma) succession located on Seymour Island, Antarctica. These data represent the highest resolution seawater sulfate record ever generated for this time interval, and are broadly in agreement with previous low-resolution estimates for the latest Cretaceous and Paleocene. A vigorous assessment of CAS preservation using sulfate oxygen, carbonate carbon and oxygen isotopes and trace element data, suggests factors affecting preservation of primary seawater CAS isotopes in ancient biogenic samples are complex, and not necessarily linked to the preservation of original carbonate mineralogy or chemistry. Primary data indicate a generally stable sulfur cycle in the early-mid Maastrichtian (69 Ma), with some fluctuations that could be related to increased pyrite burial during the 'mid-Maastrichtian Event'. This is followed by an enigmatic +4‰ increase in δ34SCAS during the late Maastrichtian (68-66 Ma), culminating in a peak in values in the immediate aftermath of the K-Pg extinction which may be related to temporary development of oceanic anoxia in the aftermath of the Chicxulub bolide impact. There is no evidence of the direct influence of Deccan volcanism on the seawater sulfate isotopic record during the late Maastrichtian, nor of a direct influence by the Chicxulub impact itself. During the early Paleocene (magnetochron C29R) a prominent negative excursion in seawater δ34S of 3-4‰ suggests that a global decline in organic carbon burial

Isotope analytics for the evaluation of the feeding influence on the isotope ratio in beef samples

International Nuclear Information System (INIS)

Herwig, Nadine

2010-01-01

Information about the origin of food and associated production systems has a high significance for food control. An extremely promising approach to obtain such information is the determination of isotope ratios of different elements. In this study the correlation of the isotope ratios C-13/C-12, N-15/N-14, Mg-25/Mg-24, and Sr-87/Sr-86 in bovine samples (milk and urine) and the corresponding isotope ratios in feed was investigated. It was shown that in the bovine samples all four isotope ratios correlate with the isotope composition of the feed. The isotope ratios of strontium and magnesium have the advantage that they directly reflect the isotope ratios of the ingested feed since there is no isotope fractionation in the bovine organism which is in contrast to the case of carbon and nitrogen isotope ratios. From the present feeding study it is evident, that a feed change leads to a significant change in the delta C-13 values in milk and urine within 10 days already. For the deltaN-15 values the feed change was only visible in the bovine urine after 49 days. Investigations of cows from two different regions (Berlin/Germany and Goestling/Austria) kept at different feeding regimes revealed no differences in the N-15/N-14 and Mg-26/Mg-24 isotope ratios. The strongest correlation between the isotope ratio of the bovine samples and the kind of ingested feed was observed for the carbon isotope ratio. With this ratio even smallest differences in the feed composition were traceable in the bovine samples. Since different regions usually coincide with different feeding regimes, carbon isotope ratios can be used to distinguish bovine samples from different regions if the delta C-13 values of the ingested feed are different. Furthermore, the determination of strontium isotope ratios revealed significant differences between bovine and feed samples of Berlin and Goestling due to the different geologic realities. Hence the carbon and strontium isotope ratios allow the best

Isotopic Generation and Confirmation of the PWR Application Model?

International Nuclear Information System (INIS)

L.B. Wimmer

2003-01-01

The objective of this calculation is to establish an isotopic database to represent commercial spent nuclear fuel (CSNF) from pressurized water reactors (PWRs) in criticality analyses performed for the proposed Monitored Geologic Repository at Yucca Mountain, Nevada. Confirmation of the conservatism with respect to criticality in the isotopic concentration values represented by this isotopic database is performed as described in Section 3.5.3.1.2 of the ''Disposal Criticality Analysis Methodology Topical Report'' (YMP 2000). The isotopic database consists of the set of 14 actinides and 15 fission products presented in Section 3.5.2.1.1 of YMP 2000 for use in CSNF burnup credit. This set of 29 isotopes is referred to as the principal isotopes. The oxygen isotope from the UO 2 fuel is also included in the database. The isotopic database covers enrichments of 235 U ranging from 1.5 to 5.5 weight percent (wt%) and burnups ranging from approximately zero to 75 GWd per metric ton of uranium (mtU). The choice of fuel assembly and operating history values used in generating the isotopic database are provided is Section 5. Tables of isotopic concentrations for the 29 principal isotopes (plus oxygen) as a function of enrichment and burnup are provided in Section 6.1. Results of the confirmation of the conservatism with respect to criticality in the isotopic concentration values are provided in Section 6.2

Sulfur and carbon geochemistry of the Santa Elena peridotites: Comparing oceanic and continental processes during peridotite alteration

Science.gov (United States)

Schwarzenbach, Esther M.; Gill, Benjamin C.; Gazel, Esteban; Madrigal, Pilar

2016-05-01

Ultramafic rocks exposed on the continent serve as a window into oceanic and continental processes of water-peridotite interaction, so called serpentinization. In both environments there are active carbon and sulfur cycles that contain abiogenic and biogenic processes, which are eventually imprinted in the geochemical signatures of the basement rocks and the calcite and magnesite deposits associated with fluids that issue from these systems. Here, we present the carbon and sulfur geochemistry of ultramafic rocks and carbonate deposits from the Santa Elena ophiolite in Costa Rica. The aim of this study is to leverage the geochemistry of the ultramafic sequence and associated deposits to distinguish between processes that were dominant during ocean floor alteration and those dominant during low-temperature, continental water-peridotite interaction. The peridotites are variably serpentinized with total sulfur concentrations up to 877 ppm that is typically dominated by sulfide over sulfate. With the exception of one sample the ultramafic rocks are characterized by positive δ34Ssulfide (up to + 23.1‰) and δ34Ssulfate values (up to + 35.0‰). Carbon contents in the peridotites are low and are isotopically distinct from typical oceanic serpentinites. In particular, δ13C of the inorganic carbon suggests that the carbon is not derived from seawater, but rather the product of the interaction of meteoric water with the ultramafic rocks. In contrast, the sulfur isotope data from sulfide minerals in the peridotites preserve evidence for interaction with a hydrothermal fluid. Specifically, they indicate closed system abiogenic sulfate reduction suggesting that oceanic serpentinization occurred with limited input of seawater. Overall, the geochemical signatures preserve evidence for both oceanic and continental water-rock interaction with the majority of carbon (and possibly sulfate) being incorporated during continental water-rock interaction. Furthermore, there is

Gaseous byproducts from high-temperature thermal conversion elemental analysis of nitrogen- and sulfur-bearing compounds with considerations for δ2H and δ18O analyses.

Science.gov (United States)

Hunsinger, Glendon B; Tipple, Christopher A; Stern, Libby A

2013-07-30

High-temperature, conversion-reduction (HTC) systems convert hydrogen and oxygen in materials into H2 and CO for δ(2)H and δ(18)O measurements by isotope ratio mass spectrometry. HTC of nitrogen- and sulfur-bearing materials produces unintended byproduct gases that could affect isotope analyses by: (1) allowing isotope exchange reactions downstream of the HTC reactor, (2) creating isobaric or co-elution interferences, and (3) causing deterioration of the chromatography. This study characterizes these HTC byproducts. A HTC system (ThermoFinnigan TC/EA) was directly connected to a gas chromatograph/quadrupole mass spectrometer in scan mode (m/z 8 to 88) to identify the volatile products generated by HTC at conversion temperatures of 1350 °C and 1450 °C for a range of nitrogen- and sulfur-bearing solids [keratin powder, horse hair, caffeine, ammonium nitrate, potassium nitrate, ammonium sulfate, urea, and three nitrated organic explosives (PETN, RDX, and TNT)]. The prominent HTC byproduct gases include carbon dioxide, hydrogen cyanide, methane, acetylene, and water for all nitrogen-bearing compounds, as well as carbon disulfide, carbonyl sulfide, and hydrogen sulfide for sulfur-bearing compounds. The 1450 °C reactor temperature reduced the abundance of most byproduct gases, but increased the significant byproduct, hydrogen cyanide. Inclusion of a post-reactor chemical trap containing Ascarite II and Sicapent, in series, eliminated the majority of byproducts. This study identified numerous gaseous HTC byproducts. The potential adverse effects of these gases on isotope ratio analyses are unknown but may be mitigated by higher HTC reactor temperatures and purifying the products with a purge-and-trap system or with chemical traps. Published in 2013. This article is a U.S. Government work and is in the public domain in the USA.

Geologic evolution of the SE.23 Sheet - Belo Horizonte, MG, Brazil

International Nuclear Information System (INIS)

Pereira, A.D.C.; Fonseca, E.G. da; Braz, E.R.C.

1987-01-01

The aim of this paper is to present a synthesis of the geologic evolution in the Belo Horizonte Sheet comprising an area about 281.210 Km 2 . Rb-Sr and K-Ar isotope dating methods are used for age estimation of geologic deposits. The geologic evolution of the cratonic area is reflected by a stable central nucleus surrounded by marginal orogenic belts. In the central area were recognized greenstone belts structures involved by granite terrains and bordered by a granulitic region. The framework of the Sao Francisco Craton involves events of metamorphism, granitogenesis, sedimentary, volcanism and plutonism developed in the Early to Late Proterozoic. The stratigraphic column is complemented by Late Jurassic-Early Cretaceous continental deposits belonging to Parana-Basin. (M.V.M.)

Gradual and stepwise pyrolyses of insoluble organic matter from the Murchison meteorite revealing chemical structure and isotopic distribution

Science.gov (United States)

Okumura, Fumiaki; Mimura, Koichi

2011-11-01

To study the detailed structural and isotopic heterogeneity of the insoluble organic matter (IOM) of the Murchison meteorite, we performed two types of pyrolytic experiments: gradual pyrolysis and stepwise pyrolysis. The pyrolysates from the IOM contained 5 specific organic groups: aliphatic hydrocarbons, aromatic hydrocarbons, sulfur-bearing compounds, nitrogen-bearing compounds, and oxygen-bearing compounds. The release temperatures and the compositions of these pyrolysates demonstrated that the IOM is composed of a thermally unstable part and a thermally stable part. The thermally unstable part mainly served as the linkage and substituent portion that bound the thermally stable part, which was dispersed throughout the IOM. The linkage and substituent portion consisted of aliphatic hydrocarbons from C 4 to C 8, aromatic hydrocarbons with up to 6 rings, sulfo and thiol groups (the main reservoirs of sulfur in the IOM), and carboxyl and hydroxyl groups (the main reservoirs of oxygen). However, the thermally stable part was composed of polycyclic aromatic hydrocarbons (PAHs) containing nitrogen heterocycles in the IOM. Isotopic data showed that the aliphatic and aromatic hydrocarbons in the linkage and substituent portion were rich in D and 13C, while the thermally stable part was deficient in D and 13C. The structural and isotopic features suggested that the IOM was formed by mixing sulfur- and oxygen-bearing compounds rich in D and 13C (e.g., polar compounds in the interstellar medium (ISM)) and nitrogen-bearing PAHs deficient in D and 13C (e.g., polymerized compounds in the ISM).

Isotopic reconstruction of ancient human migrations: A comprehensive Sr isotope reference database for France and the first case study at Tumulus de Sables, south-western France

Science.gov (United States)

Willmes, M.; Boel, C.; Grün, R.; Armstrong, R.; Chancerel, A.; Maureille, B.; Courtaud, P.

2012-04-01

Strontium isotope ratios (87Sr/86Sr) can be used for the reconstruction of human and animal migrations across geologically different terrains. Sr isotope ratios in rocks are a product of age and composition and thus vary between geologic units. From the eroding environment Sr is transported into the soils, plants and rivers of a region. Humans and animals incorporate Sr from their diet into their bones and teeth, where it substitutes for calcium. Tooth enamel contains Sr isotope signatures acquired during childhood and is most resistant to weathering and overprinting, while the dentine is often diagenetically altered towards the local Sr signature. For the reconstruction of human and animal migrations the tooth enamel 87Sr/86Sr ratio is compared to the Sr isotope signature in the vicinity of the burial site and the surrounding area. This study focuses on the establishment of a comprehensive reference map of bioavailable 87Sr/86Sr ratios for France. In a next step we will compare human and animal teeth from key archaeological sites to this reference map to investigate mobility. So far, we have analysed plant and soil samples from ~200 locations across France including the Aquitaine basin, the western and northern parts of the Paris basin, as well as three transects through the Pyrenees Mountains. The isotope data, geologic background information (BRGM 1:1M), field images, and detailed method descriptions are available through our online database iRhum (http://rses.anu.edu.au/research/ee). This database can also be used in forensic studies and food sciences. As an archaeological case study teeth from 16 adult and 8 juvenile individuals were investigated from an early Bell Beaker (2500-2000 BC) site at Le Tumulus des Sables, south-west France (Gironde). The teeth were analysed for Sr isotope ratios using laser ablation ICP-MS. Four teeth were also analysed using solution ICP-MS, which showed a significant offset to the laser ablation results. This requires further

Kinetic solvent isotope effects in the additions of bromine and 4-chlorobenzenesulfenyl chloride to alkenes and alkynes

International Nuclear Information System (INIS)

Modro, A.; Schmid, G.H.; Yates, K.

1979-01-01

The rates of bromination of selected alkenes and alkynes in methanol/methanol-d, acetic acid/acetic acid-d, and formic acid/formic acid-d have a nearly constant value of k/sub H//k/sub D/ = 1.23 +- 0.02. This kinetic solvent isotope effect is attributed to specific electrophilic solvation of the incipient bromide anion by hydrogen bonding in the rate-determining transition state. The rates of bromination were measured in two solvents having the same values of the solvent parameter Y but different nucleophilicities in order to assess the importance of nucleophilic solvation. Significant nucleophilic solvent assistance is found for only alkylacetylenes. The kinetic solvent isotope effects of the addition of 4-chlorobenzenesulfenyl chloride to selected alkenes and alkynes in acetic acid/acetic acid-d vary from 1.00 to 1.28. These data are consistent with two mechanisms: one involves a tetravalent sulfur intermediate while the second is the sulfur analogue of the S/sub N/2 mechanism

Do Strontium Isotope Ratios of Animal Bone and Teeth Really Reflect the Isotope Ratios of its birth- and growth-places?

Science.gov (United States)

Minami, M.; Goto, A.; Suzuki, K.; Kato, T.; Watanabe, K.; Hasegawa, T.

2007-12-01

Strontium enters the human body through the food chain as nutrients pass from bedrock through soil and water to plants and animals. Strontium substitutes for calcium in the hydroxyapatite mineral of skeletal tissue, and is stored there. 87Sr/86Sr ratios in an individual's bone and teeth could directly reflect the isotopic ratios found in the plants and animals that she or he consumed, which reflect the isotope ratios found in the soil and bedrock of that geologic region. Therefore, 87Sr/86Sr ratios of human skeletons could be useful tools for assessing human residential mobility in prehistory, and many studies on them have been often made. In this study, to evaluate whether the 87Sr/86Sr ratio of a bone or teeth really reflects the isotopic ratios of its birth and growth places, several bone and teeth samples were measured for 87Sr/86Sr ratios, compared with 87Sr/86Sr ratios of geological samples in their growth-places. Bone and teeth samples were leached with 5% acetic acid. After drying, samples were ashed in a muffle furnace at 825°C for 8h, and then digested in nitric acid, followed by cation exchange chromatography with 2.4M hydrochloric acid. 87Sr/86Sr ratios were measured using a thermal ionization mass Spectrometer (VG Sector 54) or an inductively coupled plasma mass spectrometer (Finnigan ELEMENT2). A modern boar bone collected at Asuke, Toyota City, Aichi prefecture, Japan showed a 87Sr/86Sr of 0.71001±0.00002 (2 σ), while stream sediments in the Asuke area showed around 0.710 (Asahara et al., 2006). The 87Sr/86Sr ratio of a modern black bass bone collected from Lake Biwa, Shiga prefecture, Japan was 0.71215±0.00002, while those of surface water in Lake Biwa was 0.71233±0.00002. The similar 87Sr/86Sr ratios between bone and its provenance geology could indicate that the 87Sr/86Sr ratios of bones reflect the isotopic ratios of the birth- and growth-places. The more results of modern and fossil skeletons will be shown in our presentation.

Extractive de-sulfurization and de-ashing of high sulfur coals by oxidation with ionic liquids

International Nuclear Information System (INIS)

Saikia, Binoy K.; Khound, Kakoli; Baruah, Bimala P.

2014-01-01

Highlights: • Extractive de-sulfurization and de-ashing process for cleaning high sulfur coals. • The process removes inorganic as well as organic sulfur components from high sulfur coals. • The process has less risk to chemists and other surroundings. - Abstract: The environmental consequences of energy production from coals are well known, and are driving the development of desulfurization technologies. In this investigation, ionic liquids were examined for extractive desulfurization and de-ashing in industrially important high sulfur sub-bituminous Indian coals. The ionic liquids, namely, 1-n-butyl-3-methylimidazolium tetrafluoroborate (IL1) and 1-n-butyl 3-methylimidazolium chloride (IL2) were employed for desulfurization of a few Indian coal samples in presence of HCOOH/H 2 O 2 and V 2 O 5 . Results show the maximum removal of 50.20% of the total sulfur, 48.00% of the organic sulfur, and 70.37 wt% of the ash in this process. The ionic liquids were recovered and subsequently used for further desulfurization. FT-IR spectra reveal the transformation of organic sulfur functionalities into the sulfoxides (S=O) and sulfones (-SO 2 ) due to the oxidative reactions. The sulfate, pyrite and sulfides (aryls) signals in the near edge X-ray absorption fine structure (NEXAFS) of the oxidized coal samples showed sulfur transformation during the desulfurization process. The study demonstrates the removal of significant amount of inorganic as well as organic sulfur (aryls) components from the original high sulfur coal samples to make them cleaner

Conductive framework of inverse opal structure for sulfur cathode in lithium-sulfur batteries.

Science.gov (United States)

Jin, Lu; Huang, Xiaopeng; Zeng, Guobo; Wu, Hua; Morbidelli, Massimo

2016-09-07

As a promising cathode inheritor for lithium-ion batteries, the sulfur cathode exhibits very high theoretical volumetric capacity and energy density. In its practical applications, one has to solve the insulating properties of sulfur and the shuttle effect that deteriorates cycling stability. The state-of-the-art approaches are to confine sulfur in a conductive matrix. In this work, we utilize monodisperse polystyrene nanoparticles as sacrificial templates to build polypyrrole (PPy) framework of an inverse opal structure to accommodate (encapsulate) sulfur through a combined in situ polymerization and melting infiltration approach. In the design, the interconnected conductive PPy provides open channels for sulfur infiltration, improves electrical and ionic conductivity of the embedded sulfur, and reduces polysulfide dissolution in the electrolyte through physical and chemical adsorption. The flexibility of PPy and partial filling of the inverse opal structure endure possible expansion and deformation during long-term cycling. It is found that the long cycling stability of the cells using the prepared material as the cathode can be substantially improved. The result demonstrates the possibility of constructing a pure conductive polymer framework to accommodate insulate sulfur in ion battery applications.

Sulfur poisoning in cattle

Energy Technology Data Exchange (ETDEWEB)

Julian, R J; Harrison, K B

1975-01-01

A case of sulfur poisoning is described in which 12 of 20 cattle died following the feeding of sulfur. Respiratory distress and abdominal pain were the prominent signs. Examination of one animal revealed vasculitis and necrosis of the rumen and abomasal wall. The possible toxic effects of sulfur are discussed.

Isotopes as tracers in a contaminated fractured chalk aquitard

Science.gov (United States)

Nativ, R.; Adar, E.

2003-04-01

Clusters of industrial plants often generate contaminant plumes with several potential sources. Prevention of further pollution and designing suitable remedial measures require identification of the contributing source among all potential ones and the sorting of currently active sources from historical ones. In the study area, an industrial complex in the Negev desert, Israel, the lateral spread of groundwater contamination combined with water level patterns and the location of wastewater storage lagoons and treatment facilities posed a serious monitoring problem. Because (1) wastewater from all plants was mixed through a central wastewater pipeline and spread in various ways and means throughout the site, and (2) a groundwater mounding area was formed upgradient of the site, the contribution of potentially contaminating individual downgradient facilities could not be inferred using site-specific contaminants and/or the increased hydraulic head. Stable isotopes of oxygen, hydrogen and sulfur, as well as tritium, proved to be an efficient monitoring tool. Isotopic characterization of the two end members, namely, the natural, uncontaminated groundwater in off-site wells, and the industrial wastewater, provided the criteria for constraining a contaminating source when several alternative sources appeared viable. The isotopic fractionation of oxygen and hydrogen isotopes could be tied to the various disposal phases of the industrial wastewater. The presented case studies illustrate the important role of isotopes as tracers at contaminated sites.

Application of benchtop micro-XRF to geological materials

DEFF Research Database (Denmark)

Flude, Stephanie; Haschke, Michael; Storey, Michael

2017-01-01

Recent developments in X-ray optics have allowed the development of a range of commercially available benchtop micro-XRF (μ-XRF) instruments that can produce X-ray spot sizes of 20–30 μm on the sample, allowing major- and trace-element analysis on a range of sample types and sizes with minimal......, by using a simple type-calibration against a reference material of similar matrix and composition. Qualitative analysis with micro-XRF can simplify and streamline sample characterization and processing for subsequent geochemical and isotopic analysis....... sample preparation. Such instruments offer quantitative analysis using fundamental parameter based 'standardless' quantification algorithms. The accuracy and precision of this quantitative analysis on geological materials, and application of micro-XRF to wider geological problems is assessed using...

Stable isotope composition of cocoa beans of different geographical origin.

Science.gov (United States)

Perini, Matteo; Bontempo, Luana; Ziller, Luca; Barbero, Alice; Caligiani, Augusta; Camin, Federica

2016-09-01

The isotopic profile (δ(13) C, δ(15) N, δ(18) O, δ(2) H, δ(34) S) was used to characterise a wide selection of cocoa beans from different renowned production areas (Africa, Asia, Central and South America). The factors most influencing the isotopic signatures of cocoa beans were climate and altitude for δ(13) C and the isotopic composition of precipitation water for δ(18) O and δ(2) H, whereas δ(15) N and δ(34) S were primarily affected by geology and fertilisation practises. Multi-isotopic analysis was shown to be sufficiently effective in determining the geographical origin of cocoa beans, and combining it with Canonical Discriminant Analysis led to more than 80% of samples being correctly reclassified. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Uranium, RADON and radon isotopes in selected brines of Poland

International Nuclear Information System (INIS)

Kozlowska, B.; Walencik, A.; Zipper, W.; Dorda, J.; Przylibski, T.A.

2010-01-01

Natural radioactive isotopes were studied in nine different types of brines from four locations in Poland. Investigated brines are exploited from various geological structures composed of the rocks of different chemical and mineral composition as well as different age and depth. All investigated brines are used in balneotherapy (i.e. baths, inhalations, showers). The main goal of this study was to obtain some basic knowledge on the activity range of natural elements such as uranium, RADON and radon in different brine types in Poland and their variability depending on their location in certain geological structures. Activities of 234,238 U, 226,228 Ra and 222 Rn isotopes were measured with the use of two nuclear spectrometry techniques: liquid scintillation and alpha spectrometry. The activity concentrations of 222 Rn vary from below 1 to 76.1±3.7 Bq/l, for the 226 Ra isotope from 0.19±0.01 to 85.5±0.4 Bq/l and for 228 Ra from below 0.03 to 2.17±0.09 Bq/l. For uranium isotopes, the concentrations are in the range from below 0.5 to 5.1±0.4 mBq/l for 238 U and from 1.6±0.4 to 45.6±2.0 mBq/l for 2 34U . The obtained results indicate high RADON activity concentrations corresponding to high mineralization of waters. (authors)

Sulfur Earth

Science.gov (United States)

de Jong, B. H.

2007-12-01

Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

Field testing the effectiveness of pumping to remove sulfur hexafluoride traced drilling air from a prototype borehole near superior, Arizona

International Nuclear Information System (INIS)

Peters, C.A.; Striffler, P.; Yang, I.C.; Ferarese, J.

1993-01-01

The US Geological Survey (USGS), Department of the Interior is conducting studies at Yucca Mountain, Nevada, to provide hydrologic, hydrochemical, and geologic information to evaluate the suitability of Yucca Mountain for development as a high-level nuclear-waste repository. The USGS unsaturated-zone hydrochemistry study involves the collection of gas and water samples from the unsaturated zone for chemical and isotopic analyses. Results from these analyses will aid in the understanding of the movement of gas and water in the rock units at Yucca Mountain. A prototype borehole designated USW UZP5 was drilled by the US Department of Energy, Yucca Mountain Site Characterization Project Office (DOE, YMSCPO) in June 1990 in the Apache Leap Tuff of southcentral Arizona. The hole was dry drilled with air using sulfur hexafluoride (SF 6 ) as a tracer. This drilling method simulated that which will be used to drill boreholes for the collection of gas and water samples at Yucca Mountain. The purpose of tracing the drilling air is to quantify its removal by pumping, prior to sampling of in situ gases. The objectives of our work in Arizona were to: (1) Determine the amount of time and the pumping rates required to remove the SF 6 -enriched drilling air without inducing additional atmospheric contamination; (2) collect core samples for uniaxial compression to determine the amount of SF 6 gas that penetrated the core during drilling; (3) test the effectiveness of the SF 6 injection and sampling system; (4) test the installation and effectiveness of the prototype packer system; and (5) test the effectiveness of several core sealing methods. 1 fig., 1 tab

Laser Isotope Enrichment for Medical and Industrial Applications

Energy Technology Data Exchange (ETDEWEB)

Leonard Bond

2006-07-01

Laser Isotope Enrichment for Medical and Industrial Applications by Jeff Eerkens (University of Missouri), Jay Kunze (Idaho State University), and Leonard Bond (Idaho National Laboratory) The principal isotope enrichment business in the world is the enrichment of uranium for commercial power reactor fuels. However, there are a number of other needs for separated isotopes. Some examples are: 1) Pure isotopic targets for irradiation to produce medical radioisotopes. 2) Pure isotopes for semiconductors. 3) Low neutron capture isotopes for various uses in nuclear reactors. 4) Isotopes for industrial tracer/identification applications. Examples of interest to medicine are targets to produce radio-isotopes such as S-33, Mo-98, Mo-100, W-186, Sn-112; while for MRI diagnostics, the non-radioactive Xe-129 isotope is wanted. For super-semiconductor applications some desired industrial isotopes are Si-28, Ga-69, Ge-74, Se-80, Te-128, etc. An example of a low cross section isotope for use in reactors is Zn-68 as a corrosion inhibitor material in nuclear reactor primary systems. Neutron activation of Ar isotopes is of interest in industrial tracer and diagnostic applications (e.g. oil-logging). . In the past few years there has been a sufficient supply of isotopes in common demand, because of huge Russian stockpiles produced with old electromagnetic and centrifuge separators previously used for uranium enrichment. Production of specialized isotopes in the USA has been largely accomplished using old ”calutrons” (electromagnetic separators) at Oak Ridge National Laboratory. These methods of separating isotopes are rather energy inefficient. Use of lasers for isotope separation has been considered for many decades. None of the proposed methods have attained sufficient proof of principal status to be economically attractive to pursue commercially. Some of the authors have succeeded in separating sulfur isotopes using a rather new and different method, known as condensation