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

Science.gov (United States)

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

A neogene seawater sulfur isotope age curve from calcareous pelagic microfossils

International Nuclear Information System (INIS)

Burdett, J.W.; Arthur, M.A.; Richardson, M.

1989-01-01

Until now, our knowledge of the sulfur isotopic composition of seawater through geologic time has depended on stable isotopic analysis of sulfate from evaporites. Owing to the sporadic occurrence of evaporites through time, the secular sulfur isotope age curve contains many gaps with little or no data. In order to fill in some of these gaps, particularly the Neogene, we have analyzed the sulfur isotopic composition of carbonate-associated sulfate in carbonate tests of planktonic foraminifera. Other investigators have shown that sulfate may occur in biogenic calcites either lattice-bound, as micro-fluid inclusions, in adsorbed phases, or as protein polysaccharides. Whatever the origin, the sulfur isotopic composition of this sulfate appears to be representative of that of the water in which the organism lived, as shown by results on recent calcareous foraminifera and macrofossils. Using this approach for study of Miocene to Recent pelagic marine sediments supplemented by new data for Miocene marine evaporites from the Gulf of Suez, we have found that the δ 34 S of seawater has decreased about 2.5per mille over the past 25 m.y. and that most of the decrease has occurred over the past 5 m.y., paralleling a decrease in the δ 13 C of dissolved oceanic bicarbonate from the same interval. Sedimentary redox models based on isotope records suggest that organic carbon and sulfide burial have both decreased over the past 5 m.y. Alternatively, an increase in weathering rates over the past 5 m.y. would not require a decrease in organic carbon or sulfide burial as long as the isotopic effect of the increased river input exceeds the isotopic effect of the burial of the reduced species. In either case, the net result would be a decrease in atmospheric p O2 . (orig.)

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

Science.gov (United States)

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

Directory of Open Access Journals (Sweden)

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)

Transport-Induced Spatial Patterns of Sulfur Isotopes (δ34S) as Biosignatures

Science.gov (United States)

Mansor, Muammar; Harouaka, Khadouja; Gonzales, Matthew S.; Macalady, Jennifer L.; Fantle, Matthew S.

2018-01-01

Cave minerals deposited in the presence of microbes may host geochemical biosignatures that can be utilized to detect subsurface life on Earth, Mars, or other habitable worlds. The sulfur isotopic composition of gypsum (CaSO4·2H2O) formed in the presence of sulfur-oxidizing microbes in the Frasassi cave system, Italy, was evaluated as a biosignature. Sulfur isotopic compositions (δ34SV-CDT) of gypsum sampled from cave rooms with sulfidic air varied from -11 to -24‰, with minor deposits of elemental sulfur having δ34S values between -17 and -19‰. Over centimeter-length scales, the δ34S values of gypsum varied by up to 8.5‰. Complementary laboratory experiments showed negligible fractionation during the oxidation of elemental sulfur to sulfate by Acidithiobacillus thiooxidans isolated from the caves. Additionally, gypsum precipitated in the presence and absence of microbes at acidic pH characteristic of the sulfidic cave walls has δ34S values that are on average 1‰ higher than sulfate. We therefore interpret the 8.5‰ variation in cave gypsum δ34S (toward more negative values) to reflect the isotopic effect of microbial sulfide oxidation directly to sulfate or via elemental sulfur intermediate. This range is similar to that expected by abiotic sulfide oxidation with oxygen, thus complicating the use of sulfur isotopes as a biosignature at centimeter-length scales. However, at the cave room (meter-length) scale, reactive transport modeling suggests that the overall ˜13‰ variability in gypsum δ34S reflects isotopic distillation of circulating H2S gas due to microbial sulfide oxidation occurring along the cave wall-atmosphere interface. Systematic variations of gypsum δ34S along gas flow paths can thus be interpreted as biogenic given that slow, abiotic oxidation cannot produce the same spatial patterns over similar length scales. The expression and preservation potential of this biosignature is dependent on gas flow parameters and diagenetic

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

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

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

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

Using stable isotopes to monitor forms of sulfur during desulfurization processes: A quick screening method

Science.gov (United States)

Liu, Chao-Li; Hackley, Keith C.; Coleman, D.D.; Kruse, C.W.

1987-01-01

A method using stable isotope ratio analysis to monitor the reactivity of sulfur forms in coal during thermal and chemical desulfurization processes has been developed at the Illinois State Geological Survey. The method is based upon the fact that a significant difference exists in some coals between the 34S/32S ratios of the pyritic and organic sulfur. A screening method for determining the suitability of coal samples for use in isotope ratio analysis is described. Making these special coals available from coal sample programs would assist research groups in sorting out the complex sulfur chemistry which accompanies thermal and chemical processing of high sulfur coals. ?? 1987.

Geology and stable isotope geochemistry of Paleoarchean sulfur. Formation, preservation and geobiology of ancient pyrite and barite

NARCIS (Netherlands)

Roerdink, D.L.|info:eu-repo/dai/nl/318834340

2013-01-01

Sulfur isotopes in ancient sulfate and sulfide minerals provide a comprehensive record of microbial processes involved in the early sulfur cycle on Earth. However, the interpretation of these isotopic signatures requires information on the geological context of such samples, because abiotic

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.

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...

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 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.

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

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

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

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.

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

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)

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

Science.gov (United States)

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.

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.

The molecular physics of photolytic fractionation of sulfur and oxygen isotopes in planetary atmospheres (Invited)

Science.gov (United States)

Johnson, M. S.; Schmidt, J. A.; Hattori, S.; Danielache, S.; Meusinger, C.; Schinke, R.; Ueno, Y.; Nanbu, S.; Kjaergaard, H. G.; Yoshida, N.

2013-12-01

Atmospheric photochemistry is able to produce large mass independent anomalies in atmospheric trace gases that can be found in geological and cryospheric records. This talk will present theoretical and experimental investigations of the molecular mechanisms producing photolytic fractionation of isotopes with special attention to sulfur and oxygen. The zero point vibrational energy (ZPE) shift and reflection principle theories are starting points for estimating isotopic fractionation, but these models ignore effects arising from isotope-dependent changes in couplings between surfaces, excited state dynamics, line densities and hot band populations. The isotope-dependent absorption spectra of the isotopologues of HCl, N2O, OCS, CO2 and SO2 have been examined in a series of papers and these results are compared with experiment and ZPE/reflection principle models. Isotopic fractionation in planetary atmospheres has many interesting applications. The UV absorption of CO2 is the basis of photochemistry in the CO2-rich atmospheres of the ancient Earth, and of Mars and Venus. For the first time we present accurate temperature and isotope dependent CO2 absorption cross sections with important implications for photolysis rates of SO2 and H2O, and the production of a mass independent anomaly in the Ox reservoir. Experimental and theoretical results for OCS have implications for the modern stratospheric sulfur budget. The absorption bands of SO2 are complex with rich structure producing isotopic fractionation in photolysis and photoexcitation.

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

Preparation of sulfur/multiple pore size porous carbon composite via gas-phase loading method for lithium-sulfur batteries

International Nuclear Information System (INIS)

Li, Long-Yan; Chen, Yan-Xiao; Guo, Xiao-Dong; Zhong, Ben-He; Zhong, Yan-Jun

2014-01-01

A porous carbon with multiple pore size distribution was synthesized, and regarded as a carrier to obtain the sulfur/carbon (S/C) composite via a gas-phase loading method. We proposed this novel gas-phase loading method by using a specially designed fluid-bed reactor to encapsulate and sequester gas-phase sulfur molecules into the porous carbon in current study. The nitrogen Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) characterizations were investigated on both the porous carbon and the sulfur/carbon composite. The results show that the gas-phase loading method contributes to the combination of sulfur molecules and matrix porous carbon. Furthermore, the sulfur/multiple pore size distribution carbon composite based on the gas-phase loading method demonstrate an excellent electrochemical property. The initial specific discharge capacity is 795.0 mAh g −1 at 800 mA g −1 , with a capacity retention of 86.3% after 100 cycles

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.

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.

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 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

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

Single and multiple ionization of sulfur atoms by electron impact

International Nuclear Information System (INIS)

Ziegler, D.L.

1982-01-01

Laboratory measurements of the cross sections for single, double, triple, and quadruple ionization of sulfur atoms by electron impact are presented for collision energies from threshold to 500 eV. The cross sections for single ionization of sulfur are measured relative to those of several elements whose absolute cross sections for single ionization are known. Cross sections for each multiple ionization process are then measured relative to those for single ionization. The configuration and operation of the apparatus for these measurements are described. The possible effects of excited sulfur reactants are examined, and the reported cross sections are felt to be characteristic of ground state sulfur atoms

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.

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)

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

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

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

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

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

Multiple-isotope separation in gas centrifuge

International Nuclear Information System (INIS)

Wood, Houston G.; Mason, T.C.; Soubbaramayer

1996-01-01

In previous works, the Onsager's pancake equation was used to provide solution to the internal counter-current flow field, which is necessary to calculate solutions to the isotope transport equation. The diffusion coefficient was assumed to be constant which is a good approximation for gases with large molecular weights, and small differences in the molecular weights of the various isotopes. A new optimization strategy was presented for determining the operating parameters of a gas centrifuge to be used for multiple-component isotope separation. Scoop drag, linear wall temperature gradient, the feed rate ant the cut have been chosen as operating parameters for the optimization. The investigation was restricted to a single centrifuge, and the problem of cascading for multiple-isotope separation was not addressed. The model describing the flow and separation phenomena in centrifuge includes a set of equations describing the fluid dynamics of the counter-current flow and the diffusion equations written for each isotope of the mixture. In this paper, an optimization algorithm is described and applied to an example for the re enrichment of spent reactor uranium

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

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

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.

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

Geological Sulfur Isotopes Indicate Elevated OCS in the Archean Atmosphere, Solving the Faint Young Sun Paradox

DEFF Research Database (Denmark)

Ueno, Yuichiro; Johnson, Matthew Stanley; Danielache, Sebastian Oscar

2009-01-01

Distributions of sulfur isotopes in geological samples would provide a record of atmospheric composition if the mechanism producing the isotope effects could be described quantitatively. We determined the UV absorption spectra of 32SO2, 33SO2, and 34SO2 and use them to interpret the geological re......-rich, reducing Archean atmosphere. The radiative forcing, due to this level of OCS, is able to resolve the faint young sun paradox. Further, the decline of atmospheric OCS may have caused the late Archean glaciation....

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

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.

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.

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 .

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

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

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

Science.gov (United States)

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

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.

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

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.

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)

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.

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

Directory of Open Access Journals (Sweden)

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.

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)

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.

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.

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

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.

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.

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.

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.

Platinum stable isotope ratio measurements by double-spike multiple collector ICPMS

DEFF Research Database (Denmark)

Creech, John; Baker, Joel; Handler, Monica

2013-01-01

We present a new technique for the precise determination of platinum (Pt) stable isotope ratios by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) using two different Pt double-spikes ( Pt-Pt and Pt-Pt). Results are expressed relative to the IRMM-010 Pt isotope standard......) can be obtained on Pt stable isotope ratios with either double-spike. Elemental doping tests reveal that double-spike corrected Pt stable isotope ratios are insensitive to the presence of relatively high (up to 10%) levels of matrix elements, although the Pt-Pt double-spike is affected by an isobaric...... = 7.308%) results in a redefined Pt atomic weight of 195.08395 ± 0.00068. Using our technique we have measured small, reproducible and statistically significant offsets in Pt stable isotope ratios between different Pt element standards and the IRMM-010 standard, which potentially indicates...

Sulfur cathode integrated with multileveled carbon nanoflake-nanosphere networks for high-performance lithium-sulfur batteries

International Nuclear Information System (INIS)

Li, S.H.; Wang, X.H.; Xia, X.H.; Wang, Y.D.; Wang, X.L.; Tu, J.P.

2017-01-01

Tailored design/construction of high-quality sulfur/carbon composite cathode is critical for development of advanced lithium-sulfur batteries. We report a powerful strategy for integrated fabrication of sulfur impregnated into three-dimensional (3D) multileveled carbon nanoflake-nanosphere networks (CNNNs) by means of sacrificial ZnO template plus glucose carbonization. The multileveled CNNNs are not only utilized as large-area host/backbone for sulfur forming an integrated S/CNNNs composite electrode, but also serve as multiple carbon blocking barriers (nanoflake infrastructure andnanosphere superstructure) to physically confine polysulfides at the cathode. The designedself-supported S/CNNNs composite cathodes exhibit superior electrochemical performances with high capacities (1395 mAh g −1 at 0.1C, and 769 mAh g −1 at 5.0C after 200 cycles) and noticeable cycling performance (81.6% retention after 200 cycles). Our results build a new bridge between sulfur and carbon networks with multiple blocking effects for polysulfides, and provide references for construction of other high-performance sulfur cathodes.

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

Properties of a novel linear sulfur response mode in a multiple flame photometric detector.

Science.gov (United States)

Clark, Adrian G; Thurbide, Kevin B

2014-01-24

A new linear sulfur response mode was established in the multiple flame photometric detector (mFPD) by monitoring HSO* emission in the red spectral region above 600nm. Optimal conditions for this mode were found by using a 750nm interference filter and oxygen flows to the worker flames of this device that were about 10mL/min larger than those used for monitoring quadratic S2* emission. By employing these parameters, this mode provided a linear response over about 4 orders of magnitude, with a detection limit near 5.8×10(-11)gS/s and a selectivity of sulfur over carbon of about 3.5×10(3). Specifically, the minimum detectable masses for 10 different sulfur analytes investigated ranged from 0.4 to 3.6ng for peak half-widths spanning 4-6s. The response toward ten different sulfur compounds was examined and produced an average reproducibility of 1.7% RSD (n=10) and an average equimolarity value of 1.0±0.1. In contrast to this, a conventional single flame S2* mode comparatively yielded respective values of 6.7% RSD (n=10) and 1.1±0.4. HSO* emission in the mFPD was also found to be relatively much less affected by response quenching due to hydrocarbons compared to a conventional single flame S2* emission mode. Results indicate that this new alternative linear mFPD response mode could be beneficial for sulfur monitoring applications. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Unravelling atmospheric photolysis and ocean redox chemistry from Paleoarchean pyrite : a multiple sulfur and iron stable isotope study

NARCIS (Netherlands)

Galić, A.

2015-01-01

This thesis brought together four individual studies on the geochemistry of three recently obtained drill cores from the Barberton Greenstone Belt, South Africa. These data were used to provide a synthesis of the iron and sulfur cycles in the Paleoarchean, with a particular focus on the nature and

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.

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.

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

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

Multiple water isotope proxy reconstruction of extremely low last glacial temperatures in Eastern Beringia (Western Arctic)

NARCIS (Netherlands)

Porter, T.J.; Froese, D.G.; Feakins, S.J.; Bindeman, I.N.; Mahony, M.E.; Pautler, B.G.; Reichart, G.-J.; Sanborn, P.T.; Simpson, M.J.; Weijers, J.W.H.

2016-01-01

Precipitation isotopes are commonly used for paleothermometry in high latitude regions. Here we present multiple water isotope proxies from the same sedimentary context – perennially frozen loess deposits in the Klondike Goldfields in central Yukon, Canada, representing parts of Marine Isotope

Multiple water isotope proxy reconstruction of extremely low last glacial temperatures in Eastern Beringia (Western Arctic)

NARCIS (Netherlands)

Porter, Trevor J.; Froese, Duane G.; Feakins, Sarah J.; Bindeman, Ilya N.; Mahony, Matthew E.; Pautler, Brent G.; Reichart, Gert-Jan; Sanborn, Paul T.; Simpson, Myrna J.; Weijers, Johan W H

2016-01-01

Precipitation isotopes are commonly used for paleothermometry in high latitude regions. Here we present multiple water isotope proxies from the same sedimentary context - perennially frozen loess deposits in the Klondike Goldfields in central Yukon, Canada, representing parts of Marine Isotope

High congruence of isotope sewage signals in multiple marine taxa

International Nuclear Information System (INIS)

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

2013-01-01

Highlights: • Sewage inputs are routinely mapped with stable isotopes ( 15 N) in organisms. • We tested whether choice of species influences spatial 15 N distributions. • Spatial gradients were consistent between algae, seagrasses, crabs, and fish. • A match of sewage-N signals in multiple marine taxa has not been reported before. • Spatially-coupled transfers in the food web produce the congruence of N imprints. -- Abstract: Assessments of sewage pollution routinely employ stable nitrogen isotope analysis (δ 15 N) in biota, but multiple taxa are rarely used. This single species focus leads to underreporting of whether derived spatial N patterns are consistent. Here we test the question of ‘reproducibility’, incorporating ‘taxonomic replication’ in the measurement of δ 15 N gradients in algae, seagrasses, crabs and fish with distance from a sewage outfall on the Adelaide coast (southern Australia). Isotopic sewage signals were equally strong in all taxa and declined at the same rate. This congruence amongst taxa has not been reported previously. It implies that sewage-N propagates to fish via a tight spatial coupling between production and consumption processes, resulting from limited animal movement that closely preserves the spatial pollution imprint. In situations such as this where consumers mirror pollution signals of primary producers, analyses of higher trophic levels will capture a broader ambit of ecological effects

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.

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

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.

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

Directory of Open Access Journals (Sweden)

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

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

than expected, given the low concentration of SO42- in precipitation, and this result reveals the existence of a spatially dispersed and significant SO42- sink, such as soil, within the MRB. The all-negative range for MRB δ34SSO4-riv indicates that oxidative weathering of both (1) reduced sulfur (e.g. biologically cycled sulfur in soil) and (2) sulfides (e.g. pyrite in coal), is the dominant source of SO42- in the MRB because all other sources of riverine SO42- have positive δ34SSO4-riv values [3]. Moreover, the Upper Ohio (UORB) and Upper Missouri (UMRB) MRB sub-basins both contain significant coalfields which are likely sources of much of the isotopically lighter SO42- in the MRB. The UORB and UMRB contributed ~1/3 of all MRB SO42- during high discharge and low discharge, respectively, and a combined 1/2 of all MRB SO42- each year in the 10-year period 1999-2009. [1]Berner, E. K., and R. A. Berner (1996), Global environment; [2]Turchyn, A. V., and D. P. Schrag (2004), Science, 303(5666), 2004-2007; [3]Rock, L., and B. Mayer (2009), Chem. Geol., 262(3-4), 121-130.

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)

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.

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.

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).

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

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.

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

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.

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)

Multiple Nebular Gas Reservoirs Recorded by Oxygen Isotope Variation in a Spinel-Rich CAI in CO3 MIL 090019

Science.gov (United States)

Simon, J. I.; Simon, S. B.; Nguyen, A. N.; Ross, D. K.; Messenger, S.

2017-07-01

We conducted NanoSIMS ion imaging studies of a primitive spinel-rich CAI from the MIL 090019 CO3 chondrite. It records radial O-isotopic heterogeneity among multiple occurrences of the same mineral, reflecting distinct nebular O-isotopic reservoirs.

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

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

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

Massive splenomegaly with multiple defects in a chronic myelogenous leukemia demonstrated by sup(99m)Tc-sulfur colloid scintigraphy

Energy Technology Data Exchange (ETDEWEB)

Shih, W J; DeLand, F H; Domstad, P A

1983-11-14

A sup(99m)Tc-sulfur colloid liver-spleen scintigram of a 78-year-old woman with a painful, large mass in the left upper quadrant of the abdomen revealed massive splenomegaly with multiple areas of absent radioactivity. Splenectomy was performed and the removed spleen, weighing 2,010 g, was confirmed to contain acute and old infarcts with leukemic cell and megakaryocyte infiltration.

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

Multiple stable isotope fronts during non-isothermal fluid flow

Science.gov (United States)

Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

2018-02-01

Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may

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).

Photoelectron Spectroscopy and Density Functional Theory Studies of Iron Sulfur (FeS)m- (m = 2-8) Cluster Anions: Coexisting Multiple Spin States.

Science.gov (United States)

Yin, Shi; Bernstein, Elliot R

2017-10-05

Iron sulfur cluster anions (FeS) m - (m = 2-8) are studied by photoelectron spectroscopy (PES) at 3.492 eV (355 nm) and 4.661 eV (266 nm) photon energies, and by density functional theory (DFT) calculations. The most probable structures and ground state spin multiplicities for (FeS) m - (m = 2-8) clusters are tentatively assigned through a comparison of their theoretical and experiment first vertical detachment energy (VDE) values. Many spin states lie within 0.5 eV of the ground spin state for the larger (FeS) m - (m ≥ 4) clusters. Theoretical VDEs of these low lying spin states are in good agreement with the experimental VDE values. Therefore, multiple spin states of each of these iron sulfur cluster anions probably coexist under the current experimental conditions. Such available multiple spin states must be considered when evaluating the properties and behavior of these iron sulfur clusters in real chemical and biological systems. The experimental first VDEs of (FeS) m - (m = 1-8) clusters are observed to change with the cluster size (number m). The first VDE trends noted can be related to the different properties of the highest singly occupied molecular orbitals (NBO, HSOMOs) of each cluster anion. The changing nature of the NBO/HSOMO of these (FeS) m - (m = 1-8) clusters from a p orbital on S, to a d orbital on Fe, and to an Fe-Fe bonding orbital is probably responsible for the observed increasing trend for their first VDEs with respect to m.

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...

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

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

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

{sub [SO4]} values (from - 2.5 to + 36.1 per mille ) in the basin relative to the margins (from + 8 per mille to + 15 per mille ) indicate that sulfur is undergoing redox cycling. The highly enriched values point to sulfate reduction that was probably mediated by bacteria. The presence of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) is also evidence of microbial reactions. The depleted signatures indicate that some oxidation of depleted sulfide occurred in the basin. It must be noted that the samples with depleted sulfur isotope values have very low sulfate concentrations and therefore even a small amount of sulfide oxidation will bias the ratio. No significant correlation was observed between {delta}{sup 34}S{sub [SO4]} values and total arsenic contents when all the samples were considered. However, the wells in the central basin do appear to become enriched in {delta}{sup 34}S{sub [SO4]} as arsenic concentration increases. Although there is evidence for sulfate reduction, it is clear that sulfate reduction does not co-precipitate or sequester arsenic. The one sample with high arsenic that is oxidizing cannot be explained by oxidation of pyrite and is likely an indication that there are multiple redox zones that control arsenic speciation but not necessarily its mobilization and contradict the possibility that Fe-oxyhydroxides sorb appreciable amounts of arsenic in this study area. It is evident that this basin like other two young sedimentary basins (Huhhot and Hetao in Inner Mongolia) of northern China with high arsenic groundwater is transporting arsenic at a very slow rate. The data are consistent with the possibility that the traditional models of arsenic mobilization, namely reductive dissolution of Fe-oxyhydroxides, reduction of As(V) to more mobile As(III), and bacteria mediated reactions, are active to varying degrees. It is also likely that different processes control arsenic mobilization at different locations of the basin and more detailed

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

- 2.5 to + 36.1 per mille ) in the basin relative to the margins (from + 8 per mille to + 15 per mille ) indicate that sulfur is undergoing redox cycling. The highly enriched values point to sulfate reduction that was probably mediated by bacteria. The presence of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) is also evidence of microbial reactions. The depleted signatures indicate that some oxidation of depleted sulfide occurred in the basin. It must be noted that the samples with depleted sulfur isotope values have very low sulfate concentrations and therefore even a small amount of sulfide oxidation will bias the ratio. No significant correlation was observed between δ 34 S [SO4] values and total arsenic contents when all the samples were considered. However, the wells in the central basin do appear to become enriched in δ 34 S [SO4] as arsenic concentration increases. Although there is evidence for sulfate reduction, it is clear that sulfate reduction does not co-precipitate or sequester arsenic. The one sample with high arsenic that is oxidizing cannot be explained by oxidation of pyrite and is likely an indication that there are multiple redox zones that control arsenic speciation but not necessarily its mobilization and contradict the possibility that Fe-oxyhydroxides sorb appreciable amounts of arsenic in this study area. It is evident that this basin like other two young sedimentary basins (Huhhot and Hetao in Inner Mongolia) of northern China with high arsenic groundwater is transporting arsenic at a very slow rate. The data are consistent with the possibility that the traditional models of arsenic mobilization, namely reductive dissolution of Fe-oxyhydroxides, reduction of As(V) to more mobile As(III), and bacteria mediated reactions, are active to varying degrees. It is also likely that different processes control arsenic mobilization at different locations of the basin and more detailed studies along major flow paths upgradient of the high

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.

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.

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.

The Archean komatiite-hosted, PGE-bearing Ni-Cu sulfide deposit at Vaara, eastern Finland: evidence for assimilation of external sulfur and post-depositional desulfurization

Science.gov (United States)

Konnunaho, J. P.; Hanski, E. J.; Bekker, A.; Halkoaho, T. A. A.; Hiebert, R. S.; Wing, B. A.

2013-12-01

Archean komatiites host important resources of Ni, Cu, Co, and PGE, particularly in Western Australia and Canada. In Finland, several small, low-grade sulfide deposits have been found in komatiites, including the ca. 2.8 Ga Vaara deposit in the Archean Suomussalmi greenstone belt. It occurs in the central part of the serpentinized olivine cumulate zone of a komatiitic extrusive body and is composed of disseminated interstitial sulfides consisting of pyrite, pentlandite, millerite, violarite, and chalcopyrite accompanied by abundant magnetite. Although currently subeconomic, the mineralization is interesting due to the very high chalcophile element contents of the sulfide fraction (38 wt% Ni, 3.4 wt% Cu, 0.7 wt% Co, 22.4 ppm Pd, and 9.5 ppm Pt). The sulfides occur in relatively Cr-poor olivine cumulates suggesting involvement of a chromite-undersaturated magma. The parental magma was an Al-undepleted komatiite with an estimated MgO content of at least 24 wt%. In contrast to the common komatiite types in the eastern Finland greenstone belts, the Vaara rocks are moderately enriched in LREE relative to MREE, suggesting that crustal contamination played an important role in the genesis of the Vaara deposit. Multiple sulfur isotope data reveal considerable mass-independent sulfur isotope fractionation both in country rock sedimentary sulfides (Δ33S ranges from -0.50 to +2.37 ‰) and in the Vaara mineralization (Δ33S ranges from +0.53 to +0.66 ‰), which provides strong evidence for incorporation of crustal sulfur. Extensive replacement of interstitial sulfides by magnetite and the presence of millerite- and violarite-bearing, pyrrhotite-free sulfide assemblages indicate significant post-magmatic, low-temperature hydrothermal oxidation of the primary magmatic pyrrhotite-pentlandite-chalcopyrite assemblages and associated sulfur loss that led to a significant upgrading of the original metal tenors of the Vaara deposit.

Multiple Nebular Gas Reservoirs Recorded by Oxygen Isotope Variation in a Spinel-rich CAI in CO3 MIL 090019

Science.gov (United States)

Simon, J. I.; Simon, S. B.; Nguyen, A. N.; Ross, D. K.; Messenger, S.

2017-01-01

We conducted NanoSIMS O-isotopic imaging of a primitive spinel-rich CAI spherule (27-2) from the MIL 090019 CO3 chondrite. Inclusions such as 27-2 are proposed to record inner nebula processes during an epoch of rapid solar nebula evolution. Mineralogical and textural analyses suggest that this CAI formed by high temperature reactions, partial melting, and condensation. This CAI exhibits radial O-isotopic heterogeneity among multiple occurrences of the same mineral, reflecting interactions with distinct nebular O-isotopic reservoirs.

Simulation of multi-photon emission isotopes using time-resolved SimSET multiple photon history generator

Energy Technology Data Exchange (ETDEWEB)

Chiang, Chih-Chieh; Lin, Hsin-Hon; Lin, Chang-Shiun; Chuang, Keh-Shih [Department of Biomedical Engineering and Environmental Sciences, National Tsing-HuaUniversity, Hsinchu, Taiwan (China); Jan, Meei-Ling [Health Physics Division, Institute of Nuclear Energy Research, Atomic Energy Council, Taoyuan, Taiwan (China)

2015-07-01

Abstract-Multiple-photon emitters, such as In-111 or Se-75, have enormous potential in the field of nuclear medicine imaging. For example, Se-75 can be used to investigate the bile acid malabsorption and measure the bile acid pool loss. The simulation system for emission tomography (SimSET) is a well-known Monte Carlo simulation (MCS) code in nuclear medicine for its high computational efficiency. However, current SimSET cannot simulate these isotopes due to the lack of modeling of complex decay scheme and the time-dependent decay process. To extend the versatility of SimSET for simulation of those multi-photon emission isotopes, a time-resolved multiple photon history generator based on SimSET codes is developed in present study. For developing the time-resolved SimSET (trSimSET) with radionuclide decay process, the new MCS model introduce new features, including decay time information and photon time-of-flight information, into this new code. The half-life of energy states were tabulated from the Evaluated Nuclear Structure Data File (ENSDF) database. The MCS results indicate that the overall percent difference is less than 8.5% for all simulation trials as compared to GATE. To sum up, we demonstrated that time-resolved SimSET multiple photon history generator can have comparable accuracy with GATE and keeping better computational efficiency. The new MCS code is very useful to study the multi-photon imaging of novel isotopes that needs the simulation of lifetime and the time-of-fight measurements. (authors)

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.

Diesel Emission Control -- Sulfur Effects (DECSE) Program; Phase I Interim Date Report No. 3: Diesel Fuel Sulfur Effects on Particulate Matter Emissions

Energy Technology Data Exchange (ETDEWEB)

DOE; ORNL; NREL; EMA; MECA

1999-11-15

The Diesel Emission Control-Sulfur Effects (DECSE) is a joint government/industry program to determine the impact of diesel fuel sulfur levels on emission control systems whose use could lower emissions of nitrogen oxides (NO{sub x}) and particulate matter (PM) from on-highway trucks in the 2002--2004 model years. Phase 1 of the program was developed with the following objectives in mind: (1) evaluate the effects of varying the level of sulfur content in the fuel on the emission reduction performance of four emission control technologies; and (2) measure and compare the effects of up to 250 hours of aging on selected devices for multiple levels of fuel sulfur content. This interim report covers the effects of diesel fuel sulfur level on particulate matter emissions for four technologies.

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.

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

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.)

Triple oxygen and sulfur isotope analyses of sulfate extracted from voluminous volcanic ashes in the Oligocene John Day Formation: insight into dry climate conditions and ozone contribution to supereruptions

Science.gov (United States)

Workman, J.; Bindeman, I. N.; Martin, E.; Retallack, G.; Palandri, J. L.; Weldon, N.

2014-12-01

Large volume pyroclastic silicic eruptions emit hundreds of megatons of SO2 into the troposphere and stratosphere that is oxidized into sulfuric acid (H2SO4) by a variety of reactions with mass independent oxygen signatures (MIF), Δ17O>0. Sulfuric acid is then preserved as gypsum in parental volcanic deposits. Diagenic effects are mass dependent and can dilute, but otherwise do not affect MIF ratios. Pleistocene Yellowstone and Bishop tuffs and modern volcanic eruptions preserved under arid climate conditions in North American playa lakes, preserve small amounts of volcanic sulfate as gypsum. This gypsum's Δ17O>0, in combination with isotopic variations of δ18O, δ33S and δ34S is distinct from sedimentary sulfate and reveals its original MIF sulfate isotopic signal and the effect of super eruptions on the atmosphere, and ozone consumption in particular. We use linear algebraic equations to resolve volcanic versus sedimentary (MIF=0) sources. We have found that many large volume ignimbrites have very high initial Δ17O in volcanic sulfate that can only be acquired from reaction with stratospheric ozone. We here investigate nine thick (>2 m) ash beds ranging in age from ~33-23 Ma in the John Day Formation of central Oregon, including massive 28.6 Ma Picture Gorge tuff of newly identified Crooked River supercaldera. The 28.6 Ma Picture Gorge tuff (PGT) has the highest measured Δ17O of 3.5‰, and other tuffs (Tin Roof, Biotite, Deep Creek) have +1.3 to 3.4‰ Δ17O excesses. Sulfate from modern smaller tropospheric eruptions studied for comparison have a resolvable 0.4‰ range consistent with liquid-phase based H2O2 oxidation. The PGT is coeval with the ignimbrite flare-up in western N. America, the 28-29 Ma eruption of the 5000 km3 Fish Canyon tuff and the 28 Ma Never Summer Field eruption in Nebraska-Colorado that have the highest measured Δ17O of 6‰ (Bao et al. 2003). We speculate on the climatic/atmospheric effects of these multiple ~28 Ma supereruptions

Development of precise analytical methods for strontium and lanthanide isotopic ratios using multiple collector inductively coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Ohno, Takeshi; Takaku, Yuichi; Hisamatsu, Shun'ichi

2007-01-01

We have developed precise analytical methods for strontium and lanthanide isotopic ratios using multiple collector-ICP-mass spectrometry (MC-ICP-MS) for experimental and environmental studies of their behavior. In order to obtain precise isotopic data using MC-ICP-MS, the mass discrimination effect was corrected by an exponential law correction method. The resulting isotopic data demonstrated that highly precise isotopic analyses (better than 0.1 per mille as 2SD) could be achieved. We also adopted a de-solvating nebulizer system to improve the sensitivity. This system could minimize the water load into the plasma and provided about five times larger intensity of analyte than a conventional nebulizer system did. (author)

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

Uranium Isotopic Analysis with the FRAM Isotopic Analysis Code

International Nuclear Information System (INIS)

Vo, D.T.; Sampson, T.E.

1999-01-01

FRAM is the acronym for Fixed-Energy Response-Function Analysis with Multiple efficiency. This software was developed at Los Alamos National Laboratory originally for plutonium isotopic analysis. Later, it was adapted for uranium isotopic analysis in addition to plutonium. It is a code based on a self-calibration using several gamma-ray peaks for determining the isotopic ratios. The versatile-parameter database structure governs all facets of the data analysis. User editing of the parameter sets allows great flexibility in handling data with different isotopic distributions, interfering isotopes, and different acquisition parameters such as energy calibration and detector type

Stable isotope ratiometer-multiple ion detector (SIRMID) unit for quantitative and qualitative stable isotope studies by gas chromatography-mass spectrometry

International Nuclear Information System (INIS)

Klein, P.D.; Haumann, J.R.; Hachey, D.L.

1975-01-01

A stable isotope ratiometer-multiple ion detector (SIRMID) unit which can drive existing gas chromatograph-quadrupole or magnetic sector mass spectrometers to monitor up to six ions in turn is described. Each of the three pairs of ions can be selected for quantitation; thus three different or successive components can be analyzed in a single GC run. A background subtraction option permits the ion intensity in the absence of sample to be subtracted automatically during sample measurement. Displays of accumulated counts and isotope ratio are updated twice per second during the measurement and can be printed out at its conclusion. All six ions can be monitored in the analog mode by parallel outputs to a multipen recorder. Experience gained in the construction of this prototype indicates that SIRMID units could be commercially available for $10K, or about 1 / 3 rd to 1 / 6 th of the cost of even an inexpensive computer system. (U.S.)

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.

Improved environmental and forensics measurements using multiple ion counters in isotope ratio mass spectrometry

International Nuclear Information System (INIS)

Goldberg, S.A.; Richter, S.; Schwieters, H.

2002-01-01

Full text: A new detector system designed for isotope ratio mass spectrometers provides improved precision on measurements of samples with very low amounts ( -11 grams) of analyte. An array of continuous dynode electron multipliers has been installed on a new ThermoFinnigan MAT Triton thermal ionization mass spectrometer acquired by the New Brunswick Laboratory. These ion counters are modifications of miniaturized, commercially-available continuous dynode electron multipliers. They can be readily installed to replace individual Faraday cups in a multi-detector mass spectrometer or bundled together and located along the detector plane with a set of Faraday cups. On the New Brunswick Laboratory mass spectrometer, nine Faraday cups, one conventional discrete dynode electron multiplier, and seven miniaturized ion counters were installed. Six of the small ion counters were bundled together and positioned on the high mass side of the Low 4 Faraday cup. One additional ion counter was positioned on the low mass side of the Low 4 Faraday cup. This arrangement allows for the simultaneous measurement of all uranium (including 233 U) or plutonium (including 244 Pu) isotopes, and allows for the measurement of larger 238 U intensities on the Faraday cup if needed. Unit mass spacing of U, Pu, or other actinides is readily achieved by the use of a mass dispersion zoom lens. The advantage of multiple ion counting is the simultaneous collection of isotopes. It overcomes many of the problems such as transient signal variation in sample emission and ionization. For a given sample, multiple ion counting generates a greater number of counts for each isotope relative to single detector ion counting and provides improved counting statistics by a factor of two or more. Initial tests indicate that the multiple ion counters exhibit high counting efficiency, a dark noise of less than 10 counts per minute and typically less than 1 count per minute, and show linear response characteristics over

Study of multiplication factor sensitivity to the spread of WWER spent fuel isotopics calculated by different codes

International Nuclear Information System (INIS)

Markova, L.

2001-01-01

As a sensitivity study the impact on the system reactivity was studied in the case that different calculational methodologies of spent fuel isotopic concentrations were used for WWER spent fuel inventory computations. The sets of isotopic concentrations obtained by calculations with different codes and libraries as a result of the CB2 international benchmark focused on WWER-440 burnup credit were used to show the spread of the calculated spent fuel system reactivity. Using the MCNP 4B code and changing the isotopics input data, the multiplication factor of an infinite array of the WWER-440 fuel pin cells was calculated. The evaluation of the results shows the sensitivity of the calculated reactivity to different calculational methodologies used for the spent fuel inventory computation. In the studied cases of the CB2 benchmark, the spread of the reference k-results relative to the mean was found less or about ±1% in spite of the fact that the data of isotopic concentrations were spread much more. (author)

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

Science.gov (United States)

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

2018-05-01

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

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

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.

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 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.

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

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.

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.

Evaluations of the trans-sulfuration pathway in multiple liver toxicity studies

International Nuclear Information System (INIS)

Schnackenberg, Laura K.; Chen Minjun; Sun, Jinchun; Holland, Ricky D.; Dragan, Yvonne; Tong Weida; Welsh, William; Beger, Richard D.

2009-01-01

Drug-induced liver injury has been associated with the generation of reactive metabolites, which are primarily detoxified via glutathione conjugation. In this study, it was hypothesized that molecules involved in the synthesis of glutathione would be diminished to replenish the glutathione depleted through conjugation reactions. Since S-adenosylmethionine (SAMe) is the primary source of the sulfur atom in glutathione, UPLC/MS and NMR were used to evaluate metabolites involved with the transulfuration pathway in urine samples collected during studies of eight liver toxic compounds in Sprague-Dawley rats. Urinary levels of creatine were increased on day 1 or day 2 in 8 high dose liver toxicity studies. Taurine concentration in urine was increased in only 3 of 8 liver toxicity studies while SAMe was found to be reduced in 4 of 5 liver toxicity studies. To further validate the results from the metabonomic studies, microarray data from rat liver samples following treatment with acetaminophen was obtained from the Gene Expression Omnibus (GEO) database. Some genes involved in the trans-sulfuration pathway, including guanidinoacetate N-methyltransferase, glycine N-methyltransferase, betaine-homocysteine methyltransferase and cysteine dioxygenase were found to be significantly decreased while methionine adenosyl transferase II, alpha increased at 24 h post-dosing, which is consistent with the SAMe and creatine findings. The metabolic and transcriptomic results show that the trans-sulfuration pathway from SAMe to glutathione was disturbed due to the administration of heptatotoxicants

Combining Solvent Isotope Effects with Substrate Isotope Effects in Mechanistic Studies of Alcohol and Amine Oxidation by Enzymes*

Science.gov (United States)

Fitzpatrick, Paul F.

2014-01-01

Oxidation of alcohols and amines is catalyzed by multiple families of flavin-and pyridine nucleotide-dependent enzymes. Measurement of solvent isotope effects provides a unique mechanistic probe of the timing of the cleavage of the OH and NH bonds, necessary information for a complete description of the catalytic mechanism. The inherent ambiguities in interpretation of solvent isotope effects can be significantly decreased if isotope effects arising from isotopically labeled substrates are measured in combination with solvent isotope effects. The application of combined solvent and substrate (mainly deuterium) isotope effects to multiple enzymes is described here to illustrate the range of mechanistic insights that such an approach can provide. PMID:25448013

Internal correction of spectral interferences and mass bias for selenium metabolism studies using enriched stable isotopes in combination with multiple linear regression.

Science.gov (United States)

Lunøe, Kristoffer; Martínez-Sierra, Justo Giner; Gammelgaard, Bente; Alonso, J Ignacio García

2012-03-01

The analytical methodology for the in vivo study of selenium metabolism using two enriched selenium isotopes has been modified, allowing for the internal correction of spectral interferences and mass bias both for total selenium and speciation analysis. The method is based on the combination of an already described dual-isotope procedure with a new data treatment strategy based on multiple linear regression. A metabolic enriched isotope ((77)Se) is given orally to the test subject and a second isotope ((74)Se) is employed for quantification. In our approach, all possible polyatomic interferences occurring in the measurement of the isotope composition of selenium by collision cell quadrupole ICP-MS are taken into account and their relative contribution calculated by multiple linear regression after minimisation of the residuals. As a result, all spectral interferences and mass bias are corrected internally allowing the fast and independent quantification of natural abundance selenium ((nat)Se) and enriched (77)Se. In this sense, the calculation of the tracer/tracee ratio in each sample is straightforward. The method has been applied to study the time-related tissue incorporation of (77)Se in male Wistar rats while maintaining the (nat)Se steady-state conditions. Additionally, metabolically relevant information such as selenoprotein synthesis and selenium elimination in urine could be studied using the proposed methodology. In this case, serum proteins were separated by affinity chromatography while reverse phase was employed for urine metabolites. In both cases, (74)Se was used as a post-column isotope dilution spike. The application of multiple linear regression to the whole chromatogram allowed us to calculate the contribution of bromine hydride, selenium hydride, argon polyatomics and mass bias on the observed selenium isotope patterns. By minimising the square sum of residuals for the whole chromatogram, internal correction of spectral interferences and mass

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.)

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

MULTIPLE ORIGINS OF NITROGEN ISOTOPIC ANOMALIES IN METEORITES AND COMETS

International Nuclear Information System (INIS)

Aleon, Jerome

2010-01-01

Isotopic fractionation and mixing calculations compared with coupled hydrogen and nitrogen isotopic composition of organic molecules from primitive chondrites, interplanetary dust particles (IDPs), and comets C/1995 O1 (Hale-Bopp) and 81P/Wild2 reveal that meteoritic and cometary organic matter contains three different isotopic components of different origins. (1) A major component of carbonaceous chondrites, IDPs, and comets Hale-Bopp and Wild2 shows correlated H and N isotopic compositions attributable to isotope exchange between an organic matter of solar composition and a reservoir formed by ion-molecule reactions at T 15 N-rich component having identical 15 N and D enrichments relative to the protosolar gas. Temperatures > 100 K deduced from the low D/H ratio and an anti-correlation between the abundance of this component and meteoritic age indicate a late origin in the solar protoplanetary disk. N 2 self-shielding and the non-thermal nucleosynthesis of 15 N upon irradiation are possible but unlikely sources of this component, and a chemical origin is preferred. (3) An interstellar component with highly fractionated hydrogen isotopes and unfractionated nitrogen isotopes is present in ordinary chondrites. A dominantly solar origin of D and 15 N excesses in primitive solar system bodies shows that isotopic anomalies do not necessarily fingerprint an interstellar origin and implies that only a very small fraction of volatile interstellar matter survived the events of solar system formation.

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)

Neutron Multiplicity Analysis

Energy Technology Data Exchange (ETDEWEB)

Frame, Katherine Chiyoko [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2017-06-28

Neutron multiplicity measurements are widely used for nondestructive assay (NDA) of special nuclear material (SNM). When combined with isotopic composition information, neutron multiplicity analysis can be used to estimate the spontaneous fission rate and leakage multiplication of SNM. When combined with isotopic information, the total mass of fissile material can also be determined. This presentation provides an overview of this technique.

13C Kinetic isotopic effect of polymerization on monomers with multiple bond

International Nuclear Information System (INIS)

Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

1988-01-01

13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

Analysis of Atmospheric Nitrate Deposition in Lake Tahoe Using Multiple Oxygen Isotopes

Science.gov (United States)

McCabe, J. R.; Michalski, G. M.; Hernandez, L. P.; Thiemens, M. H.; Taylor, K.; Kendall, C.; Wankel, S. D.

2002-12-01

Lake Tahoe in the Sierra Nevada Mountain Range is world renown for its depth and water clarity bringing 2.2 million visitors per year resulting in annual revenue of \\1.6 billion from tourism. In past decades the lake has suffered from decreased water clarity (from 32 m plate depth to less than 20), which is believed to be largely the result of algae growth initiated by increased nutrient loading. Lake nutrients have also seen a shift from a nitrogen limited to a phosphorous limited system indicating a large increase in the flux of fixed nitrogen. Several sources of fixed nitrogen of have been suggested including surface runoff, septic tank seepage from ground water and deposition from the atmosphere. Bio-available nitrogen in the form of nitrate (NO_{3}$-) is a main component of this system. Recent studies have estimated that approximately 50% of the nitrogen input into the lake is of atmospheric origin (Allison et al. 2000). However, the impact and magnitude of atmospheric deposition is still one of the least understood aspects of the relationship between air and water quality in the Basin (TRPA Threshold Assessment 2002). The utility of stable isotopes as tracers of nitrate reservoirs has been shown in several studies (Bohlke et al. 1997, Kendall and McDonnell 1998, Durka et al. 1994). Stable nitrogen (δ15N) and oxygen (δ18O) isotopes have been implemented in a dual isotope approach to characterize the various nitrate sources to an ecosystem. While δ18O distinguishes between atmospheric and soil sources of nitrate, processes such as denitrification can enrich the residual nitrate in δ18O leaving a misleading atmospheric signature. The benefit of δ15N as a tracer for NO3- sources is the ability to differentiate natural soil, fertilizer, and animal or septic waste, which contain equivalent δ18O values. The recent implementation of multiple oxygen isotopes to measure Δ17O in nitrate has proven to be a more sensitive tracer of atmospheric deposition. The

Statistical model of hadrons multiple production in space of total angular momentum and isotopic spin

International Nuclear Information System (INIS)

Gridneva, S.A.; Rus'kin, V.I.

1980-01-01

Basic features of the statistical model of multiple hadron production based on microcanonical distribution and taking into account the laws of conservation of total angular momentum, isotopic spin, p-, G-, C-eveness and Bose-Einstein statistics requirements are given. The model predictions are compared with experimental data on anti NN annihilation at rest and e + e - annihilation in hadrons at annihilation total energy from 2 to 3 GeV [ru

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....

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

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.

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).

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

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 separation process

International Nuclear Information System (INIS)

Lyon, R.K.

1976-01-01

The instant invention relates to a process for separating a material into two or more parts in each of which the abundances of the isotopes of a given element differ from the abundances of the isotopes of the same material in said material. In one embodiment, the invention relates to a method for the isotopically selective excitation of gas phase molecules by multiple infrared photon absorption followed by selective dissociation of said excited molecules by the absorption of a single photon of visible or ultraviolet light. This invention is useful for, but not limited to, the separation of the principal isotopes of uranium. 11 Claims, 2 Drawing Figures

Application of heavy stable isotopes in forensic isotope geochemistry: A review

International Nuclear Information System (INIS)

Aggarwal, Jugdeep; Habicht-Mauche, Judith; Juarez, Chelsey

2008-01-01

Light stable isotopes have been used for many years to characterize the source and transport of materials. More recently heavy isotope systems such as Sr, Nd and Pb have been added to this list in order to aid source identification. With the advent of multiple collector ICP-MS, the range of isotopic tools now available has increased considerably, however, until the isotope systematics of these new non-traditional isotope systems have become better understood, they will not be as useful in characterizing material source and transportation. Applications using heavy metal stable isotopes (mostly traditional heavy isotopes) have reached most avenues in science, including earth sciences, archaeology, anthropology, animal physiology, ecology and toxicology. This field will continue to grow as new applications are developed and techniques become simpler and quicker. This paper provides a review of how this field has grown and presents two new applications using Pb and Sr isotopes in glazes to determine the source of ore used in glazes, and using Sr isotopes to determine the origin of undocumented deceased Mexican border crossers

Application of heavy stable isotopes in forensic isotope geochemistry: A review

Energy Technology Data Exchange (ETDEWEB)

Aggarwal, Jugdeep [W.M. Keck Isotope Laboratory, Department of Earth Sciences, University of California, Santa Cruz, CA 95064 (United States)], E-mail: jaggarwal@pmc.ucsc.edu; Habicht-Mauche, Judith; Juarez, Chelsey [Department of Anthropology, University of California, Santa Cruz, CA 95064 (United States)

2008-09-15

Light stable isotopes have been used for many years to characterize the source and transport of materials. More recently heavy isotope systems such as Sr, Nd and Pb have been added to this list in order to aid source identification. With the advent of multiple collector ICP-MS, the range of isotopic tools now available has increased considerably, however, until the isotope systematics of these new non-traditional isotope systems have become better understood, they will not be as useful in characterizing material source and transportation. Applications using heavy metal stable isotopes (mostly traditional heavy isotopes) have reached most avenues in science, including earth sciences, archaeology, anthropology, animal physiology, ecology and toxicology. This field will continue to grow as new applications are developed and techniques become simpler and quicker. This paper provides a review of how this field has grown and presents two new applications using Pb and Sr isotopes in glazes to determine the source of ore used in glazes, and using Sr isotopes to determine the origin of undocumented deceased Mexican border crossers.

A simple and reliable anion-exchange resin method for sulfate extraction and purification suitable for multiple O- and S-isotope measurements.

Science.gov (United States)

Le Gendre, Erwann; Martin, Erwan; Villemant, Benoit; Cartigny, Pierre; Assayag, Nelly

2017-01-15

The O- and S-isotope compositions of sulfates can be used as key tracers of the fate and sink of sulfate in both terrestrial and extra-terrestrial environments. However, their application remains limited in those geological systems where sulfate occurs in low concentrations. Here we present a simple and reliable method to extract, purify and concentrate sulfate from natural samples. The method allows us to take into account the separation of nitrate, which is known to be an issue in O-isotope analysis. The separation and concentration of sulfate from other anions in any aqueous solution are performed within a few hours via anion-exchange resin. The possible O- (δ 18 O and Δ 17 O) and S- (δ 34 S, Δ 33 S and Δ 36 S) isotope exchanges, fractionations and/or contaminations are for the first time monitored during the whole procedure using initial O- and S-mass-dependent and mass-independent sulfate solutions. After elution in HCl, pure sulfate is fully retrieved and precipitated into BaSO 4 , which is suitable for O- and S-isotopic measurements using established techniques. The analysis of retrieved barite presents no variation within 2σ uncertainties: ±0.5‰ and ±0.1‰ in O- (δ 18 O, Δ 17 O) and ±0.2‰, ±0.02‰ and ±0.09‰ in S- (δ 34 S, Δ 33 S and Δ 36 S) isotope ratios, respectively. This study shows that the resin method for sulfate extraction and purification, in addition to being cheap, simple and quick, is applicable for the measurements of all O- and S-isotopic ratios in sulfates (including the Δ 17 O, Δ 33 S and Δ 36 S values). Therefore, this method can be easily used for a high range of natural samples in which sulfate occurs in low concentration including aerosols, ice cores, sediments, volcanic deposits, (paleo)soils and rainwater, and thus it can be a key to our understanding of the sulfur cycle on Earth. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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.

Climatic signals in multiple highly resolved stable isotope records from Greenland

DEFF Research Database (Denmark)

Vinther, Bo Møllesøe; Dahl-Jensen, Dorthe; Johnsen, Sigfus Johann

2010-01-01

are found to correspond better with winter stable isotope data than with summer or annual average stable isotope data it is suggested that a strong local Greenland temperature signal can be extracted from the winter stable isotope data even on centennial to millennial time scales. Udgivelsesdato: Feb....

Sulfur dioxide: foe or friend for life?

Science.gov (United States)

Wang, Xin-Bao; Cui, Hong; Liu, Xiaohong; Du, Jun-Bao

2017-12-01

Sulfur dioxide (SO₂) is a toxic gas and air pollutant. The toxic effects of SO₂ have been extensively studied. Oxidative damage due to SO₂ can occur in multiple organs. Inhaled SO₂ can also cause chromosomal aberrations, DNA damage and gene mutations in mammals. However, SO₂ can also be generated from the sulfur-containing amino acid, L-cysteine. Recent studies have shown that SO₂ has a vasorelaxant effect, and ameliorates pulmonary hypertension and vascular remodeling. SO₂ can also reduce lung injury and myocardial injury in rats. In addition, SO₂ reduces myocardial ischemia-reperfusion injury and atherosclerotic lesions. Therefore, SO₂ exerts both detrimental and protective effects in mammals. Is SO₂ a foe or friend for life?.

Performance of the multiple target He/PbI sub 2 aerosol jet system for mass separation of neutron-deficient actinide isotopes

CERN Document Server

Ichikawa, S; Asai, M; Haba, H; Sakama, M; Kojima, Y; Shibata, M; Nagame, Y; Oura, Y; Kawade, K

2002-01-01

A multiple target He/PbI sub 2 aerosol jet system coupled with a thermal ion source was installed in the isotope separator on line (JAERI-ISOL) at the JAERI tandem accelerator facility. The neutron-deficient americium and curium isotopes produced in the sup 2 sup 3 sup 3 sup , sup 2 sup 3 sup 5 U( sup 6 Li, xn) and sup 2 sup 3 sup 7 Np( sup 6 Li, xn) reactions were successfully mass-separated and the overall efficiency including the ionization of Am atoms was evaluated to be 0.3-0.4%. The identification of a new isotope sup 2 sup 3 sup 7 Cm with the present system is reported.

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...

Flexible three-dimensional electrodes of hollow carbon bead strings as graded sulfur reservoirs and the synergistic mechanism for lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Yang, Dan [College of Materials Science and Engineering, Sichuan University, Chengdu, 610064 (China); Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900 (China); Ni, Wei, E-mail: niwei@iccas.ac.cn [Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900 (China); Cheng, Jianli; Wang, Zhuanpei; Wang, Ting; Guan, Qun [Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900 (China); Zhang, Yun, E-mail: y_zhang@scu.edu.cn [College of Materials Science and Engineering, Sichuan University, Chengdu, 610064 (China); Wu, Hao [College of Materials Science and Engineering, Sichuan University, Chengdu, 610064 (China); Li, Xiaodong [Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900 (China); Wang, Bin, E-mail: edward.bwang@gmail.com [Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900 (China)

2017-08-15

Graphical abstract: Flexible three-dimensional electrode comprised of stringed N-doped hollow carbon spheres shows a synergistic sulfur confinement mechanism and a higher energy/power density for the promising lithium-sulfur batteries compared with traditional electrodes. - Highlights: • Hollow carbon beads on string structure was first prepared. • Flexible 3D electrodes as graded reservoirs for polysulfides were conducted. • Synergistic effect for enhanced polysulfides storage was claimed. - Abstract: Three-dimensional (3D) flexible electrodes of stringed hollow nitrogen-doped (N-doped) carbon nanospheres as graded sulfur reservoirs and conductive frameworks were elaborately designed via a combination of the advantages of hollow structures, 3D electrodes and flexible devices. The as-prepared electrodes by a synergistic method of electrospinning, template sacrificing and activation for Li–S batteries without any binder or conductive additives but a 3D interconnected conductive network offered multiple transport paths for electrons and improved sulfur utilization and facilitated an easy access to Li{sup +} ingress/egress. With the increase of density of hollow carbon spheres in the strings, the self-supporting composite electrode reveals an enhanced synergistic mechanism for sulfur confinement and displays a better cycling stability and rate performance. It delivers a high initial specific capacity of 1422.6 mAh g{sup −1} at the current rate of 0.2C with the high sulfur content of 76 wt.%, and a much higher energy density of 754 Wh kg{sup −1} and power density of 1901 Wh kg{sup −1}, which greatly improve the energy/power density of traditional lithium–sulfur batteries and will be promising for further commercial applications.

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.

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.)

Isotope separation process

International Nuclear Information System (INIS)

Lyon, R.K.

1979-01-01

A method is described for the isotopically selective excitation of gas phase molecules by multiple infrared photon absorption after which more of the excited molecules than nonexcited molecules are converted to a chemically different form which may be separated by means known in the art. This invention is useful for, but not limited to, the separation of the principal isotopes of uranium

Isotope separation process

International Nuclear Information System (INIS)

Thomas, W.R.L.

1979-01-01

The instant invention relates to an improved process for separating a material into two or more parts in each of which the abundances of the isotopes of a given element differ from the abundances of the isotopes of the same element in said material. More particularly, the invention relates to a method for the isotopically selective excitation of gas phase molecules by multiple infrared photon absorption followed by a step wherein more of the excited molecules than non-excited molecules are converted to a chemically different form which may be separated by means known in the art. This invention is useful for, but not limited to, the separation of the principal isotopes of uranium

Isotope separation process

International Nuclear Information System (INIS)

Lyon, R.K.

1977-01-01

The instant invention relates to a process for separating a material into two or more parts in each of which the abundances of the isotopes of a given element differ from the abundances of the isotopes of the same material in said material. More particularly, the invention relates to a method for the isotopically selective excitation of gas phase molecules by multiple infrared photon absorption followed by a step wherein more of the excited molecules than nonexcited molecules are converted to a chemically different form which may be separated by means known in the art. This invention is useful for, but not limited to, the separation of the principal isotopes of uranium. 15 claims, 1 figure

High-precision measurement of variations in calcium isotope ratios in urine by multiple collector inductively coupled plasma mass spectrometry

Science.gov (United States)

Morgan, J.L.L.; Gordon, G.W.; Arrua, R.C.; Skulan, J.L.; Anbar, A.D.; Bullen, T.D.

2011-01-01

We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making high-precision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizing HBr achieves the purity required to accurately and precisely measure two Ca isotope ratios (44Ca/42Ca and 44Ca/43Ca) on a Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS) in urine. Purification requirements for Sr, Ti, and K (Ca/Sr > 10000; Ca/Ti > 10000000; and Ca/K > 10) were determined by addition of these elements to Ca standards of known isotopic composition. Accuracy was determined by (1) comparing Ca isotope results for samples and standards to published data obtained using thermal ionization mass spectrometry (TIMS), (2) adding a Ca standard of known isotopic composition to a urine sample purified of Ca, and (3) analyzing mixtures of urine samples and standards in varying proportions. The accuracy and precision of δ44/42Ca measurements of purified samples containing 25 μg of Ca can be determined with typical errors less than ±0.2‰ (2σ).

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.

Mass fractionation processes of transition metal isotopes

Science.gov (United States)

Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

2002-06-01

Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

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

Stable carbon isotope fractionation of chlorinated ethenes by a microbial consortium containing multiple dechlorinating genes.

Science.gov (United States)

Liu, Na; Ding, Longzhen; Li, Haijun; Zhang, Pengpeng; Zheng, Jixing; Weng, Chih-Huang

2018-08-01

The study aimed to determine the possible contribution of specific growth conditions and community structures to variable carbon enrichment factors (Ɛ- carbon ) values for the degradation of chlorinated ethenes (CEs) by a bacterial consortium with multiple dechlorinating genes. Ɛ- carbon values for trichloroethylene, cis-1,2-dichloroethylene, and vinyl chloride were -7.24% ± 0.59%, -14.6% ± 1.71%, and -21.1% ± 1.14%, respectively, during their degradation by a microbial consortium containing multiple dechlorinating genes including tceA and vcrA. The Ɛ- carbon values of all CEs were not greatly affected by changes in growth conditions and community structures, which directly or indirectly affected reductive dechlorination of CEs by this consortium. Stability analysis provided evidence that the presence of multiple dechlorinating genes within a microbial consortium had little effect on carbon isotope fractionation, as long as the genes have definite, non-overlapping functions. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

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

High Precision Zinc Stable Isotope Measurement of Certified Biological Reference Materials Using the Double Spike Technique and Multiple Collector-ICP-MS.

Science.gov (United States)

Moore, Rebekah E T; Larner, Fiona; Coles, Barry J; Rehkämper, Mark

2017-04-01

Biological reference materials with well-characterised stable isotope compositions are lacking in the field of 'isotope biochemistry', which seeks to understand bodily processes that rely on essential metals by determining metal stable isotope ratios. Here, we present Zn stable isotope data for six biological reference materials with certified trace metal concentrations: fish muscle, bovine muscle, pig kidney, human hair, human blood serum and human urine. Replicate analyses of multiple aliquots of each material achieved reproducibilities (2sd) of 0.04-0.13‰ for δ 66/64 Zn (which denotes the deviation of the 66 Zn/ 64 Zn ratio of a sample from a pure Zn reference material in parts per 1000). This implies only very minor isotopic heterogeneities within the samples, rendering them suitable as quality control materials for Zn isotope analyses. This endorsement is reinforced by (i) the close agreement of our Zn isotope data for two of the samples (bovine muscle and human blood serum) to previously published results for different batches of the same material and (ii) the similarity of the isotopic data for the samples (δ 66/64 Zn ≈ -0.8 to 0.0‰) to previously published Zn isotope results for similar biological materials. Further tests revealed that the applied Zn separation procedure is sufficiently effective to enable accurate data acquisition even at low mass resolving power (M/ΔM ≈ 400), as measurements and analyses conducted at much higher mass resolution (M/ΔM ≈ 8500) delivered essentially identical results.

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.

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

Full Text Available Introduction The Baqoroq Cu-Zn-As deposit is located northeast of the town ofAnarak in Isfahan province, in theeast central areaof Iran. Copper mineralization occursin upper cretaceous carbonate rocks.Studyof thegeologyof the Nakhlak area, the location ofa carbonate-hosted base metaldeposit, indicatesthe importance of stratigraphic, lithological and structural controls in the placement of this ore deposit. (Jazi et al., 2015.Some of the most world’s most important epigenetic, stratabound and discordant copperdeposits are the carbonate hosted Tsumeb and Kipushi type deposits,located in Africa. The Baqoroq deposit is believed to be of this type. Materials and methods In the current study, fifty rock samples were collected from old tunnels and surface mineralization. Twenty-two thin sections, ten polished sections and four thin-polished sections were prepared for microscopic study. Ten samples were selected for elemental analysis by ICP-OES (Inductively coupled plasma optical emission spectrometry by the Zar Azma Company (Tehran and AAS (Atomic absorption spectrometry at the Ferdowsi University of Mashhad. Seven doubly polished sections of barite mineralization were prepared for microthermometric analysis. Homogenization and last ice-melting temperatures were measured using a Linkam THMSG 600 combined heating and freezing stage at Ferdowsi University of Mashhad. Sulfur isotopes of five barite samples were determined by the Iso-Analytical Ltd. Company of the UK. The isotopic ratios are presented in per mil (‰notation relative to the Canyon Diablo Troilite. Results The upper Cretaceoushost rocks of the Baqoroq deposit include limestone, sandstone, and conglomerate units. Mineralization is controlled by two main factors: lithostratigraphy and structure. Epigenetic Cu-Zn mineralizationoccurs in ore zones as stratabound barite and barite-calcite veins and minor disseminated mineralization. Open space filling occurred as breccia matrix

Performance Enhancement of a Sulfur/Carbon Cathode by Polydopamine as an Efficient Shell for High-Performance Lithium-Sulfur Batteries.

Science.gov (United States)

Zhang, Xuqing; Xie, Dong; Zhong, Yu; Wang, Donghuang; Wu, Jianbo; Wang, Xiuli; Xia, Xinhui; Gu, Changdong; Tu, Jiangping

2017-08-04

Lithium-sulfur batteries (LSBs) are considered to be among the most promising next-generation high-energy batteries. It is a consensus that improving the conductivity of sulfur cathodes and impeding the dissolution of lithium polysulfides are two key accesses to high-performance LSBs. Herein we report a sulfur/carbon black (S/C) cathode modified by self-polymerized polydopamine (pDA) with the assistance of polymerization treatment. The pDA acts as a novel and effective shell on the S/C cathode to stop the shuttle effect of polysulfides. By the synergistic effect of enhanced conductivity and multiple blocking effect for polysulfides, the S/C@pDA electrode exhibits improved electrochemical performances including large specific capacity (1135 mAh g -1 at 0.2 C), high rate capability (533 mAh g -1 at 5 C) and long cyclic life (965 mAh g -1 after 200 cycles). Our smart design strategy may promote the development of high-performance LSBs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Laser isotope separation studies in JAERI

International Nuclear Information System (INIS)

Arisawa, Takashi; Shiba, Koreyuki

1986-01-01

For uranium enrichment, Japan Atomic Energy Research Institute (JAERI) has been studying atomic vapor laser isotope separation since 1976, in addition to such separation methods as gas diffusion, chemical exchange and gas-dynamic techniques. Studies carried out to date in JAERI is briefly summarized in the first part of the report. Then, some major separation techniques which have been studied in JAERI are outlined, and typical results obtained are presented. A large part is devoted to the multiple-photon photoionization technique, which is commonly known as the atomic laser isotope separation method for uranium enrichment. It has such advantages as 1) very high spectral selectivity for the relevant isotope and 2) highly improved photoionizing effect by means of two- and three-step resonance photoionization processes. Here, the atomic laser isotope separation method is discussed in detail with respect to the evaporation process, energy levels, photoionization, selectivity, photoionization schemes, ion recovery, separation in macroscopic amounts, and separation of trace amounts of isotopes. Typical observed and claculated results related to these subjects are shown. In addition, the report briefly describes some other separation processes including laser induced chemical reaction, multiple photo-dissociation, multiple-photo excitation and UV dissociation, laser induced thermal diffusion, and laser centrifugation. (Nogami, K.)

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.

Anaerobic Copper Toxicity and Iron-Sulfur Cluster Biogenesis in Escherichia coli.

Science.gov (United States)

Tan, Guoqiang; Yang, Jing; Li, Tang; Zhao, Jin; Sun, Shujuan; Li, Xiaokang; Lin, Chuxian; Li, Jianghui; Zhou, Huaibin; Lyu, Jianxin; Ding, Huangen

2017-08-15

are under aerobic conditions. Under anaerobic conditions, E. coli cells accumulate excess intracellular copper, which specifically targets iron-sulfur proteins by blocking iron-sulfur cluster biogenesis. Since iron-sulfur proteins are involved in diverse and vital physiological processes, inhibition of iron-sulfur cluster biogenesis by copper disrupts multiple cellular functions and ultimately inhibits cell growth. The results from this study illustrate a new interplay between intracellular copper toxicity and iron-sulfur cluster biogenesis in bacterial cells under anaerobic conditions. Copyright © 2017 American Society for Microbiology.

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.

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

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

Isotopic evidence for multiple contributions to felsic magma chambers

DEFF Research Database (Denmark)

Waight, Tod Earle; Wiebe, R.A.; Krogstad, E.J.

2007-01-01

The Gouldsboro Granite forms part of the Coastal Maine Magmatic Province, a region characterized by granitic plutons that are intimately linked temporally and petrogenetically with abundant co-existing mafic magmas. The pluton is complex and preserves a felsic magma chamber underlain...... with identical isotopic compositions to more mafic dikes suggest that closed system fractionation may be occurring in deeper level chambers prior to injection to shallower levels. The granitic portion of the pluton has the highest Nd isotopic composition (eNd=+3.0) of plutons in the region whereas the mafic...

Isotopic analysis of calcium in blood plasma and bone from mouse samples by multiple collector-ICP-mass spectrometry

International Nuclear Information System (INIS)

Hirata, Takafumi; Tanoshima, Mina; Suga, Akinobu; Tanaka, Yu-ki; Nagata, Yuichi; Shinohara, Atsuko; Chiba, Momoko

2008-01-01

The biological processing of Ca produces significant stable isotope fractionation. The level of isotopic fractionation can provide key information about the variation in dietary consumption or Ca metabolism. To investigate this, we measured the 43 Ca/ 42 Ca and 44 Ca/ 42 Ca ratios for bone and blood plasma samples collected from mice of various ages using multiple collector-ICP-mass spectrometry (MC-ICP-MS). The 44 Ca/ 42 Ca ratio in bones was significantly (0.44 - 0.84 per mille) lower than the corresponding ratios in the diet, suggesting that Ca was isotopically fractionated during Ca metabolism for bone formation. The resulting 44 Ca/ 42 Ca ratios for blood plasma showed almost identical, or slightly higher, values (0.03 - 0.2 per mille) than found in a corresponding diet. This indicates that a significant amount of Ca in the blood plasma was from dietary sources. Unlike that discovered for Fe, there were not significant differences in the measured 44 Ca/ 42 Ca ratios between female and male specimens (for either bone or blood plasma samples). Similarity, the 44 Ca/ 42 Ca ratios suggests that there were no significant differences in Ca dietary consumption or Ca metabolism between female and male specimens. In contrast, the 44 Ca/ 42 Ca ratios of blood plasma from mother mice during the lactation period were significantly higher than those for all other adult specimens. This suggests that Ca supplied to infants through lactation was isotopically lighter, and the preferential supply of isotropically lighter Ca resulted in isotopically heavier Ca in blood plasma of mother mice during the lactation period. The data obtained here clearly demonstrate that the Ca isotopic ratio has a potential to become a new tool for evaluating changes in dietary consumption, or Ca metabolism of animals. (author)

Multiple taxon multiple locality approach to providing oxygen isotope evidence for warm-blooded theropod dinosaurs

Science.gov (United States)

Fricke, Henry C.; Rogers, Raymond R.

2000-09-01

Oxygen isotope ratios of fossil remains of coexisting taxa from several different localities can be used to help investigate dinosaur thermoregulation. Focusing on the Late Cretaceous, oxygen isotope ratios of crocodile tooth enamel from four separate localities exhibit less of a decrease with latitude than do ratios of tooth enamel from coexisting theropod dinosaurs. A shallower latitudinal gradient for crocodiles is consistent with how oxygen isotope ratios should vary for heterothermic animals having body temperatures coupled with their environments (“cold blooded”), while a steeper gradient for theropods is consistent with how these ratios should vary for homeothermic animals having constant body temperatures independent of their environments (“warm blooded”). This inferred homoethermy in theropods is likely due to higher rates of metabolic heat production relative to crocodiles and is not an artifact of body size.

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...

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.)

Evaluating the skills of isotope-enabled general circulation models against in situ atmospheric water vapor isotope observations

DEFF Research Database (Denmark)

Steen-Larsen, Hans Christian; Risi, C.; Werner, M.

2017-01-01

The skills of isotope-enabled general circulation models are evaluated against atmospheric water vapor isotopes. We have combined in situ observations of surface water vapor isotopes spanning multiple field seasons (2010, 2011, and 2012) from the top of the Greenland Ice Sheet (NEEM site: 77.45°N......: 2014). This allows us to benchmark the ability to simulate the daily water vapor isotope variations from five different simulations using isotope-enabled general circulation models. Our model-data comparison documents clear isotope biases both on top of the Greenland Ice Sheet (1-11% for δ18O and 4...... boundary layer water vapor isotopes of the Baffin Bay region show strong influence on the water vapor isotopes at the NEEM deep ice core-drilling site in northwest Greenland. Our evaluation of the simulations using isotope-enabled general circulation models also documents wide intermodel spatial...

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

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.

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.

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

Against the odds? De novo structure determination of a pilin with two cysteine residues by sulfur SAD.

Science.gov (United States)

Gorgel, Manuela; Bøggild, Andreas; Ulstrup, Jakob Jensen; Weiss, Manfred S; Müller, Uwe; Nissen, Poul; Boesen, Thomas

2015-05-01

Exploiting the anomalous signal of the intrinsic S atoms to phase a protein structure is advantageous, as ideally only a single well diffracting native crystal is required. However, sulfur is a weak anomalous scatterer at the typical wavelengths used for X-ray diffraction experiments, and therefore sulfur SAD data sets need to be recorded with a high multiplicity. In this study, the structure of a small pilin protein was determined by sulfur SAD despite several obstacles such as a low anomalous signal (a theoretical Bijvoet ratio of 0.9% at a wavelength of 1.8 Å), radiation damage-induced reduction of the cysteines and a multiplicity of only 5.5. The anomalous signal was improved by merging three data sets from different volumes of a single crystal, yielding a multiplicity of 17.5, and a sodium ion was added to the substructure of anomalous scatterers. In general, all data sets were balanced around the threshold values for a successful phasing strategy. In addition, a collection of statistics on structures from the PDB that were solved by sulfur SAD are presented and compared with the data. Looking at the quality indicator R(anom)/R(p.i.m.), an inconsistency in the documentation of the anomalous R factor is noted and reported.

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.

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)

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

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.

Ion microprobe analyses of oxygen three-isotope ratios of chondrules from the Sayh al Uhaymir 290 CH chondrite using a multiple-hole disk

Digital Repository Service at National Institute of Oceanography (India)

Nakashima, D.; Ushikubo, T.; Gowda, R.N.; Kita, N.T.; Valley, J.W.; Naga, K.

Author version: Meteorit. Planet. Sci., vol.46(6); 2011; 857-874 Ion microprobe analyses of oxygen three isotope ratios of chondrules from the Sayh al Uhaymir 290 CH chondrite using a multiple-hole disk Daisuke Nakashima 1,2,* , Takayuki Ushikubo...

Correlation of isotopic cisternographic patterns in multiple sclerosis with CSF IgG values

International Nuclear Information System (INIS)

Bartolini, S.; Inzitari, D.; Castagnoli, A.; Amaducci, L.

1982-01-01

Thirty-eight patients with multiple sclerosis (MS) were examined with isotopic cisternography (IC) in order to study cerebrospinal fluid (CSF) dynamics. Cisternography was also performed in 15 patients with amyotrophic lateral sclerosis and in 14 with senile dementia of the Alzheimer type as controls. IC pattern of ''mixed'' type was found in 18 MS patients and all those with Alzheimer senile dementia examined, while the IC examination did not show abnormality in any of 15 patients with amyotrophic lateral sclerosis. In MS patients, the abnormal IC picture proved to be significantly correlated with the CSF IgG values as calculated by Link's and Tourtelotte's formulas. The abnormal IC in MS may be due to altered CSF reabsorption or increased transependymal flow, or it may be related to the abnormal concentration of IgG

Advances in laser isotope separation

International Nuclear Information System (INIS)

Herman, I.P.; Bernhardt, A.F.

1988-01-01

The physical and chemical concepts required to understand laser isotope separation are presented and discussed. The numerous successful demonstrations of separating isotopes using lasers are reviewed to 1983. Emphasis is placed on the separation of 235-U from 238-U by multi-step selective ioniation of uranium atomic vapor, and on the separation of D and H and of T from D, by pulsed infrared laser multiple-photon dissociation of fluoroform and chloroform, respectively, because they are among the most successful and important examples of laser isotope separation to date. 161 refs.; 7 figs

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).

Redox State of the Neoarchean Earth Environment

Science.gov (United States)

Zerkle, Aubrey L.; Claire, Mark W.; Domagal-Goldman, Shawn; Farquhar, James; Poulton, Simon W.

2011-01-01

A Titan-like organic haze has been hypothesized for Earth's atmosphere prior to widespread surface oxygenation approx.2.45 billion years ago (Ga). We present a high-resolution record of quadruple sulfur isotopes, carbon isotopes, and Fe speciation from the approx.2.65-2.5 Ga Ghaap Group, South Africa, which suggest a linkage between organic haze and the biogeochemical cycling of carbon, sulfur, oxygen, and iron on the Archean Earth. These sediments provide evidence for oxygen production in microbial mats and localized oxygenation of surface waters. However, this oxygen production occurred under a reduced atmosphere which existed in multiple distinct redox states that correlate to changes in carbon and sulfur isotopes. The data are corroborated by photochemical model results that suggest bi-stable transitions between organic haze and haze-free atmospheric conditions in the Archean. These geochemical correlations also extend to other datasets, indicating that variations in the character of anomalous sulfur fractionation could provide insight into the role of carbon-bearing species in the reducing Archean atmosphere.

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

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.

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

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

Laser Isotope Enrichment for Medical and Industrial Applications

International Nuclear Information System (INIS)

Leonard Bond

2006-01-01

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

Environmental Monitoring of Agro-Ecosystem Using Environmental Isotope Tracer Technology

International Nuclear Information System (INIS)

Chung, Byung Yeoup; Kim, Jae Sung; Cho, Jae Young

2004-10-01

This report has provided the counterparts the knowledge and skills on the use of environmental isotope tracer technology for obtaining valuable information on agricultural non-point pollution source in agro-ecosystem. The contamination from agricultural watersheds has been brought into attention as a potential contaminant of streams and tributaries, since majority of them caused water quality degradation, eutrophication of reservoir and negative effect on agro-environment. To prevent the contamination from these watersheds, it is necessary to find out the source of the contamination. However, accurate contaminants outflows from various types of non-point sources have not yet been elucidated due to the fact that the extent of non-point source contaminants related to uncontrollable climatic events and irrigation conditions may differ greatly from place to place and year to year. The dominant use of isotopes in environmental ecosystem research in the last few decades has been to trace sources of waters and solutes. The environmental isotope tracer technology using stable isotopes such as oxygen, hydrogen, carbon, nitrogen, and sulfur has extensively been used for tracing the fate of environmental pollutants and for identification of environmental pollutants sources in agro-ecosystems

Sulfur problems in Swedish agriculture

Energy Technology Data Exchange (ETDEWEB)

Johansson, O

1959-01-01

The present paper deals with some aspects of the sulfur situation in Swedish agriculture with special emphasis on the importance of and relationships among various sources of sulfur supply. An inventory of the sulfur content of Swedish soils and hay crops includes 649 soil samples and a corresponding number of hay samples from 59 locations. In a special investigation the samples were found to be representative of normal Swedish farm land. It is concluded that the amount of sulfur compounds in the air is the primary factor which determines the amount of sulfur added to the soil from the atmosphere. Compared with values obtained in other countries, the amount of sulfur added by the precipitation in Sweden is very low. The distribution in air and precipitation of sulfur from an industrial source was studied in a special investigation. An initial reason for the present study was the damage to vegetation caused by smoke from an industrial source. It was concluded that the average conditions in the vicinity of the industrial source with respect to smoke constituents in the air and precipitation were unfavorable only to the plants directly within a very narrow region. Relationships among the sulfur contents of air, of precipitation, of soils and of plants have been subject to special investigations. In the final general discussion and conclusions it is pointed out that the results from these investigations indicate evident differences in the sulfur status of Swedish soils. The present trend toward the use of more highly concentrated fertilizers poor in sulfur may be expected to cause a considerable change in the sulfur situation in Swedish agriculture. 167 references, 40 figures, 44 tables.

Isotope ratio measurements of pg-size plutonium samples using TIMS in combination with the 'Multiple Ion Counting' and filament carburization

Energy Technology Data Exchange (ETDEWEB)

Jakopic, Rozle; Richter, Stephan; Kuehn, Heinz; Aregbe, Yetunde [European Commission, Directorate General Joint Research Centre Institute for Reference Materials and Measurements, IRMM Retieseweg 111, B-2440 Geel (Belgium)

2008-07-01

A new sample preparation procedure for isotopic measurements using the Triton TIMS (Thermal Ionization Mass Spectrometer) was developed which employed the technique of carburization of rhenium filaments. Carburized filaments were prepared in a special vacuum chamber in which the filaments were heated and exposed to benzene vapor. Ionization efficiency was improved by an order of magnitude. Additionally, a new 'multi-dynamic' measurement technique was developed for Pu isotope ratio measurements using the 'multiple ion counting' (MIC) system. This technique was further combined with the filament carburization technique and applied to the NBL-137 isotopic standard and samples of the NUSIMEP 5 inter-laboratory comparison campaign. The results clearly show an improved precision and accuracy for the 'multi-dynamic' measurement procedure, compared to measurements carried out either in peak-jumping or in static mode using the MIC system with non-carburized filaments. (authors)

Biogenic sulfur compounds and the global sulfur cycle

International Nuclear Information System (INIS)

Aneja, V.P.; Aneja, A.P.; Adams, D.F.

1982-01-01

Field measurements of biogenic sulfur compounds shows a great variation in concentrations and emission rates for H 2 S, DMS, CS 2 and COS. Measurements by the chamber method and estimates from micrometeorological sampling are employed to determine the earth-atmosphere flux of these gases. Much of the variation can be attributed to differences of climate and surface conditions, with marshes being a large source of biogenic sulfur (mean contribution 4 x 10 to the 6th ton/year maximum contribution 142 x 10 to the 6th ton/year). Considering that the estimated biogenic contribution needed to balance the global sulfur cycle ranges from 40- 230 x 10 to the 6th tons/year, the mean values are not sufficient to balance this cycle. Further experimental investigations are suggested in order to characterize the biogenic processes adequately

Evaluation of lead isotope compositions of NIST NBS 981 measured by thermal ionization mass spectrometer and multiple-collector inductively coupled plasma mass spectrometer

Directory of Open Access Journals (Sweden)

Honglin Yuan

2016-09-01

Full Text Available Because Pb isotopes can be used for tracing, they are widely used in many disciplines. The detection and analysis of Pb isotopes of bulk samples are usually conducted using thermal ionization mass spectrometer (TIMS and multiple-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, both of which need external reference materials with known isotopic compositions to correct for the mass discrimination effect produced during analysis. NIST NBS 981 is the most widely used reference material for Pb isotope analysis; however, the isotopic compositions reported by various analytical laboratories, especially those using TIMS, vary from each other. In this study, we statistically evaluated 229 reported TIMS analysis values collected by GeoReM in the last 30 years, 176 reported MC-ICP-MS analysis values, and 938 MC-ICP-MS analysis results from our laboratory in the last five years. After careful investigation, only 40 TIMS results were found to have double or triple spikes. The ratios of the overall weighted averages, 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb, obtained from 40 spiked TIMS reports and 1114 MC-ICP-MS results of NIST NBS 981 isotopes were 16.9406 ± 0.0003 (2s, 15.4957 ± 0.0002 (2s, and 36.7184 ± 0.0007 (2s, respectively.

Diesel Emission Control -- Sulfur Effects (DECSE) Program; Phase I Interim Data Report No. 1

Energy Technology Data Exchange (ETDEWEB)

DOE; ORNL; NREL; EMA; MECA

1999-08-15

The Diesel Emission Control-Sulfur Effects (DECSE) is a joint government/industry program to determine the impact of diesel fuel sulfur levels on emission control systems whose use could lower emissions of nitrogen oxides (NO{sub x}) and particulate matter (PM) from on-highway trucks in the 2002--2004 model years. Phase 1 of the program was developed with the following objectives in mind: (1) evaluate the effects of varying the level of sulfur content in the fuel on the emission reduction performance of four emission control technologies; and (2) measure and compare the effects of up to 250 hours of aging on selected devices for multiple levels of fuel sulfur content. This interim data report summarizes results as of August, 1999, on the status of the test programs being conducted on three technologies: lean-NO{sub x} catalysts, diesel particulate filters and diesel oxidation catalysts.

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.

Determining origin of underground water in coal mines by means of natural isotopes and other geochemical parameters

Energy Technology Data Exchange (ETDEWEB)

Dolenec, T; Pezdic, J; Herlec, U; Kuscer, D; Mitrevski, G [Institut Josef Stefan, Ljubljana (Yugoslavia)

1989-07-01

Presents a preliminary report on origin of water in Slovenian brown coal mines. Water, coal and strata samples from the Hrastnik and Ojstro mines were analyzed for changes in chemical composition. Water samples were also analyzed for changes in isotopic composition and inorganic carbon and sulfur contents. Chemical, isotopic and geochemical techniques are described and results are presented with 21 diagrams. An attempt is made to explain the origin and age of water flowing from mine aquifers into mine rooms, and to explain the interdependence of surface and underground water flow. 10 refs.

Sulfur dimers adsorbed on Au(111) as building blocks for sulfur octomers formation: A density functional study

International Nuclear Information System (INIS)

Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian; Pujals, Daniel Codorniu; Mikosch, Hans; Hernández, Mayra P.

2014-01-01

Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO 2 gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage

Sulfur dimers adsorbed on Au(111) as building blocks for sulfur octomers formation: A density functional study

Energy Technology Data Exchange (ETDEWEB)

Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian [Laboratory of Computational and Theoretical Chemistry (LQCT), Faculty of Chemistry, Havana University, Havana 10400 (Cuba); Pujals, Daniel Codorniu [Higher Institute of Technologies and Applied Sciences (InSTEC), Havana 10400 (Cuba); Mikosch, Hans [Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/E164-EC, 1060 Vienna (Austria); Hernández, Mayra P., E-mail: mayrap@imre.oc.uh.cu [Instituto de Ciencias y Tecnologías de Materiales (IMRE), Havana 10400 (Cuba)

2014-07-28

Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO{sub 2} gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage.

Application of isotope techniques to investigate groundwater pollution

International Nuclear Information System (INIS)

1998-10-01

This publication is a compilation of scientific results from the Co-ordinated Research Project (CRP) on the Application of Isotope Techniques to Investigate Groundwater Pollution which was implemented from 1995 to 1997. The conclusions of the CRP were presented by scientists from the following participating Member States: Austria, Brazil, China, Czech Republic, France, Hungary, India, Israel, Italy, New Zealand, Pakistan, Poland, Senegal and the United Kingdom. The CRP was implemented in recognition of the importance of protecting groundwater resources, and promoting the role of isotope techniques when integrated to classical hydrological methods to identify the sources and mechanisms of by which pollution takes place. The results of the CRP are expected to find practical applications in tackling hydrological problems encountered in technical co-operation projects of the IAEA. This publication could also provide a contribution toward the continuing efforts of various sectors to investigate, mitigate and control the threat of groundwater pollution. This publication includes the results of 16 investigations dealing with isotopes of hydrogen, carbon, nitrogen, oxygen and sulfur integrated to some extent with the classical hydrological tools of investigation. Each document in this compilation is provided with abstract and index

Enhanced recycling of organic matter and Os-isotopic evidence for multiple magmatic or meteoritic inputs to the Late Permian Panthalassic Ocean, Opal Creek, Canada

Science.gov (United States)

Georgiev, Svetoslav V.; Stein, Holly J.; Hannah, Judith L.; Henderson, Charles M.; Algeo, Thomas J.

2015-02-01

The geochemical record for the Permian-Triassic boundary in northern latitudes is essential to evaluation of global changes associated with the most profound extinction of life on Earth. We present inorganic and organic geochemical data, and Re-Os isotope systematics in a critical stratigraphic interval of pre- and post-extinction Upper Permian-Lower Triassic sediments from Opal Creek, western Canada (paleolatitude of ∼30°N). We document significant and long-lived changes in Panthalassa seawater chemistry that were initiated during the first of four magmatic or meteoritic inputs to Late Permian seawater, evidenced by notable decreases of Os isotopic ratios upsection. Geochemical signals indicate establishment of anoxic bottom waters shortly after regional transgression reinitiated sedimentation in the Late Permian. Euxinic signals are most prominent in the Upper Permian sediments with low organic carbon and high sulfur contents, and gradually wane in the Lower Triassic. The observed features may have been generated in a strongly euxinic ocean in which high bacterioplankton productivity sustained prolific microbial sulfate reduction in the sediment and/or water column, providing hydrogen sulfide to form pyrite. This scenario requires nearly complete anaerobic decomposition of predominantly labile marine organic matter (OM) without the necessity for a complete collapse of primary marine productivity. Similar geochemical variations could have been achieved by widespread oxidation of methane by sulfate reducers after a methanogenic burst in the Late Permian. Both scenarios could have provided similar kill mechanisms for the latest Permian mass extinction. Despite the moderate thermal maturity of the section, OM in all studied samples is dominantly terrestrial and/or continentally derived, recycled and refractory ancient OM. We argue that, as such, the quantity of the OM in the section mainly reflects changes in terrestrial vegetation and/or weathering, and not in

Genomic and Evolutionary Perspectives on Sulfur Metabolism in Green Sulfur Bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Bryant, Donald A.

2008-01-01

Green sulfur bacteria (GSB) are anaerobic photoautotrophs that oxidize sulfide, elemental sulfur, thiosulfate, ferrous iron, and hydrogen for growth. We present here an analysis of the distribution and evolution of enzymes involved in oxidation of sulfur compounds in GSB based on genome sequence......, in combination with phylogenetic analyses, suggests that the Dsr system in GSB could be a recent acquisition, which was obtained by lateral gene transfer in part from sulfideoxidizing bacteria and in part from sulfate-reducing bacteria. All thiosulfate-utilizing GSB strains have an identical sox gene cluster...

Acidithiobacillus caldus sulfur oxidation model based on transcriptome analysis between the wild type and sulfur oxygenase reductase defective mutant.

Directory of Open Access Journals (Sweden)

Linxu Chen

Full Text Available Acidithiobacillus caldus (A. caldus is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox system (omitting SoxCD, non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR. The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system.An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor was created and its growth abilities were measured in media using elemental sulfur (S(0 and tetrathionate (K(2S(4O(6 as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR of the wild type and the Δsor mutant in S(0 and K(2S(4O(6 media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO and heterodisulfide reductase (HDR, the truncated Sox pathway, and the S(4I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media.An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized.

Biomimetic Ant-Nest Electrode Structures for High Sulfur Ratio Lithium-Sulfur Batteries.

Science.gov (United States)

Ai, Guo; Dai, Yiling; Mao, Wenfeng; Zhao, Hui; Fu, Yanbao; Song, Xiangyun; En, Yunfei; Battaglia, Vincent S; Srinivasan, Venkat; Liu, Gao

2016-09-14

The lithium-sulfur (Li-S) rechargeable battery has the benefit of high gravimetric energy density and low cost. Significant research currently focuses on increasing the sulfur loading and sulfur/inactive-materials ratio, to improve life and capacity. Inspired by nature's ant-nest structure, this research results in a novel Li-S electrode that is designed to meet both goals. With only three simple manufacturing-friendly steps, which include slurry ball-milling, doctor-blade-based laminate casting, and the use of the sacrificial method with water to dissolve away table salt, the ant-nest design has been successfully recreated in an Li-S electrode. The efficient capabilities of the ant-nest structure are adopted to facilitate fast ion transportation, sustain polysulfide dissolution, and assist efficient precipitation. High cycling stability in the Li-S batteries, for practical applications, has been achieved with up to 3 mg·cm(-2) sulfur loading. Li-S electrodes with up to a 85% sulfur ratio have also been achieved for the efficient design of this novel ant-nest structure.

Determination of isotopic composition of uranium in microparticles by secondary ion mass spectrometry

International Nuclear Information System (INIS)

Veniaminov, N.N.; Kolesnikov, O.N.; Stebel'kov, V.A.

1992-01-01

Aerosol particles including uranium in their composition are specific atmospheric polutants. Uranium is used as nuclear fuel in atomic power stations and in spacecraft power units, and also as a component of nuclear warheads. In order to monitor the discharge of uranium-containing aerosol particles to the atmosphere, they must first be identified. As an example, one may cite an investigation of the elemental composition and radioactivity of particles formed in the accident at the Chernobyl atomic power station. One of the most informative indicators of the origin of uranium-containing aerosol particles is the isotopic composition of the uranium. Secondary ion mass spectrometry (SIMS) offers unique possibilities for the measurement of isotope ratios in individual microscopic objects. At the same time, a measurement of isotope ratios of sulfur in microsection of galenite PbS 2 has shown that the application of SIMS for these purposes is seriously limited by the difference in yield of secondary ions for isotopes with different masses. These discrimination effects, in the case of light elements such as boron, may result in distortion of the isotope ratios by several percent. In the case of heavy elements, however, the effect is less significant, amounting to about 0.5% for lead isotopes. 13 refs., 3 figs., 1 tab

Capacity Fade Analysis of Sulfur Cathodes in Lithium–Sulfur Batteries

Science.gov (United States)

Yan, Jianhua; Liu, Xingbo

2016-01-01

Rechargeable lithium–sulfur (Li–S) batteries are receiving ever‐increasing attention due to their high theoretical energy density and inexpensive raw sulfur materials. However, their rapid capacity fade has been one of the key barriers for their further improvement. It is well accepted that the major degradation mechanisms of S‐cathodes include low electrical conductivity of S and sulfides, precipitation of nonconductive Li2S2 and Li2S, and poly‐shuttle effects. To determine these degradation factors, a comprehensive study of sulfur cathodes with different amounts of electrolytes is presented here. A survey of the fundamentals of Li–S chemistry with respect to capacity fade is first conducted; then, the parameters obtained through electrochemical performance and characterization are used to determine the key causes of capacity fade in Li–S batteries. It is confirmed that the formation and accumulation of nonconductive Li2S2/Li2S films on sulfur cathode surfaces are the major parameters contributing to the rapid capacity fade of Li–S batteries. PMID:27981001

Mineralogy, Geochemistry and Stable Isotope Investigation of Gürkuyu Sb Mineralization (Gediz-Kütahya-NW Turkey

Directory of Open Access Journals (Sweden)

Yeşim ÖZEN

2016-11-01

Full Text Available Abstract. The Gürkuyu Sb mineralization is located in the western part of Anatolian tectonic belt, in southern part of İzmir-Ankara zone and in northern part of Menderes Massif. The mineralization located at west of the Koca hill in east of Gürkuyu village of Gediz (Kütahya-Turkey has been characterized through the detailed examinations involving sulfur and oxygen isotope. Serpentinites of Dağardı melange and crystallized limestones of Budağan limestone were hydrothermally altered by hydrothermal solutions, come from fissures and fractures due to tectonic movement during the thrust of melange and occurred silicified zone. Gürkuyu Sb mineralization suggest that occurred in this silicified zone. In Gürkuyu mineralization, primary ore minerals are antimonite and pyrite, secondary ore minerals are senarmontite, valentinite, orpiment and realgar. Quartz and calcite are the most common gangue minerals. In Gürkuyu Sb mineralization, δ34S values of stibnite are ranged from 1.0 ‰ to 1.3 ‰. δ18O values of quartz are ranged is 15.8 ‰ in Gürkuyu mineralization. Sulfur and oxygen isotope values are similar to the values for magmatic rocks and to the values for fluids of magmatic origin.Keywords: Stable isotope, Gürkuyu, Sb mineralization, Gediz, Kütahya, NW Turkey.

Separation of hafnium from zirconium in sulfuric acid solutions using pressurized ion exchange

International Nuclear Information System (INIS)

Hurst, F.J.

1981-01-01

High-resolution pressurized ion exchange has been used successfully to study and separate hafnium and zirconium sulfate complexes by chromatographic elution from Dowex 50W-X8 (15 to 25 μm) resin with sulfuric acid solutions. Techniques were developed to continuously monitor the column effluents for zirconium and hafnium by reaction with fluorometric and colorimetric reagents. Since neither reagent was specific for either metal ion, peak patterns were initially identified by using the stable isotopes 90 Zr and 180 Hf as fingerprints of their elution position. Distribution ratios for both zirconium and hafnium decrease as the inverse fourth power of the sulfuric acid concentration below 2N and as the inverse second power at higher acid concentration. The hafnium-to-zirconium separation factor is approximately constant (approx. 8) over the 0.5 to 3N range. Under certain conditions, an unseparated fraction was observed that was not retained by the resin. The amount of this fraction which is thought to be a polymeric hydrolysis product appears to be a function of metal and sulfuric acid concentrations. Conditions are being sought to give the highest zirconium concentration and the lowest acid concentration that can be used as a feed material for commercial scale-up in the continuous annular chromatographic (CAC) unit without formation of the polymer

Layered sulfur/PEDOT:PSS nano composite electrodes for lithium sulfur cell applications

Science.gov (United States)

Anilkumar, K. M.; Jinisha, B.; Manoj, M.; Pradeep, V. S.; Jayalekshmi, S.

2018-06-01

Lithium-Sulfur (Li-S) cells are emerging as the next generation energy storage devices owing to their impressive electrochemical properties with high theoretical specific capacity of 1675 mAh/g. Lack of electronic conductivity of sulfur, its volume expansion during high lithium intake and the shuttling effect due to the formation of soluble polysulfides are the main limitations, delaying the commercialization of this technology. To address these challenges, in the present work, the conducting polymer PEDOT:PSS is used as the covering matrix over the sulfur particles to improve their Li storage properties. The sulfur/PEDOT:PSS nanocomposite is synthesised using the hydrothermal process and its formation with the polymer coating over sulfur nanoparticles is established from the XRD, Raman spectroscopy, FE-SEM and TEM studies. The electrochemical studies show that the cells assembled using the sulfur/PEDOT:PSS nanocomposite as the cathode, with the components taken in the weight ratio of 9:1, offer a reversible capacity of 1191 mAh g-1 at 0.1C rate. These cells display stable electrochemical capacities over 200 cycles at gradually increasing current rates. The polymer layer facilitates electronic conduction and suppresses the polysulfide formation and the volume expansion of sulfur. A reversible capacity of 664 mAh g-1 is observed after 200 cycles at 1C rate with the capacity retention of 75 % of the initial stable capacity. The highlight of the present work is the possibility to achieve high discharge capacities at high C rates and the retention of a good percentage of the initial capacity over 200 cycles, for these Li-S cells.

Demand outlook for sulfur and high-sulfur petroleum coke

Energy Technology Data Exchange (ETDEWEB)

Koshkarov, V.Ya.; Danil' yan, P.G.; Feotov, V.E.; Gimaev, R.N.; Koshkarova, M.E.; Sadykova, S.R.; Vodovichenko, N.S.

1980-01-01

The feasibility of using sulfur and high-sulfur petroleum coke fines in pyrometallurgical processes and also in the chemical and coal-tar chemical industry is examined. Results of industrial tests on briquetting fines of petroleum coke with a petroleum binder are presented. The feasibility of using the obtained briquets in shaft furnace smelting of oxidized nickel ores, production of anode stock, and also in the chemical industry are demonstrated.

SULFUR POLYMER ENCAPSULATION

International Nuclear Information System (INIS)

KALB, P.

2001-01-01

Sulfur polymer cement (SPC) is a thermoplastic polymer consisting of 95 wt% elemental sulfur and 5 wt% organic modifiers to enhance long-term durability. SPC was originally developed by the U.S. Bureau of Mines as an alternative to hydraulic cement for construction applications. Previous attempts to use elemental sulfur as a construction material in the chemical industry failed due to premature degradation. These failures were caused by the internal stresses that result from changes in crystalline structure upon cooling of the material. By reacting elemental sulfur with organic polymers, the Bureau of Mines developed a product that successfully suppresses the solid phase transition and significantly improves the stability of the product. SPC, originally named modified sulfur cement, is produced from readily available, inexpensive waste sulfur derived from desulfurization of both flue gases and petroleum. The commercial production of SPC is licensed in the United States by Martin Resources (Odessa, Texas) and is marketed under the trade name Chement 2000. It is sold in granular form and is relatively inexpensive ((approx)$0.10 to 0.12/lb). Application of SPC for the treatment of radioactive, hazardous, and mixed wastes was initially developed and patented by Brookhaven National Laboratory (BNL) in the mid-1980s (Kalb and Colombo, 1985; Colombo et al., 1997). The process was subsequently investigated by the Commission of the European Communities (Van Dalen and Rijpkema, 1989), Idaho National Engineering Laboratory (Darnell, 1991), and Oak Ridge National Laboratory (Mattus and Mattus, 1994). SPC has been used primarily in microencapsulation applications but can also be used for macroencapsulation of waste. SPC microencapsulation has been demonstrated to be an effective treatment for a wide variety of wastes, including incinerator hearth and fly ash; aqueous concentrates such as sulfates, borates, and chlorides; blowdown solutions; soils; and sludges. It is not

Confine sulfur in mesoporous metal–organic framework @ reduced graphene oxide for lithium sulfur battery

International Nuclear Information System (INIS)

Bao, Weizhai; Zhang, Zhian; Qu, Yaohui; Zhou, Chengkun; Wang, Xiwen; Li, Jie

2014-01-01

Highlights: • Metal organic framework @ reduced graphene oxide was applied for sulfur cathode. • MIL-101(Cr)@rGO/S composites are synthesized by a facile two-step liquid method. • Cycling stability of MIL-101(Cr)@rGO/S sulfur cathode was improved. -- Abstract: Mesoporous metal organic framework @ reduced graphene oxide (MIL-101(Cr)@rGO) materials have been used as a host material to prepare the multi-composite sulfur cathode through a facile and effective two-step liquid phase method successfully, which is different from the simple MIL-101(Cr)/S mixed preparation method. The successful reduced graphene oxide coating in the MIL-101(Cr)@rGO improve the electronic conductivity of meso-MOFs effectively. The discharge capacity and capacity retention rate of MIL-101(Cr)@rGO/S composite sulfur cathode are as high as 650 mAh g −1 and 66.6% at the 50th cycle at the current density of 335 mA g −1 . While the discharge capacity and capacity retention rate of MIL-101(Cr)/S mixed sulfur cathode is 458 mAh g −1 and 37.3%. Test results indicate that the MIL-101(Cr)@rGO is a promising host material for the sulfur cathode in the lithium–sulfur battery applications

Stability of sulfur slopes on Io

Science.gov (United States)

Clow, G. D.; Carr, M. H.

1980-01-01

The mechanical properties of elemental sulfur are such that the upper crust of Io cannot be primarily sulfur. For heat flows in the range 100-1000 ergs/sq cm sec sulfur becomes ductile within several hundred meters of the surface and would prevent the formation of calderas with depths greater than this. However, the one caldera for which precise depth data are available is 2 km deep, and this value may be typical. A study of the mechanical equilibrium of simple slopes shows that the depth to the zone of rapid ductile flow strongly controls the maximum heights for sulfur slopes. Sulfur scarps with heights greater than 1 km will fail for all heat flows greater than 180 ergs/sq cm sec and slope angles greater than 22.5 deg. The observed relief on Io is inconsistent with that anticipated for a predominantly sulfur crust. However, a silicate crust with several percent sulfur included satisfies both the mechanical constraints and the observed presence of sulfur on Io.

40 CFR 52.1881 - Control strategy: Sulfur oxides (sulfur dioxide).

Science.gov (United States)

2010-07-01

....0 pounds of sulfur dioxide per million BTU actual heat input for the coal-fired boiler and 0.4... BTU actual heat input for coal-fired boiler C exiting through stack 5. (3) 2.24 pounds of sulfur dioxide per million BTU acutal heat input for coal-fired boiler D exiting through stack 6. (E) In lieu of...

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)

Process for removing sulfur from sulfur-containing gases: high calcium fly-ash

Science.gov (United States)

Rochelle, Gary T.; Chang, John C. S.

1991-01-01

The present disclosure relates to improved processes for treating hot sulfur-containing flue gas to remove sulfur therefrom. Processes in accordance with the present invention include preparing an aqueous slurry composed of a calcium alkali source and a source of reactive silica and/or alumina, heating the slurry to above-ambient temperatures for a period of time in order to facilitate the formation of sulfur-absorbing calcium silicates or aluminates, and treating the gas with the heat-treated slurry components. Examples disclosed herein demonstrate the utility of these processes in achieving improved sulfur-absorbing capabilities. Additionally, disclosure is provided which illustrates preferred configurations for employing the present processes both as a dry sorbent injection and for use in conjunction with a spray dryer and/or bagfilter. Retrofit application to existing systems is also addressed.

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

Science.gov (United States)

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

2018-06-01

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

Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

International Nuclear Information System (INIS)

Dong, Kang; Wang, Shengping; Zhang, Hanyu; Wu, Jinping

2013-01-01

Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al 2 O 3 can provide surface area for the deposition of Li 2 S and Li 2 S 2 . ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g −1 , and the remaining capacity was 585 mAh g −1 after 50 cycles at 0.25 mA cm −2 . Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process

Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

Energy Technology Data Exchange (ETDEWEB)

Abedinzadeh, Z. [Lab. de Chimie Physique, UMR, Univ. Rene Descartes, Paris (France)

2001-02-01

Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS{sup .}, RSS{sup .}, RS{sup .+}, (RSSR){sup .+}] and their implications for biological systems. (author)

Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

International Nuclear Information System (INIS)

Abedinzadeh, Z.

2001-01-01

Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS . , RSS . , RS .+ , (RSSR) .+ ] and their implications for biological systems. (author)

Danburite decomposition by sulfuric acid

International Nuclear Information System (INIS)

Mirsaidov, U.; Mamatov, E.D.; Ashurov, N.A.

2011-01-01

Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by sulfuric acid. The process of decomposition of danburite concentrate by sulfuric acid was studied. The chemical nature of decomposition process of boron containing ore was determined. The influence of temperature on the rate of extraction of boron and iron oxides was defined. The dependence of decomposition of boron and iron oxides on process duration, dosage of H 2 SO 4 , acid concentration and size of danburite particles was determined. The kinetics of danburite decomposition by sulfuric acid was studied as well. The apparent activation energy of the process of danburite decomposition by sulfuric acid was calculated. The flowsheet of danburite processing by sulfuric acid was elaborated.

Sulfur polymer cement concrete

International Nuclear Information System (INIS)

Weber, H.H.; McBee, W.C.

1990-01-01

Sulfur-based composite materials formulated using sulfur polymer cement (SPC) and mineral aggregates are described and compared with conventional portland cement based materials. Materials characteristics presented include mechanical strength, chemical resistance, impact resistance, moisture permeation, and linear shrinkage during placement and curing. Examples of preparation and placement of sulfur polymer cement concrete (SC) are described using commercial scale equipment. SC applications presented are focused into hostile chemical environments where severe portland cement concrete (PCC) failure has occurred

Development of an accurate, sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine, sulfur, and heavy metals) in coal samples

International Nuclear Information System (INIS)

Boulyga, Sergei F.; Heilmann, Jens; Heumann, Klaus G.; Prohaska, Thomas

2007-01-01

A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for 35 Cl + to more than 6 x 10 5 cps for 238 U + for 1 μg of trace element per gram of coal sample. Detection limits vary from 450 ng g -1 for chlorine and 18 ng g -1 for sulfur to 9.5 pg g -1 for mercury and 0.3 pg g -1 for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis. (orig.)

Development of an accurate, sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine, sulfur, and heavy metals) in coal samples.

Science.gov (United States)

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

2007-10-01

A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for (35)Cl+ to more than 6 x 10(5) cps for (238)U+ for 1 microg of trace element per gram of coal sample. Detection limits vary from 450 ng g(-1) for chlorine and 18 ng g(-1) for sulfur to 9.5 pg g(-1) for mercury and 0.3 pg g(-1) for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis.

Sulfur and lead isotope characteristics of the Pontes e Lacerda gold deposits, SW Amazonian Craton Brazil

International Nuclear Information System (INIS)

Geraldes, M.C.; Tassinari, C.C.G.; Babinski; M; Iyer, S

2001-01-01

This work deals with the characterization of the S and Pb isotope signatures in sulfides from the Pontes e Lacerda mesothermal gold deposits located in the SW sector of Amazonian craton. Stable and radiogenic isotopes have played an important role in the study of ore deposited and hydrothermal processes and they are most useful when can be used together. The purpose of this study is to constrain the sources and the mechanisms of gold deposition in Pontes e Lacerda region which may be a helpful contribution to an exploratory model in the area (au)

Formation of CuxS Layers on Polypropylene Sulfurized by Molten Sulfur

Directory of Open Access Journals (Sweden)

Rasa ALABURDAITĖ

2011-11-01

Full Text Available The processes of formation of electrically conductive layers of copper sulfides CuxS by the sorption-diffusion method on polypropylene (PP using molten sulfur as sulfurizing agent was investigated. The amount of sorbed sulfur increased with the increase of the duration of treatment. Copper sulfide layers were formed on the surface of polypropylene after the treatment of sulfurized polymer with Cu(II/I salt solution. The amount of copper sulfide in layer increased with the increase of treatment duration in copper salt solution. XRD spectra of PP films treated for 3 min with molten sulfur and then with Cu(II/I salt solution for the different time showed that the copper sulfide phases, mostly digenite, Cu2-xS and a-chalcocite, Cu2S were formed in the layers. Electromotive force measurement results confirmed the composition of formed CuxS layers on PP. The phase composition of layers also changed after the annealing. The value of electrical resistance of copper sulfide layers on PP varied from 20 W/cm2 to 80 W/cm2 and after annealing at 80 °C - in the interval of 10 W/cm2 - 60 W/cm2.http://dx.doi.org/10.5755/j01.ms.17.4.776

Removal of sulfur from process streams

International Nuclear Information System (INIS)

Brignac, D.G.

1984-01-01

A process wherein water is added to a non-reactive gas stream, preferably a hydrogen or hydrogen-containing gas stream, sufficient to raise the water level thereof to from about 0.2 percent to about 50 percent, based on the total volume of the process gas stream, and the said moist gas stream is contacted, at elevated temperature, with a particulate mass of a sulfur-bearing metal alumina spinel characterized by the formula MAl 2 O 4 , wherein M is chromium, iron, cobalt, nickel, copper, cadmium, mercury, or zinc to desorb sulfur thereon. In the sulfur sorption cycle, due to the simultaneous adsorption of water and sulfur, the useful life of the metal alumina spinel for sulfur adsorption can be extended, and the sorbent made more easily regenerable after contact with a sulfur-bearing gas stream, notably sulfur-bearing wet hydrogen or wet hydrogen-rich gas streams

Biogeochemical and isotopic gradients in a BTEX/PAH contaminant plume: Model-based interpretation of a high-resolution field data set

DEFF Research Database (Denmark)

Prommer, H.; Anneser, B.; Rolle, Massimo

2009-01-01

of toluene, which is the most rapidly degrading compound and the most important reductant at the site. The resulting depth profiles at the observation well show distinct differences between the small isotopic enrichment in the contaminant plume core and the much stronger enrichment of up to 3.3 parts per......A high spatial resolution data set documenting carbon and sulfur isotope fractionation at a tar oil-contaminated, sulfate-reducing field site was analyzed with a reactive transport model. Within a comprehensive numerical model, the study links the distinctive observed isotope depth profiles...... with the degradation of various monoaromatic and polycyclic aromatic hydrocarbon compounds (BTEX/PAHs) under sulfate-reducing conditions. In the numerical model, microbial dynamics were simulated explicitly and isotope fractionation was directly linked to the differential microbial uptake of lighter and heavier carbon...

Analysis of sulfur-iodine thermochemical cycle for solar hydrogen production. Part 1: decomposition of sulfuric acid

Energy Technology Data Exchange (ETDEWEB)

Huang, Cunping; T-Raissi, Ali [Central Florida Univ., Florida Solar Energy Center, Cocoa, FL (United States)

2005-05-01

The sulfur-iodine (S-I) thermochemical water splitting cycle is one of the most studied cycles for hydrogen (H{sub 2}) production. S-I cycle consists of four sections: (I) acid production and separation and oxygen purification, (II) sulfuric acid concentration and decomposition, (III) hydroiodic acid (HI) concentration, and (IV) HI decomposition and H{sub 2} purification. Section II of the cycle is an endothermic reaction driven by the heat input from a high temperature source. Analysis of the S-I cycle in the past thirty years have been focused mostly on the utilization of nuclear power as the high temperature heat source for the sulfuric acid decomposition step. Thermodynamic as well as kinetic considerations indicate that both the extent and rate of sulfuric acid decomposition can be improved at very high temperatures (in excess of 1000 deg C) available only from solar concentrators. The beneficial effect of high temperature solar heat for decomposition of sulfuric acid in the S-I cycle is described in this paper. We used Aspen Technologies' HYSYS chemical process simulator (CPS) to develop flowsheets for sulfuric acid (H{sub 2}SO{sub 4}) decomposition that include all mass and heat balances. Based on the HYSYS analyses, two new process flowsheets were developed. These new sulfuric acid decomposition processes are simpler and more stable than previous processes and yield higher conversion efficiencies for the sulfuric acid decomposition and sulfur dioxide and oxygen formation. (Author)

High Mass-Loading of Sulfur-Based Cathode Composites and Polysulfides Stabilization for Rechargeable Lithium/Sulfur Batteries

International Nuclear Information System (INIS)

Hara, Toru; Konarov, Aishuak; Mentbayeva, Almagul; Kurmanbayeva, Indira; Bakenov, Zhumabay

2015-01-01

Although sulfur has a high theoretical gravimetric capacity, 1672 mAh/g, its insulating nature requires a large amount of conducting additives: this tends to result in a low mass-loading of active material (sulfur), and thereby, a lower capacity than expected. Therefore, an optimal choice of conducting agents and of the method for sulfur/conducting-agent integration is critically important. In this paper, we report that the areal capacity of 4.9 mAh/cm 2 was achieved at sulfur mass loading of 4.1 mg/cm 2 by casting sulfur/polyacrylonitrile/ketjenblack (S/PAN/KB) cathode composite into carbon fiber paper. This is the highest value among published/reported ones even though it does not contain expensive nanosized carbon materials such as carbon nanotubes, graphene, or graphene derivatives, and competitive enough with the conventional LiCoO 2 -based cathodes (e.g., LiCoO 2 , <20 mg/cm 2 corresponding to <2.8 mAh/cm 2 ). Furthermore, the combination of sulfur/PAN-based composite and PAN-based carbon fiber paper enabled the sulfur-based composite to be used even in carbonate-based electrolyte solution that many lithium/sulfur battery researchers avoid the use of it because of severer irreversible active material loss than in electrolyte solutions without carbonate-based solutions, and even at the highest mass-loading ever reported (the more sulfur is loaded, the more decomposed sulfides deposit at an anode surface).

Developing porous carbon with dihydrogen phosphate groups as sulfur host for high performance lithium sulfur batteries

Science.gov (United States)

Cui, Yanhui; Zhang, Qi; Wu, Junwei; Liang, Xiao; Baker, Andrew P.; Qu, Deyang; Zhang, Hui; Zhang, Huayu; Zhang, Xinhe

2018-02-01

Carbon matrix (CM) derived from biomass is low cost and easily mass produced, showing great potential as sulfur host for lithium sulfur batteries. In this paper we report on a dihydrogen phosphate modified CM (PCM-650) prepared from luffa sponge (luffa acutangula) by phosphoric acid treatment. The phosphoric acid not only increases the surface area of the PCM-650, but also introduces dihydrogen phosphate onto PCM-650 (2.28 at% P). Sulfur impregnated (63.6 wt%) PCM-650/S, in comparison with samples with less dihydrogen phosphate LPCM-650/S, shows a significant performance improvement. XPS analysis is conducted for sulfur at different stages, including sulfur (undischarged), polysulfides (discharge to 2.1 V) and short chain sulfides (discharge to 1.7 V). The results consistently show chemical shifts for S2p in PCM-650, suggesting an enhanced adsorption effect. Furthermore, density functional theory (DFT) calculations is used to clarify the molecular binding: carbon/sulfur (0.86 eV), carbon/Li2S (0.3 eV), CH3-O-PO3H2/sulfur (1.24 eV), and CH3-O-PO3H2/Li2S (1.81 eV). It shows that dihydrogen phosphate group can significantly enhance the binding with sulfur and sulfide, consistent with XPS results. Consequently a CM functionalised with dihydrogen phosphate shows great potential as the sulfur host in a Li-S battery.

Isotopic biases for actinide-only burnup credit

International Nuclear Information System (INIS)

Rahimi, M.; Lancaster, D.; Hoeffer, B.; Nichols, M.

1997-01-01

The primary purpose of this paper is to present the new methodology for establishing bias and uncertainty associated with isotopic prediction in spent fuel assemblies for burnup credit analysis. The analysis applies to the design of criticality control systems for spent fuel casks. A total of 54 spent fuel samples were modeled and analyzed using the Shielding Analyses Sequence (SAS2H). Multiple regression analysis and a trending test were performed to develop isotopic correction factors for 10 actinide burnup credit isotopes. 5 refs., 1 tab

Effect of commercial activated carbons in sulfur cathodes on the electrochemical properties of lithium/sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Park, Jin-Woo; Kim, Icpyo [School of Materials Science and Engineering, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of); Kim, Ki-Won; Nam, Tae-Hyun; Cho, Kwon-Koo; Ahn, Jou-Hyeon [Department of Materials Engineering and Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of); Ryu, Ho-Suk [Department of Material and Energy Engineering, Gyeongwoon University, 730, Gangdong-ro, Sandong-myeon, Gumi, Gyeongbuk, 39160 (Korea, Republic of); Ahn, Hyo-Jun, E-mail: ahj@gnu.ac.kr [School of Materials Science and Engineering, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of); Department of Materials Engineering and Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of)

2016-10-15

Highlights: • The sulfur/activated carbon composite is fabricated using commercial activated carbons. • The sulfur/activated carbon composite with coal shows the best performance. • The Li/S battery has capacities of 1240 mAh g{sup −1} at 1 C and 567 mAh g{sup −1} at 10 C. - Abstract: We prepared sulfur/active carbon composites via a simple solution-based process using the following commercial activated carbon-based materials: coal, coconut shells, and sawdust. Although elemental sulfur was not detected in any of the sulfur/activated carbon composites based on Thermogravimetric analysis, X-ray diffraction, and Raman spectroscopy, Energy-dispersive X-ray spectroscopy results confirmed its presence in the activated carbon. These results indicate that sulfur was successfully impregnated in the activated carbon and that all of the activated carbons acted as sulfur reservoirs. The sulfur/activated carbon composite cathode using coal exhibited the highest discharge capacity and best rate capability. The first discharge capacity at 1 C (1.672 A g{sup −1}) was 1240 mAh g{sup −1}, and a large reversible capacity of 567 mAh g{sup −1} was observed at 10 C (16.72 A g{sup −1}).

Advanced Sulfur Cathode Enabled by Highly Crumpled Nitrogen-Doped Graphene Sheets for High-Energy-Density Lithium-Sulfur Batteries.

Science.gov (United States)

Song, Jiangxuan; Yu, Zhaoxin; Gordin, Mikhail L; Wang, Donghai

2016-02-10

Herein, we report a synthesis of highly crumpled nitrogen-doped graphene sheets with ultrahigh pore volume (5.4 cm(3)/g) via a simple thermally induced expansion strategy in absence of any templates. The wrinkled graphene sheets are interwoven rather than stacked, enabling rich nitrogen-containing active sites. Benefiting from the unique pore structure and nitrogen-doping induced strong polysulfide adsorption ability, lithium-sulfur battery cells using these wrinkled graphene sheets as both sulfur host and interlayer achieved a high capacity of ∼1000 mAh/g and exceptional cycling stability even at high sulfur content (≥80 wt %) and sulfur loading (5 mg sulfur/cm(2)). The high specific capacity together with the high sulfur loading push the areal capacity of sulfur cathodes to ∼5 mAh/cm(2), which is outstanding compared to other recently developed sulfur cathodes and ideal for practical applications.

Using dual isotopic data to track the sources and behaviors of dissolved sulfate in the western North China Plain

International Nuclear Information System (INIS)

Zhang, Dong; Li, Xiao-Dong; Zhao, Zhi-Qi; Liu, Cong-Qiang

2015-01-01

Highlights: • Dual sulfate isotopes were used to elucidate natural and anthropogenic sources in alluvial aquifers. • Infiltration, mixing and bacterial reduction were main processes controlling sulfate behaviors in groundwater. • Enrichment factors and ratio of sulfur and oxygen isotope of sulfate had been calculated. • Local sulfur cycles model had been establish for further management of groundwater. - Abstract: This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ 34 S SO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ 18 O SO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ 34 S SO4 and δ 18 O SO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II 1 ) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ 34 S SO4 and δ 18 O SO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II 2 ) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ 34 S SO4 and δ 18 O SO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II 3

Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Dong, Kang [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China); Wang, Shengping, E-mail: spwang@cug.edu.cn [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China); Zhang, Hanyu; Wu, Jinping [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China)

2013-06-01

Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al{sub 2}O{sub 3} can provide surface area for the deposition of Li{sub 2}S and Li{sub 2}S{sub 2}. ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g{sup −1}, and the remaining capacity was 585 mAh g{sup −1} after 50 cycles at 0.25 mA cm{sup −2}. Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process.

Clues to early diagenetic sulfurization processes from mild chemical cleavage of labile sulfur-rich geomacromolecules

Science.gov (United States)

Adam, P.; Schneckenburger, P.; Schaeffer, P.; Albrecht, P.

2000-10-01

Macromolecular fractions, isolated from the solvent extract of sulfur-rich Recent (Siders Pond, USA; Lake Cadagno, Switzerland; Walvis Bay, Namibia) and immature sediments (Gibellina, Messinian of Sicily; Vena del Gesso, Messinian of Italy), were investigated by chemical degradation using sodium ethanethiolate/methyliodide. This mild reagent which cleaves polysulfide bonds to yield methylsulfides has the advantage over other methods of leaving intact other functionalities (like double bonds) and preserving sulfur atoms at their incorporation site. The method is, therefore, well-suited to the molecular level investigation of sulfur-rich macromolecules from Recent sediments containing highly functionalized polysulfide-bound subunits. In Recent anoxic sulfur-rich sediments, the release of various methylthioethers clearly demonstrates that intermolecular sulfurization of organic matter does occur at the earliest stages of diagenesis. Steroids and phytane derivatives are the major sulfurized lipids, a feature also observed in more mature sulfur-rich sediments. Several phytene derivatives, such as cis and trans 1-methylthiophyt-2-enes, as well as methylthiosteroids, including 5α- and 5β-3-(methylthio)-cholest-2-enes, were identified by comparison with synthesized standards. Steroid methylthioenolethers are released from polysulfide-bound steroid enethiols present in the macromolecular fractions. The latter, which correspond to thioketones, can be considered as intermediates in the reductive sulfurization pathway leading from steroid ketones to polysulfide-bound saturated steroid skeletons and are characterized for the first time in the present study. Thus, it could be shown that the major part of the polysulfide-bound lipids occurring in Recent sediments is apparently the result of sulfurization processes affecting carbonyls (aldehydes and ketones). The unsaturated methylthioethers obtained from Recent sediments were not present in more mature evaporitic samples, which

Sulfur equilibrium desulfurization of sulfur containing products of combustion

International Nuclear Information System (INIS)

Woodroffe, J.A.; Abichandani, J.S.

1990-01-01

This patent describes the method for the combustion of a carbon- and sulfur-containing fuel for substantially reducing emission of gaseous sulfur compounds formed during combustion of the fuel in a combustion zone. The zone having one or more fuel inlets and one or more oxidizer inlets, and having a combustion products outlet spaced therefrom, and having one or more inorganic sorbent inlets downstream of the fuel inlet(s) and oxidizer inlet(s) and upstream of the combustion products outlet

A sulfur host based on titanium monoxide@carbon hollow spheres for advanced lithium-sulfur batteries.

Science.gov (United States)

Li, Zhen; Zhang, Jintao; Guan, Buyuan; Wang, Da; Liu, Li-Min; Lou, Xiong Wen David

2016-10-20

Lithium-sulfur batteries show advantages for next-generation electrical energy storage due to their high energy density and cost effectiveness. Enhancing the conductivity of the sulfur cathode and moderating the dissolution of lithium polysulfides are two key factors for the success of lithium-sulfur batteries. Here we report a sulfur host that overcomes both obstacles at once. With inherent metallic conductivity and strong adsorption capability for lithium-polysulfides, titanium monoxide@carbon hollow nanospheres can not only generate sufficient electrical contact to the insulating sulfur for high capacity, but also effectively confine lithium-polysulfides for prolonged cycle life. Additionally, the designed composite cathode further maximizes the lithium-polysulfide restriction capability by using the polar shells to prevent their outward diffusion, which avoids the need for chemically bonding all lithium-polysulfides on the surfaces of polar particles.

Risk management for sulfur dioxide abatement under multiple uncertainties

Science.gov (United States)

Dai, C.; Sun, W.; Tan, Q.; Liu, Y.; Lu, W. T.; Guo, H. C.

2016-03-01

In this study, interval-parameter programming, two-stage stochastic programming (TSP), and conditional value-at-risk (CVaR) were incorporated into a general optimization framework, leading to an interval-parameter CVaR-based two-stage programming (ICTP) method. The ICTP method had several advantages: (i) its objective function simultaneously took expected cost and risk cost into consideration, and also used discrete random variables and discrete intervals to reflect uncertain properties; (ii) it quantitatively evaluated the right tail of distributions of random variables which could better calculate the risk of violated environmental standards; (iii) it was useful for helping decision makers to analyze the trade-offs between cost and risk; and (iv) it was effective to penalize the second-stage costs, as well as to capture the notion of risk in stochastic programming. The developed model was applied to sulfur dioxide abatement in an air quality management system. The results indicated that the ICTP method could be used for generating a series of air quality management schemes under different risk-aversion levels, for identifying desired air quality management strategies for decision makers, and for considering a proper balance between system economy and environmental quality.

A composite of hollow carbon nanospheres and sulfur-rich polymers for lithium-sulfur batteries

Science.gov (United States)

Zeng, Shao-Zhong; Yao, Yuechao; Zeng, Xierong; He, Qianjun; Zheng, Xianfeng; Chen, Shuangshuang; Tu, Wenxuan; Zou, Jizhao

2017-07-01

Lithium-sulfur batteries are the most promising candidates for future high-energy applications because of the unparalleled capacity of sulfur (1675 mAh g-1). However, lithium-sulfur batteries have limited cycle life and rate capability due to the dissolution of polysulfides and the extremely low electronic conductivity of sulfur. To solve these issues, various porous carbons including hollow carbon nanospheres (HCNs) have been used for improving the conductivity. However, these methods still suffer from polysulfides dissolution/loss owing to their weak physical adsorption to polysulfides. Herein, we introduced a covalent grafting route to composite the HCNs and the vulcanized trithiocyanuric acid (TTCA). The composite exhibits a high loading of the vulcanized TTCA by the HCNs with high surface area and large pore volume, and covalent bonds to sulfur, effectively depressing the dissolution of polysulfides. The first discharge capacity of the composite reaches 1430 mAh g-1 at 0.1 C and 1227 mAh g-1 at 0.2 C.

Interpreting isotopic analyses of microbial sulfate reduction in oil reservoirs

Science.gov (United States)

Hubbard, C. G.; Engelbrektson, A. L.; Druhan, J. L.; Cheng, Y.; Li, L.; Ajo Franklin, J. B.; Coates, J. D.; Conrad, M. E.

2013-12-01

Microbial sulfate reduction in oil reservoirs is often associated with secondary production of oil where seawater (28 mM sulfate) is commonly injected to maintain reservoir pressure and displace oil. The hydrogen sulfide produced can cause a suite of operating problems including corrosion of infrastructure, health exposure risks and additional processing costs. We propose that monitoring of the sulfur and oxygen isotopes of sulfate can be used as early indicators that microbial sulfate reduction is occurring, as this process is well known to cause substantial isotopic fractionation. This approach relies on the idea that reactions with reservoir (iron) minerals can remove dissolved sulfide, thereby delaying the transport of the sulfide through the reservoir relative to the sulfate in the injected water. Changes in the sulfate isotopes due to microbial sulfate reduction may therefore be measurable in the produced water before sulfide is detected. However, turning this approach into a predictive tool requires (i) an understanding of appropriate fractionation factors for oil reservoirs, (ii) incorporation of isotopic data into reservoir flow and reactive transport models. We present here the results of preliminary batch experiments aimed at determining fractionation factors using relevant electron donors (e.g. crude oil and volatile fatty acids), reservoir microbial communities and reservoir environmental conditions (pressure, temperature). We further explore modeling options for integrating isotope data and discuss whether single fractionation factors are appropriate to model complex environments with dynamic hydrology, geochemistry, temperature and microbiology gradients.

Kinetic isotope effect studies of the S-adenosylmethionine synthetase reaction

International Nuclear Information System (INIS)

Markham, G.D.; Parkin, D.W.; Schramm, V.L.

1986-01-01

S-adenosylmethionine (AdoMet) synthetase catalyzes a unique substitution reaction at the 5' carbon of MgATP. Kinetic isotope effect (V/K) measurements have been used to investigate the mechanism of AdoMet synthetase from E. coli. Changes in 3 H/ 14 C ratios when AdoMet is formed from a mixture of either ([5'- 14 C]ATP and [5'- 12 C,1'- 3 H]ATP) or ([5'- 3 H]ATP and [5'- 1 H,1'- 14 C]ATP) were examined. The effects of varying the concentrations of the co-substrate methionine and the monovalent cation activator K + were investigated. Substitution of 14 C for 12 C at the 5' position of ATP yields a primary V/K kinetic isotope effect ( 12 C/ 14 C) of 1.128 +/- 0.004 at low K + and methionine concentrations. The observed isotope effect diminishes slightly to 1.107 +/- 0.003 when both K + and methionine are present at saturating concentrations, suggesting that MgATP has only a low commitment to catalysis from at conditions near Vmax. No secondary V/K 3 H isotope effect from [5'- 3 H]ATP was detected ( 1 H/ 3 H) = 0.997 +/- 0.003. The magnitude of the primary 14 C isotope effect and the small secondary 3 H effect demonstrate that AdoMet synthesis occurs with a S/sub N/ 2 transition state which is symmetric with respect to the sulfur nucleophile and the departing tripolyphosphate group

Copper isotopic zonation in the Northparkes porphyry Cu-Au deposit, SE Australia

Science.gov (United States)

Li, Weiqiang; Jackson, Simon E.; Pearson, Norman J.; Graham, Stuart

2010-07-01

Significant, systematic Cu isotopic variations have been found in the Northparkes porphyry Cu-Au deposit, NSW, Australia, which is an orthomagmatic porphyry Cu deposit. Copper isotope ratios have been measured in sulfide minerals (chalcopyrite and bornite) by both solution and laser ablation multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The results from both methods show a variation in δ 65Cu of hypogene sulfide minerals of greater than 1‰ (relative to NIST976). Significantly, the results from four drill holes through two separate ore bodies show strikingly similar patterns of Cu isotope variation. The patterns are characterized by a sharp down-hole decrease from up to 0.8‰ (0.29 ± 0.56‰, 1 σ, n = 20) in the low-grade peripheral alteration zones (phyllic-propylitic alteration zone) to a low of ˜-0.4‰ (-0.25 ± 0.36‰, 1 σ, n = 30) at the margins of the most mineralized zones (Cu grade >1 wt%). In the high-grade cores of the systems, the compositions are more consistent at around 0.2‰ (0.19 ± 0.14‰, 1 σ, n = 40). The Cu isotopic zonation may be explained by isotope fractionation of Cu between vapor, solution and sulfides at high temperature, during boiling and sulfide precipitation processes. Sulfur isotopes also show an isotopically light shell at the margins of the high-grade ore zones, but these are displaced from the low δ 65Cu shells, such that there is no correlation between the Cu and S isotope signatures. Fe isotope data do not show any discernable variation along the drill core. This work demonstrates that Cu isotopes show a large response to high-temperature porphyry mineralizing processes, and that they may act as a vector to buried mineralization.

Aircraft exhaust sulfur emissions

Energy Technology Data Exchange (ETDEWEB)

Brown, R C; Anderson, M R; Miake-Lye, R C; Kolb, C E [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A A; Buriko, Y I [Scientific Research Center ` Ecolen` , Moscow (Russian Federation)

1998-12-31

The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

Aircraft exhaust sulfur emissions

Energy Technology Data Exchange (ETDEWEB)

Brown, R.C.; Anderson, M.R.; Miake-Lye, R.C.; Kolb, C.E. [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A.A.; Buriko, Y.I. [Scientific Research Center `Ecolen`, Moscow (Russian Federation)

1997-12-31

The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

Oxidation of inorganic sulfur compounds in acidophilic prokaryotes

Energy Technology Data Exchange (ETDEWEB)

Rohwerder, T.; Sand, W. [Universitaet Duisburg-Essen, Biofilm Centre, Aquatic Biotechnology, Duisburg (Germany)

2007-07-15

The oxidation of reduced inorganic sulfur compounds to sulfuric acid is of great importance for biohydrometallurgical technologies as well as the formation of acidic (below pH 3) and often heavy metal-contaminated environments. The use of elemental sulfur as an electron donor is the predominant energy-yielding process in acidic natural sulfur-rich biotopes but also at mining sites containing sulfidic ores. Contrary to its significant role in the global sulfur cycle and its biotechnological importance, the microbial fundamentals of acidophilic sulfur oxidation are only incompletely understood. Besides giving an overview of sulfur-oxidizing acidophiles, this review describes the so far known enzymatic reactions related to elemental sulfur oxidation in acidophilic bacteria and archaea. Although generally similar reactions are employed in both prokaryotic groups, the stoichiometry of the key enzymes is different. Bacteria oxidize elemental sulfur by a sulfur dioxygenase to sulfite whereas in archaea, a sulfur oxygenase reductase is used forming equal amounts of sulfide and sulfite. In both cases, the activation mechanism of elemental sulfur is not known but highly reactive linear sulfur forms are assumed to be the actual substrate. Inhibition as well as promotion of these biochemical steps is highly relevant in bioleaching operations. An efficient oxidation can prevent the formation of passivating sulfur layers. In other cases, a specific inhibition of sulfur biooxidation may be beneficial for reducing cooling and neutralization costs. In conclusion, the demand for a better knowledge of the biochemistry of sulfur-oxidizing acidophiles is underlined. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

Sandwich-like graphene-mesoporous carbon as sulfur host for enhanced lithium-sulfur batteries

Science.gov (United States)

Tian, Ting; Li, Bin; Zhu, Mengqi; Liu, Jianhua; Li, Songmei

2017-10-01

Graphene-mesoporous carbon/sulfur composites (G-MPC/S) were constructed by melt-infiltration of sulfur into graphene-mesoporous carbon which was synthesized by soft template method. The SEM and BET results of the graphene-mesoporous carbon show that the as-prepared sandwich-like G-MPC composites with a unique microporous-mesoporous structure had a high specific surface area of 554.164 m2 · g-1 and an average pore size of about 13 nm. The XRD analysis presents the existence of orthorhombic sulfur in the G-MPC/S composite, which indicates the complete infiltration of sulfur into the pores of the G-MPC. When the graphene-mesoporous carbon/surfur composites (G-MPC/S) with 53.9 wt.% sulfur loading were used as the cathode for lithium-sulfur (Li-S) batteries, it exhibited an outstanding electrochemical performance including excellent initial discharge specific capacity of 1393 mAh · g-1 at 0.1 °C, high cycle stability (731 mAh · g-1 at 200 cycles) and good rate performance (1038 mAh · g-1, 770 mAh · g-1, 518 mAh · g-1 and 377 mAh · g-1 at 0.1 °C, 0.2 °C, 0.5 °C and 1 °C, respectively), which suggested the important role of the G-MPC composite in providing more electrons and ions channels, in addition, the shuttle effect caused by the dissolved polysulfide was also suppressed.

Metallic and highly conducting two-dimensional atomic arrays of sulfur enabled by molybdenum disulfide nanotemplate

Science.gov (United States)

Zhu, Shuze; Geng, Xiumei; Han, Yang; Benamara, Mourad; Chen, Liao; Li, Jingxiao; Bilgin, Ismail; Zhu, Hongli

2017-10-01

Element sulfur in nature is an insulating solid. While it has been tested that one-dimensional sulfur chain is metallic and conducting, the investigation on two-dimensional sulfur remains elusive. We report that molybdenum disulfide layers are able to serve as the nanotemplate to facilitate the formation of two-dimensional sulfur. Density functional theory calculations suggest that confined in-between layers of molybdenum disulfide, sulfur atoms are able to form two-dimensional triangular arrays that are highly metallic. As a result, these arrays contribute to the high conductivity and metallic phase of the hybrid structures of molybdenum disulfide layers and two-dimensional sulfur arrays. The experimentally measured conductivity of such hybrid structures reaches up to 223 S/m. Multiple experimental results, including X-ray photoelectron spectroscopy (XPS), transition electron microscope (TEM), selected area electron diffraction (SAED), agree with the computational insights. Due to the excellent conductivity, the current density is linearly proportional to the scan rate until 30,000 mV s-1 without the attendance of conductive additives. Using such hybrid structures as electrode, the two-electrode supercapacitor cells yield a power density of 106 Wh kg-1 and energy density 47.5 Wh kg-1 in ionic liquid electrolytes. Our findings offer new insights into using two-dimensional materials and their Van der Waals heterostructures as nanotemplates to pattern foreign atoms for unprecedented material properties.

Parameters Influencing Sulfur Speciation in Environmental Samples Using Sulfur K-Edge X-Ray Absorption Near-Edge Structure

Directory of Open Access Journals (Sweden)

Siwatt Pongpiachan

2012-01-01

Full Text Available This paper aims to enhance the credibility of applying the sulfur K-edge XANES spectroscopy as an innovative “fingerprint” for characterizing environmental samples. The sensitivities of sulfur K-edge XANES spectra of ten sulfur compound standards detected by two different detectors, namely, Lytle detector (LyD and Germanium detector (GeD, were studied and compared. Further investigation on “self-absorption” effect revealed that the maximum sensitivities of sulfur K-edge XANES spectra were achieved when diluting sulfur compound standards with boron nitride (BN at the mixing ratio of 0.1%. The “particle-size” effect on sulfur K-edge XANES spectrum sensitivities was examined by comparing signal-to-noise ratios of total suspended particles (TSP and particulate matter of less than 10 millionths of a meter (PM10 collected at three major cities of Thailand. The analytical results have demonstrated that the signal-to-noise ratios of sulfur K-edge XANES spectra were positively correlated with sulfate content in aerosols and negatively connected with particle sizes. The combination of hierarchical cluster analysis (HCA and principal component analysis (PCA has proved that sulfur K-edge XANES spectrum can be used to characterize German terrestrial soils and Andaman coastal sediments. In addition, this study highlighted the capability of sulfur K-edge XANES spectra as an innovative “fingerprint” to distinguish tsunami backwash deposits (TBD from typical marine sediments (TMS.

A distinct section of the Early Bronze Age society? Stable isotope investigations of burials in settlement pits and multiple inhumations of the Únětice culture in central Germany.

Science.gov (United States)

Knipper, Corina; Fragata, Matthias; Nicklisch, Nicole; Siebert, Angelina; Szécsényi-Nagy, Anna; Hubensack, Vera; Metzner-Nebelsick, Carola; Meller, Harald; Alt, Kurt W

2016-03-01

Inhumations in so-called settlement pits and multiple interments are subordinate burial practices of the Early Bronze Age Únětice culture in central Germany (2200-1700/1650 BC). The majority of the Únětice population was entombed as single inhumations in rectangular grave pits with a normative position of the body. The goal of the study was to test archaeological hypotheses that the deviant burials may represent socially distinct or nonlocal individuals. The study comprised up to two teeth and one bone each of 74 human individuals from eight sites and faunal comparative samples. The inhumations included regular, deviant burials in so-called settlement or storage pits, and multiple burials. We investigated radiogenic strontium isotope compositions of tooth enamel ((87) Sr/(86) Sr) and light stable isotope ratios of carbon and nitrogen of bone collagen (δ(13) C, δ(15) N) aiming at the disclosure of residential changes and dietary patterns. Site-specific strontium isotope data ranges mirror different geological properties including calcareous bedrock, loess, and glacial till. Independent from burial types, they disclose low portions of nonlocal individuals of up to some 20% at the individual sites. The light stable isotope ratios of burials in settlement pits and rectangular graves overlap widely and indicate highly similar dietary habits. The analytical results let to conclude that inhumations in settlement pits and multiple burials were two of the manifold burial practices of the Early Bronze Age. The selection criteria of the individuals for the different forms of inhumation remained undisclosed. © 2015 Wiley Periodicals, Inc.

Effect of sulfur dioxide partial pressure on the reaction of iodine, sulfur dioxide and water

International Nuclear Information System (INIS)

Nakajima, Hayato; Imai, Yoshiyuki; Kasahara, Seiji; Kubo, Shinji; Onuki, Kaoru

2007-01-01

Effect of sulfur dioxide partial pressure on the reaction of iodine, sulfur dioxide and water, which is a unit reaction in the IS process for thermochemical hydrogen production, was studied experimentally at 323 K under iodine saturation. Quasi-equilibrium state was observed in the presence of sulfur dioxide gas at constant pressure. The composition of the poly-hydriodic acid solution formed was discussed assuming an ideal desulfurization by the reverse reaction of the Bunsen reaction. The value of HI/(HI+H 2 O) of the desulfurized solution was large at high sulfur dioxide pressure and reached the maximum of 15.7 ± 0.3 mol%. (author)

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

Flow injection gas chromatography with sulfur chemiluminescence detection for the analysis of total sulfur in complex hydrocarbon matrixes.

Science.gov (United States)

Hua, Yujuan; Hawryluk, Myron; Gras, Ronda; Shearer, Randall; Luong, Jim

2018-01-01

A fast and reliable analytical technique for the determination of total sulfur levels in complex hydrocarbon matrices is introduced. The method employed flow injection technique using a gas chromatograph as a sample introduction device and a gas phase dual-plasma sulfur chemiluminescence detector for sulfur quantification. Using the technique described, total sulfur measurement in challenging hydrocarbon matrices can be achieved in less than 10 s with sample-to-sample time ideal for fast analysis or trace sulfur analysis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A primer on sulfur for the planetary geologist

Science.gov (United States)

Theilig, E.

1982-01-01

Sulfur has been proposed as the dominant composition for the volcanic material on Io. Sulfur is a complex element which forms many intramolecular and intermolecular allotropes exhibiting a variety of physical properties. Cyclo-S8 sulfur is the most abundant and stable molecular form. The important molecular species within liquid sulfur change in concentration with temperature. Concentrations of the allotropes control the physical properties of the melt. Discontinuities in density, viscosity, and thermal properties reflect the polymerization process within liquid sulfur. Variations in the melting point are related to autodissociation of the liquid. Many solids forms of sulfur have been identified but only orthorhombic alpha and monoclinic beta sulfur, both composed of cyclo-S8 sulfur, are stable under terrestrial conditions. Physical properties of solid sulfur are dependent on the allotrope and, in some cases, the thermal history. Three natural terrestrial sulfur flows are described: (1) Siretoko-Iosan, Japan; (2) Volcan Azufre, Galapagos Islands; and (3) Mauna Loa, Hawaii. All of the flows are associated with fumarolic areas and are considered to have formed by the melting and mobilization of sulfur deposits. Surface textures of the flows indicate a behavior of molten sulfur similar to that of silicate lava. Channels, rivulets, and lobate edges were described for the flows. The solidification of man-made sulfur flows formed as part of the Frasch mining process by which sulfur is removed from the subsurface in a liquid state is described.

Mercury adsorption properties of sulfur-impregnated adsorbents

Science.gov (United States)

Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

2002-01-01

Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

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

Science.gov (United States)

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

2018-04-01

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

Comparative analysis of the mechanisms of sulfur anion oxidation and reduction by dsr operon to maintain environmental sulfur balance.

Science.gov (United States)

Ghosh, Semanti; Bagchi, Angshuman

2015-12-01

Sulfur metabolism is one of the oldest known redox geochemical cycles in our atmosphere. These redox processes utilize different sulfur anions and the reactions are performed by the gene products of dsr operon from phylogenetically diverse sets of microorganisms. The operon is involved in the maintenance of environmental sulfur balance. Interestingly, the dsr operon is found to be present in both sulfur anion oxidizing and reducing microorganisms and in both types of organisms DsrAB protein complex plays a vital role. Though there are various reports regarding the genetics of dsr operon there are practically no reports dealing with the structural aspects of sulfur metabolism by dsr operon. In our present study, we tried to compare the mechanisms of sulfur anion oxidation and reduction by Allochromatium vinosum and Desulfovibrio vulgaris respectively through DsrAB protein complex. We analyzed the modes of bindings of sulfur anions to the DsrAB protein complex and observed that for sulfur anion oxidizers, sulfide and thiosulfate are the best substrates whereas for reducers sulfate and sulfite have the best binding abilities. We analyzed the binding interaction pattern of the DsrA and DsrB proteins while forming the DsrAB protein complexes in Desulfovibrio vulgaris and Allochromatium vinosum. To our knowledge this is the first report that analyzes the differences in binding patterns of sulfur substrates with DsrAB protein from these two microorganisms. This study would therefore be essential to predict the biochemical mechanism of sulfur anion oxidation and reduction by these two microorganisms i.e., Desulfovibrio vulgaris (sulfur anion reducer) and Allochromatium vinosum (sulfur anion oxidizer). Our observations also highlight the mechanism of sulfur geochemical cycle which has important implications in future study of sulfur metabolism as it has a huge application in waste remediation and production of industrial bio-products viz. vitamins, bio-polyesters and bio

The status of isotopic investigations of the Limpopo mobile belt

International Nuclear Information System (INIS)

Barton, J.M. Jr.

1981-01-01

The Limpopo Belt is a zone of multiple deformed metamorphic rocks situated between the Rhodesian and Kaapvaal Cratons of Southern Africa. During the duration of the International Geodynamics Project, geochronologic and isotopic investigations were undertaken in the nothern Transvaal of rocks of the Central Zone, Southern Marginal Zone and Soutpansberg Supergroup. Strontium 86, strontium 87 and lead isotopes were used in the isotopic investigations

Isotope ratio measurements with multiple collection inductively coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Platzner, I.T.; Segal, I.; Halicz, L.

2003-01-01

In the studies summarized in this review, it has been shown that IRM of lead in silicates can be carried out without lead separation and purification. Because of time independent mass discrimination and lack of chemical interaction at high plasma temperatures, simple interference corrections are feasible. This data further support the observation that MC-ICP-MS provides data with superior precision comparing to TIMS. Furthermore, it should be noted that the multi collection instrumental configuration exhibits the capability to perform a single IRM with excellent precision and high accuracy for elements with a large number of isotopes. Four of the discussed elements have six (Er) and seven (Dy, Yb, Os) isotopes

Isotope geochemistry of drainage from an acid mine impaired watershed, Oakland, California

International Nuclear Information System (INIS)

Butler, Thomas W.

2007-01-01

Oxidation of sulfides at the Leona Heights Sulfur Mine has resulted in the liberation of acid, SO 4 and metals to Leona Creek. Previous research at the site has indicated Fe(II) oxidation at rates faster than would be predicted by abiotic oxidation alone, particularly in the segment of stream between the Adit and Leona Street sample stations. In order to assess the mechanisms responsible for sulfide oxidation, samples were collected for isotopic analysis of water and SO 4 , the results of which were used to develop a stoichiometric isotope-balance model. This exercise indicated that the percentage of water-derived oxygen in SO 4 increased spatially from between 56% and 64% at the Adit to between 71% and 72% at Leona Street, illustrating that increased sulfide oxidation via Fe(III) was occurring within, or as water flows over, the waste rock, relative to water emanating directly from the former mine. The incorporation of water-derived oxygen in SO 4 during pyrite oxidation is a process controlled by Fe oxidizing bacteria such as A. ferrooxidans at low pH. The role of bacteria was further supported by estimates of the rate constant for Fe oxidation between sampling stations, yielding values that were approximately 10 6 faster than abiotic Fe oxidation alone. Stable isotopic analysis of water further indicates a close correlation of adit spring water to the local meteoric water line, while 3 H data indicate a groundwater apparent age, or time of travel from its primary zone of recharge, of 34 S data, in conjunction with reported albitized feldspars within the Leona Rhyolite host rock, indicate a magmatic origin of ore sulfur, contrary to previous interpretations at the site

46 CFR 151.50-21 - Sulfuric acid.

Science.gov (United States)

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Sulfuric acid. 151.50-21 Section 151.50-21 Shipping... BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-21 Sulfuric acid. (a) How sulfuric acid may be carried. (1) Sulfuric acid of concentration of 77.5 percent (1.7019 specific gravity) (59.8...

46 CFR 153.1046 - Sulfuric acid.

Science.gov (United States)

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Sulfuric acid. 153.1046 Section 153.1046 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK....1046 Sulfuric acid. No person may liquefy frozen or congealed sulfuric acid other than by external tank...

Sensing sulfur oxides and other sulfur bearing pollutants with solid electrolyte pellets. I. Gas concentration cells

Energy Technology Data Exchange (ETDEWEB)

Chamberland, A M; Gauthier, J M

1977-01-01

A new sensing technique using a solid electrolyte has been demonstrated for sulfur-bearing pollutants. Based on potentiometric measurements across a pellet of potassium sulfate, this sensor allows concentrations of sulfur dioxides, sulfur trioxide, hydrogen sulfide, methyl mercaptan and carbonyl sulfide in air to be measured with accuracy. Its operational concentration range at the present time is 0.1 ppM up to at least 10,000 ppM. The presence of other common pollutants such as carbon dioxide, methane, nitric oxide and nitrogen dioxide does not interfere with the measurement of air samples containing sulfur-bearing pollutants.

Finite mixture models for the computation of isotope ratios in mixed isotopic samples

Science.gov (United States)

Koffler, Daniel; Laaha, Gregor; Leisch, Friedrich; Kappel, Stefanie; Prohaska, Thomas

2013-04-01

Finite mixture models have been used for more than 100 years, but have seen a real boost in popularity over the last two decades due to the tremendous increase in available computing power. The areas of application of mixture models range from biology and medicine to physics, economics and marketing. These models can be applied to data where observations originate from various groups and where group affiliations are not known, as is the case for multiple isotope ratios present in mixed isotopic samples. Recently, the potential of finite mixture models for the computation of 235U/238U isotope ratios from transient signals measured in individual (sub-)µm-sized particles by laser ablation - multi-collector - inductively coupled plasma mass spectrometry (LA-MC-ICPMS) was demonstrated by Kappel et al. [1]. The particles, which were deposited on the same substrate, were certified with respect to their isotopic compositions. Here, we focus on the statistical model and its application to isotope data in ecogeochemistry. Commonly applied evaluation approaches for mixed isotopic samples are time-consuming and are dependent on the judgement of the analyst. Thus, isotopic compositions may be overlooked due to the presence of more dominant constituents. Evaluation using finite mixture models can be accomplished unsupervised and automatically. The models try to fit several linear models (regression lines) to subgroups of data taking the respective slope as estimation for the isotope ratio. The finite mixture models are parameterised by: • The number of different ratios. • Number of points belonging to each ratio-group. • The ratios (i.e. slopes) of each group. Fitting of the parameters is done by maximising the log-likelihood function using an iterative expectation-maximisation (EM) algorithm. In each iteration step, groups of size smaller than a control parameter are dropped; thereby the number of different ratios is determined. The analyst only influences some control

21 CFR 582.1095 - Sulfuric acid.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Sulfuric acid. 582.1095 Section 582.1095 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1095 Sulfuric acid. (a) Product. Sulfuric acid. (b) Conditions of use. This substance is generally...

Io's theothermal (sulfur) - Lithosphere cycle inferred from sulfur solubility modeling of Pele's magma supply

Science.gov (United States)

Battaglia, Steven M.; Stewart, Michael A.; Kieffer, Susan W.

2014-06-01

Surface deposits of volatile compounds such as water (Earth) or sulfur (Io) on volcanically active bodies suggest that a magmatic distillation process works to concentrate volatiles in surface reservoirs. On Earth, this is the combined hydrologic and tectonic cycle. On Io, sulfurous compounds are transferred from the interior to the surface reservoirs through a combination of a mantle-sourced magmatic system, vertical cycling of the lithosphere, and a sulfur-dominated crustal thermal system that we here call the "theothermal" system. We present a geochemical analysis of this process using previously inferred temperature and oxygen fugacity constraints of Pele's basaltic magma to determine the behavior of sulfur in the ionian magmas. Sulfate to sulfide ratios of Pele's magma are -4.084 ± 0.6 and -6.442 ± 0.7 log10 units, comparable to or lower than those of mid-ocean ridge basalts. This reflects the similarity of Io's oxidation state with Earth's depleted mantle as previously suggested by Zolotov and Fegley (Zolotov, M.Y., Fegley, B. [2000]. Geophys. Res. Lett. 27, 2789-2792). Our calculated limits of sulfur solubility in melts from Pele's patera (˜1100-1140 ppm) are also comparable to terrestrial mid-ocean ridge basalts, reflecting a compositional similarity of mantle sources. We propose that the excess sulfur obvious on Io's surface comes from two sources: (1) an insoluble sulfide liquid phase in the magma and (2) theothermal near-surface recycling.