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Sample records for multiple sulfur isotopes

  1. Identification of sulfur sources and isotopic equilibria in submarine hot-springs using multiple sulfur isotopes

    NASA Astrophysics Data System (ADS)

    McDermott, Jill M.; Ono, Shuhei; Tivey, Margaret K.; Seewald, Jeffrey S.; Shanks, Wayne C.; Solow, Andrew R.

    2015-07-01

    Multiple sulfur isotopes were measured in metal sulfide deposits, elemental sulfur, and aqueous hydrogen sulfide to constrain sulfur sources and the isotopic systematics of precipitation in seafloor hydrothermal vents. Areas studied include the Eastern Manus Basin and Lau Basin back-arc spreading centers and the unsedimented basalt-hosted Southern East Pacific Rise (SEPR) and sediment-hosted Guaymas Basin mid-ocean ridge spreading centers. Chalcopyrite and dissolved hydrogen sulfide (H2S) δ34S values range from -5.5‰ to +5.6‰ in Manus Basin samples, +2.4‰ to +6.1‰ in Lau Basin samples, and +3.7‰ to +5.7‰ in SEPR samples. Values of δ34S for cubic cubanite and H2S range from -1.4‰ to +4.7‰ in Guaymas Basin samples. Multiple sulfur isotope systematics in fluid-mineral pairs from the SEPR and Lau Basin show that crustal host rock and thermochemical reduction of seawater-derived dissolved sulfate (SO4) are the primary sources of sulfur in mid-ocean ridge and some back-arc systems. At PACMANUS and SuSu Knolls hydrothermal systems in the Eastern Manus Basin, a significant contribution of sulfur is derived from disproportionation of magmatic sulfur dioxide (SO2), while the remaining sulfur is derived from crustal host rocks and SO4 reduction. At the sedimented Guaymas Basin hydrothermal system, sulfur sources include crustal host rock, reduced seawater SO4, and biogenic sulfide. Vent fluid flow through fresher, less-mature sediment supplies an increased quantity of reactant organic compounds that may reduce 34S-enriched SO4, while fluid interaction with more highly-altered sediments results in H2S characterized by a small, but isotopically-significant input of 34S-depleted biogenic sulfides. Near-zero Δ33S values in all samples implicate the abiotic processes of SO4 reduction and leaching of host rock as the major contributors to sulfur content at a high temperature unsedimented mid-ocean ridge and at a back-arc system. Δ33S values indicate that SO2

  2. Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs

    PubMed Central

    2014-01-01

    Background The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling. Results Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6 μmol L-1) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The δ34S values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools δ34S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH < 4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur–polysulfide – hydrogen sulfide system. Triple sulfur isotope (32S, 33S, 34S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ∆33S among

  3. Multiple sulfur isotope composition of oxidized Samoan melts and the implications of a sulfur isotope 'mantle array' in chemical geodynamics

    NASA Astrophysics Data System (ADS)

    Labidi, J.; Cartigny, P.; Jackson, M. G.

    2015-05-01

    To better address how subducted protoliths drive the Earth's mantle sulfur isotope heterogeneity, we report new data for sulfur (S) and copper (Cu) abundances, S speciation and multiple S isotopic compositions (32S, 33S, 34S, 36S) in 15 fresh submarine basaltic glasses from the Samoan archipelago, which defines the enriched-mantle-2 (EM2) endmember. Bulk S abundances vary between 835 and 2279 ppm. About 17 ± 11% of sulfur is oxidized (S6+) but displays no consistent trend with bulk S abundance or any other geochemical tracer. The S isotope composition of both dissolved sulfide and sulfate yield homogeneous Δ33S and Δ36S values, within error of Canyon Diablo Troilite (CDT). In contrast, δ34S values are variable, ranging between +0.11 and +2.79‰ (±0.12‰ 1σ) for reduced sulfur, whereas oxidized sulfur values vary between +4.19 and +9.71‰ (±0.80‰, 1σ). Importantly, δ34S of the reduced S pool correlates with the 87Sr/86Sr ratios of the glasses, in a manner similar to that previously reported for South-Atlantic MORB, extending the trend to δ34S values up to + 2.79 ± 0.04 ‰, the highest value reported for undegassed oceanic basalts. As for EM-1 basalts from the South Atlantic ridge, the linear δ34S-87Sr/86Sr trend requires the EM-2 endmember to be relatively S-rich, and only sediments can account for these isotopic characteristics. While many authors argue that both the EM-1 and EM-2 mantle components record subduction of various protoliths (e.g. upper or lower continental crust, lithospheric mantle versus intra-metasomatized mantle, or others), it is proposed here that they primarily reflect sediment recycling. Their distinct Pb isotope variation can be accounted for by varying the proportion of S-poor recycled oceanic crust in the source of mantle plumes.

  4. Temperature effects on the fractionation of multiple sulfur isotopes by Thermodesulfobacterium and Desulfovibrio strains

    NASA Astrophysics Data System (ADS)

    Wang, P.; Sun, C.; Ono, S.; Lin, L.

    2012-12-01

    Microbial dissimilatory sulfate reduction is one of the major mechanisms driving anaerobic mineralization of organic matter in global ocean. While sulfate-reducing prokaryotes are well known to fractionate sulfur isotopes during dissimilatory sulfate reduction, unraveling the isotopic compositions of sulfur-bearing minerals preserved in sedimentary records could provide invaluable constraints on the evolution of seawater chemistry and metabolic pathways. Variations in the sulfur isotope fractionations are partly due to inherent differences among species and also affected by environmental conditions. The isotope fractionations caused by microbial sulfate reduction have been interpreted to be a sequence of enzyme-catalyzed isotope fractionation steps. Therefore, the fractionation factor depends on (1) the sulfate flux into and out of the cell, and (2) the flux of sulfur transformation between the internal pools. Whether the multiple sulfur isotope effect could be quantitatively predicted using such a metabolic flux model would provide insights into the cellular machinery catalyzing with sulfate reduction. This study examined the multiple sulfur isotope fractionation patterns associated with a thermophilic Thermodesulfobacterium-related strain and a mesophilic Desulfovibrio gigas over a wide temperature range. The Thermodesulfobacterium-related strain grew between 34 and 79°C with an optimal temperature at 72°C and the highest cell-specific sulfate reduction rate at 77°C. The 34ɛ values ranged between 8.2 and 31.6‰ with a maximum at 68°C. The D. gigas grew between 10 and 45 °C with an optimal temperature at 30°C and the highest cell-specific sulfate reduction rate at 41°C. The 34ɛ values ranged between 10.3 and 29.7‰ with higher magnitude at both lower and higher temperatures. The results of multiple sulfur isotope measurements expand the previously reported range and cannot be described by a solution field of the metabolic flux model, which calculates

  5. The multiple sulfur isotopic composition of iron meteorites: Implications for nebular evolution

    NASA Astrophysics Data System (ADS)

    Antonelli, Michael Ariel

    2013-12-01

    Multiple sulfur isotopic measurements of troilite from 61 different iron meteorites were undertaken in order to test for sulfur isotopic homogeneity within (and between) 8 different iron meteorite groups. It was found that different members within a given group of iron meteorites have homogeneous Delta 33S compositions, but that these Delta33S compositions differ between groups. This thesis shows that iron meteorites from the groups IC, IIAB, IIIAB, IIIF, and IVA have small yet resolvable enrichments or depletions in Delta33S relative to Canyon Diablo Troilite (CDT) and troilite from other non-magmatic (IAB and IIE) iron meteorites. The observed anomalous sulfur isotopic compositions in magmatic iron meteorites are most consistent with Lyman-alpha photolysis of H2S, pointing towards inheritance of an unexpected photolytically-derived sulfur component in magmatic iron meteorite groups which is absent in non-magmatic iron meteorites, chondrites, and the Earth-Moon System.

  6. Triple oxygen and multiple sulfur isotope constraints on the evolution of the post-Marinoan sulfur cycle

    NASA Astrophysics Data System (ADS)

    Crockford, Peter W.; Cowie, Benjamin R.; Johnston, David T.; Hoffman, Paul F.; Sugiyama, Ichiko; Pellerin, Andre; Bui, Thi Hao; Hayles, Justin; Halverson, Galen P.; Macdonald, Francis A.; Wing, Boswell A.

    2016-02-01

    Triple oxygen isotopes within post-Marinoan barites have played an integral role in our understanding of Cryogenian glaciations. Reports of anomalous Δ17O values within cap carbonate hosted barites however have remained restricted to South China and Mauritania. Here we extend the Δ17O anomaly to northwest Canada with our new measurements of barites from the Ravensthroat cap dolostone with a minimum Δ17O value of - 0.75 ‰. For the first time we pair triple oxygen with multiple sulfur isotopic data as a tool to identify the key processes that controlled the post-Marinoan sulfur cycle. We argue using a dynamic 1-box model that the observed isotopic trends both in northwest Canada and South China can be explained through the interplay between sulfide weathering, microbial sulfur cycling and pyrite burial. An important outcome of this study is a new constraint placed on the size of the post-Marinoan sulfate reservoir (≈0.1% modern), with a maximum concentration of less than 10% modern. Through conservative estimates of sulfate fluxes from sulfide weathering and under a small initial sulfate reservoir, we suggest that observed isotopic trends are the product of a dynamic sulfur cycle that saw both the addition and removal of the Δ17O anomaly over four to five turnovers of the post-Marinoan marine sulfate reservoir.

  7. High-Resolution Multiple Sulfur Isotope Studies of Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Mojzsis, S. J.

    2000-01-01

    Sensitive, high resolution measurements of S-32, S-31, and S-34 in individual pyrite grains in martian meteorite ALH84001 by an in situ ion microprobe multi-collection technique reveal mass-independent anomalies in Delta.S-33 (Delta.S-33 = delta.S-33 - 0.516delta.S-34) in addition to the lowest 634S found in an extraterrestrial material. Low delta.S-34 values in two pyrite grains intimately associated with carbonate in ALH84001 can be explained by the sensitivity of sulfur to fractionations in the geologic environment. Anomalies in Delta.S-33 recorded in ALH84001 pyrites probably formed by gas-phase reactions in the early martian atmosphere (>4 Ga). The discovery of clearly resolvable Delta-S33 anomalies in 2 of 12 ALH84001 pyrites analyzed in their petrographic context in thin section, is considered strong evidence for crust-atmosphere exchange and the global cycling of volatile sulfur species on early Mars. These results corroborate previous measurements by Farquhar and co-workers who used a different technique that measures that bulk Delta.S-33 values of martian meteorites. These independent techniques, and their results, suggest that sulfur affected by mass-independent fractionation is common on Mars.

  8. Multiple sulfur isotope evidence for massive oceanic sulfate depletion in the aftermath of Snowball Earth

    NASA Astrophysics Data System (ADS)

    Sansjofre, Pierre; Cartigny, Pierre; Trindade, Ricardo I. F.; Nogueira, Afonso C. R.; Agrinier, Pierre; Ader, Magali

    2016-07-01

    The terminal Neoproterozoic Era (850-542 Ma) is characterized by the most pronounced positive sulfur isotope (34S/32S) excursions in Earth's history, with strong variability and maximum values averaging δ34S~+38‰. These excursions have been mostly interpreted in the framework of steady-state models, in which ocean sulfate concentrations do not fluctuate (that is, sulfate input equals sulfate output). Such models imply a large pyrite burial increase together with a dramatic fluctuation in the isotope composition of marine sulfate inputs, and/or a change in microbial sulfur metabolisms. Here, using multiple sulfur isotopes (33S/32S, 34S/32S and 36S/32S ratios) of carbonate-associated sulfate, we demonstrate that the steady-state assumption does not hold in the aftermath of the Marinoan Snowball Earth glaciation. The data attest instead to the most impressive event of oceanic sulfate drawdown in Earth's history, driven by an increased pyrite burial, which may have contributed to the Neoproterozoic oxygenation of the oceans and atmosphere.

  9. Multiple sulfur isotope evidence for massive oceanic sulfate depletion in the aftermath of Snowball Earth.

    PubMed

    Sansjofre, Pierre; Cartigny, Pierre; Trindade, Ricardo I F; Nogueira, Afonso C R; Agrinier, Pierre; Ader, Magali

    2016-01-01

    The terminal Neoproterozoic Era (850-542 Ma) is characterized by the most pronounced positive sulfur isotope ((34)S/(32)S) excursions in Earth's history, with strong variability and maximum values averaging δ(34)S∼+38‰. These excursions have been mostly interpreted in the framework of steady-state models, in which ocean sulfate concentrations do not fluctuate (that is, sulfate input equals sulfate output). Such models imply a large pyrite burial increase together with a dramatic fluctuation in the isotope composition of marine sulfate inputs, and/or a change in microbial sulfur metabolisms. Here, using multiple sulfur isotopes ((33)S/(32)S, (34)S/(32)S and (36)S/(32)S ratios) of carbonate-associated sulfate, we demonstrate that the steady-state assumption does not hold in the aftermath of the Marinoan Snowball Earth glaciation. The data attest instead to the most impressive event of oceanic sulfate drawdown in Earth's history, driven by an increased pyrite burial, which may have contributed to the Neoproterozoic oxygenation of the oceans and atmosphere. PMID:27447895

  10. Multiple sulfur isotope evidence for massive oceanic sulfate depletion in the aftermath of Snowball Earth

    PubMed Central

    Sansjofre, Pierre; Cartigny, Pierre; Trindade, Ricardo I. F.; Nogueira, Afonso C. R.; Agrinier, Pierre; Ader, Magali

    2016-01-01

    The terminal Neoproterozoic Era (850–542 Ma) is characterized by the most pronounced positive sulfur isotope (34S/32S) excursions in Earth's history, with strong variability and maximum values averaging δ34S∼+38‰. These excursions have been mostly interpreted in the framework of steady-state models, in which ocean sulfate concentrations do not fluctuate (that is, sulfate input equals sulfate output). Such models imply a large pyrite burial increase together with a dramatic fluctuation in the isotope composition of marine sulfate inputs, and/or a change in microbial sulfur metabolisms. Here, using multiple sulfur isotopes (33S/32S, 34S/32S and 36S/32S ratios) of carbonate-associated sulfate, we demonstrate that the steady-state assumption does not hold in the aftermath of the Marinoan Snowball Earth glaciation. The data attest instead to the most impressive event of oceanic sulfate drawdown in Earth's history, driven by an increased pyrite burial, which may have contributed to the Neoproterozoic oxygenation of the oceans and atmosphere. PMID:27447895

  11. Matrix effects of calcium on high-precision sulfur isotope measurement by multiple-collector inductively coupled plasma mass spectrometry.

    PubMed

    Liu, Chenhui; Bian, Xiao-Peng; Yang, Tao; Lin, An-Jun; Jiang, Shao-Yong

    2016-05-01

    Multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has been successfully applied in the rapid and high-precision measurement for sulfur isotope ratios in recent years. During the measurement, the presence of matrix elements would affect the instrumental mass bias for sulfur and these matrix-induced effects have aroused a lot of researchers' interest. However, these studies have placed more weight on highlighting the necessity for their proposed correction protocols (e.g., chemical purification and matrix-matching) while less attention on the key property of the matrix element gives rise to the matrix effects. In this study, four groups of sulfate solutions, which have different concentrations of sulfur (0.05-0.60mM) but a constant sequence of atomic calcium/sulfur ratios (0.1-50), are investigated under wet (solution) and dry (desolvation) plasma conditions to make a detailed evaluation on the matrix effects from calcium on sulfur isotope measurement. Based on a series of comparative analyses, we indicated that, the matrix effects of calcium on both measured sulfur isotope ratios and detected (32)S signal intensities are dependent mainly on the absolute calcium concentration rather than its relative concentration ratio to sulfur (i.e., atomic calcium/sulfur ratio). Also, for the same group of samples, the matrix effects of calcium under dry plasma condition are much more significant than that of wet plasma. This research affords the opportunity to realize direct and relatively precise sulfur isotope measurement for evaporite gypsum, and further provides some suggestions with regard to sulfur isotope analytical protocols for sedimentary pore water. PMID:26946020

  12. Sulfur isotopic data

    SciTech Connect

    Rye, R.O.

    1987-01-01

    Preliminary sulfur isotope data have been determined for samples of the Vermillion Creek coal bed and associated rocks in the Vermillion Creek basin and for samples of evaporites collected from Jurassic and Triassic formations that crop out in the nearby Uinta Mountains. The data are inconclusive, but it is likely that the sulfur in the coal was derived from the evaporites.

  13. Separation of sulfur isotopes

    DOEpatents

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

    1976-06-22

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

  14. Complex, multiple ore fluids in the world class southeast Missouri Pb-Zn-Cu MVT deposits: Sulfur isotope evidence

    SciTech Connect

    Burstein, I.B.; Shelton, K.L. ); Gregg, J.M.; Hagni, R.D. . Dept. of Geology Geophysics)

    1993-03-01

    More than 625 sulfur isotope data from all of the mines in the Viburnum Trend Pb-Zn-Cu MVT district of southeast Missouri have identified large temporal variations of sulfur isotope composition within the complex mineral paragenesis of each mine as well as large spatial variations in sulfur isotope composition within and among mines. The general trend of [delta][sup 34]S values with increasing paragenetic time is: Early pyrite, [minus]9 to [minus]1[per thousand]; Early bornite-chalcopyrite, [minus]9 to +16[per thousand]; Massive chalcopyrite, [minus]14 to +9[per thousand]; Main sphalerite, +12 to +26[per thousand]; Cuboctahedral galena, +5 to +22[per thousand]; Main marcasite, [minus]19 to +9[per thousand]; Cubic galena, [minus]2 to +13[per thousand] Late sphalerite, +6 to +13[per thousand]; Late marcasite, +10 to +19[per thousand]; Late chalcopyrite, +2 to +33[per thousand]. Spatial correlation of [delta][sup 34]S values of the Main stages of sulfide mineralization in the West Fork mine may indicate that the cuboctahedral galena in this mine was precipitated from a Pb-rich, S-poor fluid that incorporated sulfur from reaction with earlier marcasite. In the rest of the district, ore precipitation may have occurred by mixing of Pb-rich, S-poor fluids with Pb-poor, S-rich fluids. Complex mineral parageneses and sulfur isotope systematics within the southeast Missouri Pb-Zn-Cu MVT deposits are compatible with multiple, metal-specific fluids and multiple precipitation mechanisms, as well as multiple sulfur sources.

  15. Multiple sulfur isotope systematics of Icelandic geothermal fluids and the source and reactions of sulfur in volcanic geothermal systems at divergent plate boundaries

    NASA Astrophysics Data System (ADS)

    Stefánsson, Andri; Keller, Nicole S.; Robin, Jóhann Gunnarsson; Ono, Shuhei

    2015-09-01

    Multiple sulfur isotope systematics of geothermal fluids at Krafla, Northeast Iceland, were studied in order to determine the source and reactions of sulfur in this system, as an example of a geothermal system hosted on a divergent plate boundary. Fluid temperatures ranged from 192 to 437 °C, and the fluids have low Cl concentration between ∼10 and ∼150 ppm, with liquid water and vapor being present in the reservoir. Dissolved sulfide (S-II) and sulfate (SVI) predominated in the water phase with trace concentrations of thiosulfate (S2O32-) whereas sulfide (S-II) was the only species observed in the vapor phase. The reconstructed sulfur isotope ratios of the reservoir fluids based on samples collected at surface from two-phase and vapor only well discharges indicated that δ34S and Δ33S of sulfide in the reservoir fluid ranged from -1.5 to +1.1‰ and -0.001 to -0.017‰, respectively, whereas δ34S and Δ33S of sulfate were significantly different and ranged from +3.4 to +13.4‰ and 0.000 to -0.036‰, respectively. Depressurization boiling upon fluid ascent coupled with progressive fluid-rock interaction and sulfide mineral (pyrite) formation results in the liquid phase becoming progressively isotopically lighter with respect to both δ34S and Δ33S. In contrast, H2S in the vapor phase and pyrite become isotopically heavier. The observed Δ33S and δ34S systematics for geothermal fluids at Krafla suggest that the source of sulfide in the reservoir fluids is the basaltic magma, either through degassing or upon dissolution of unaltered basalts. At high temperatures, insignificant SO4 was observed in the fluids but below ∼230 °C significant concentrations of SO4 were observed, the source inferred to be H2S oxidation. The two key factors controlling the multiple sulfur isotope systematics of geothermal fluids are: (1) the isotopic composition of the source material and (2) the isotope fractionation associated with aqueous and vapor speciation and how these

  16. Atmospheric record in the Hadean Eon from multiple sulfur isotope measurements in Nuvvuagittuq Greenstone Belt (Nunavik, Quebec)

    PubMed Central

    Thomassot, Emilie; O’Neil, Jonathan; Francis, Don; Cartigny, Pierre; Wing, Boswell A.

    2015-01-01

    Mass-independent fractionation of sulfur isotopes (S-MIF) results from photochemical reactions involving short-wavelength UV light. The presence of these anomalies in Archean sediments [(4–2.5 billion years ago, (Ga)] implies that the early atmosphere was free of the appropriate UV absorbers, of which ozone is the most important in the modern atmosphere. Consequently, S-MIF is considered some of the strongest evidence for the lack of free atmospheric oxygen before 2.4 Ga. Although temporal variations in the S-MIF record are thought to depend on changes in the abundances of gas and aerosol species, our limited understanding of photochemical mechanisms complicates interpretation of the S-MIF record in terms of atmospheric composition. Multiple sulfur isotope compositions (δ33S, δ34S, and δ36S) of the >3.8 billion-year-old Nuvvuagittuq Greenstone Belt (Ungava peninsula) have been investigated to track the early origins of S-MIF. Anomalous S-isotope compositions (Δ33S up to +2.2‰) confirm a sedimentary origin of sulfide-bearing banded iron and silica-rich formations. Sharp isotopic transitions across sedimentary/igneous lithological boundaries indicate that primary surficial S-isotope compositions have been preserved despite a complicated metamorphic history. Furthermore, Nuvvuagittuq metasediments recorded coupled variations in 33S/32S, 34S/32S, and 36S/32S that are statistically indistinguishable from those identified several times later in the Archean. The recurrence of the same S-isotope pattern at both ends of the Archean Eon is unexpected, given the complex atmospheric, geological, and biological pathways involved in producing and preserving this fractionation. It implies that, within 0.8 billion years of Earth’s formation, a common mechanism for S-MIF production was established in the atmosphere. PMID:25561552

  17. Atmospheric record in the Hadean Eon from multiple sulfur isotope measurements in Nuvvuagittuq Greenstone Belt (Nunavik, Quebec).

    PubMed

    Thomassot, Emilie; O'Neil, Jonathan; Francis, Don; Cartigny, Pierre; Wing, Boswell A

    2015-01-20

    Mass-independent fractionation of sulfur isotopes (S-MIF) results from photochemical reactions involving short-wavelength UV light. The presence of these anomalies in Archean sediments [(4-2.5 billion years ago, (Ga)] implies that the early atmosphere was free of the appropriate UV absorbers, of which ozone is the most important in the modern atmosphere. Consequently, S-MIF is considered some of the strongest evidence for the lack of free atmospheric oxygen before 2.4 Ga. Although temporal variations in the S-MIF record are thought to depend on changes in the abundances of gas and aerosol species, our limited understanding of photochemical mechanisms complicates interpretation of the S-MIF record in terms of atmospheric composition. Multiple sulfur isotope compositions (δ(33)S, δ(34)S, and δ(36)S) of the >3.8 billion-year-old Nuvvuagittuq Greenstone Belt (Ungava peninsula) have been investigated to track the early origins of S-MIF. Anomalous S-isotope compositions (Δ(33)S up to +2.2‰) confirm a sedimentary origin of sulfide-bearing banded iron and silica-rich formations. Sharp isotopic transitions across sedimentary/igneous lithological boundaries indicate that primary surficial S-isotope compositions have been preserved despite a complicated metamorphic history. Furthermore, Nuvvuagittuq metasediments recorded coupled variations in (33)S/(32)S, (34)S/(32)S, and (36)S/(32)S that are statistically indistinguishable from those identified several times later in the Archean. The recurrence of the same S-isotope pattern at both ends of the Archean Eon is unexpected, given the complex atmospheric, geological, and biological pathways involved in producing and preserving this fractionation. It implies that, within 0.8 billion years of Earth's formation, a common mechanism for S-MIF production was established in the atmosphere. PMID:25561552

  18. Multiple sulfur and carbon isotope composition of sediments from the Belingwe Greenstone Belt (Zimbabwe): A biogenic methane regulation on mass independent fractionation of sulfur during the Neoarchean?

    NASA Astrophysics Data System (ADS)

    Thomazo, Christophe; Nisbet, Euan G.; Grassineau, Nathalie V.; Peters, Marc; Strauss, Harald

    2013-11-01

    To explore the linkage between mass-independent sulfur isotope fractionation (MIF-S) and δ13Corg excursions during the Neoarchean, as well as the contemporary redox state and biogeochemical cycling of carbon and sulfur, we report the results of a detailed carbon and multiple sulfur (δ34S, δ33S, δ36S) isotopic study of the ∼2.7 Ga Manjeri and ∼2.65 Ga Cheshire formations of the Ngezi Group (Belingwe Greenstone Belt, Zimbabwe). Multiple sulfur isotope data show non-zero Δ33S and Δ36S values for sediments older than 2.4 Ga (i.e. prior to the Great Oxidation Event, GOE), indicating MIF-S thought to be associated with low atmospheric oxygen concentration. However, in several 2.7-2.5 Ga Neoarchean localities, small-scale variations in MIF-S signal (magnitude) seem to correlate with negative excursion in δ13Corg, possibly reflecting a global connection between the relative reaction rate of different MIF-S source reaction and sulfur exit channels and the biogenic flux of methane into the atmosphere during periods of localized, microbiologically mediated, shallow surface-water oxygenation. The Manjeri Formation black shales studied here display a wide range of δ13Corg between -35.4‰ and -16.2‰ (average of -30.3 ± 6.0‰, 1σ), while the Cheshire Formation shales have δ13Corg between -47.7‰ and -35.1‰ (average -41.3 ± 3‰, 1σ). The δ34S values of sedimentary sulfides from Manjeri Formation vary between -15.15‰ and +2.37‰ (average -1.71 ± 4.76‰, 1σ), showing very small and mostly negative Δ33S values varying from -0.58‰ to 0.87‰ (average 0.02 ± 0.43‰, 1σ). Cheshire Formation black shale sulfide samples measured in this study have δ34S values ranging from -2.11‰ to 2.39‰ (average 0.25 ± 1.08‰, 1σ) and near zero and solely positive Δ33S anomalies between 0.14‰ and 1.17‰ (average 0.56 ± 0.29‰, 1σ). Moreover, Δ36S/Δ33S in the two formations are comparable with a slope of -1.38 (Manjeri Formation) and -1.67 (Cheshire

  19. Multiple sulfur isotopes in Paleoarchean barites identify an important role for microbial sulfate reduction in the early marine environment

    NASA Astrophysics Data System (ADS)

    Roerdink, Desiree L.; Mason, Paul R. D.; Farquhar, James; Reimer, Thomas

    2012-05-01

    Bedded barites from the Barberton greenstone belt (South Africa and Swaziland) preserve a comprehensive record of atmospheric, oceanic and microbial processes involved in the formation and evolution of the Paleoarchean (3.6-3.2 Ga) oceanic sulfate reservoir. Here, we report multiple sulfur isotopic compositions from four of these barite occurrences. Relatively constant mass-independent signatures (Δ36S/Δ33S = - 1.0 ± 0.2) within deposits support an important role for atmospheric photolysis in the production of oxidized sulfur, whereas 34S enrichments relative to the inferred composition of photolytic sulfate suggest drawdown of 34S by microbial sulfate reduction. Strong compositional overlap with barites from India and Western Australia indicates the presence of a large-scale and well-mixed marine sulfate pool. Covariation between δ34S and Δ33S within individual deposits also suggests a role for processes occurring in semi-closed basins fed by this global reservoir. Based on modeling results, we interpret variations in δ34S by local microbial sulfate reduction and correlations with Δ33S by weak inputs of sulfur from magmatic sources, microbial sulfide oxidation or sulfur disproportionation. This agrees with the early occurrence of sulfate reducers in the geological record as inferred from published microscopic pyrite data, and identifies their role as important in both global oceans and local basins in the Paleoarchean.

  20. Multiple oxygen and sulfur isotope compositions of atmospheric sulfate in Baton Rouge, LA, USA

    NASA Astrophysics Data System (ADS)

    Jenkins, Kathryn A.; Bao, Huiming

    Secondary atmospheric sulfates (SAS) is the ultimate oxidation product and sink for sulfur gases of biological, volcanic, and anthropogenic origins on Earth. Their presence in the atmosphere as aqueous or solid phases contributes to acid rain and climate change, thus, understanding SAS formation pathways is pertinent. There has been extensive measurement of δ34S values for SAS, which mainly aimed at source identification. Relatively fewer oxygen isotope compositions ( δ18O, Δ 17O), which are most useful for resolving competing oxidation pathways, were available, however. This study represents the first effort to characterize the Δ 17O, δ18O, and δ34S simultaneously for SAS in a tropospheric air shed. We measured a total of 20 samples collected in Baton Rouge (LA, USA) during a 600-day period. The isotope compositions for atmospheric sulfate range from +0.25‰ to +1.43‰ for Δ 17O, +11.8‰ to +19.3‰ for δ18O, and -1.4‰ to +3.8‰ for δ34S. No apparent correlation is found among Δ 17O, δ18O, or δ34S values. The Δ 17O has no seasonal variation and its values are consistent with an oxidation pathway dominated by aqueous H 2O 2. The δ18O and δ34S are within the range of those observed in other sites around the world and are not characteristic for Baton Rouge. Despite the huge variability in atmospheric condition among mid-latitude sites, the long-term average Δ 17O value for SAS appears to fall within a fairly narrow range from +0.6‰ to +0.8‰, which is ˜1‰ to 2‰ lower than those in polar sites.

  1. Multiple oxygen and sulfur isotope compositions of secondary atmospheric sulfate in a mega-city in central China

    NASA Astrophysics Data System (ADS)

    Li, Xiaoqian; Bao, Huiming; Gan, Yiqun; Zhou, Aiguo; Liu, Yunde

    2013-12-01

    Sulfate aerosol is an important atmosphere constituent that can be formed secondarily through the oxidation of sulfur gases. Atmospheric sulfur oxidation can take different pathways depending on meteorological conditions, which affects sulfate aerosol size and composition and therefore local or global climate. The magnitude of 17O enrichment (Δ17O) in secondary atmospheric sulfate (SAS) is a tracer for the apportionment of different sulfur oxidation pathways. Atmospheric chemistry-transport models predict a low 17O enrichment (Δ17O < 1‰) for SAS in mid-latitude continental sites. However, there are few long-term site observations to test the prediction, and data from interior metropolitan sites are entirely absent. We report here multiple oxygen and sulfur isotope compositions (Δ17O, δ18O, and δ34S) of SAS collected over a 950-day period in the city of Wuhan, central China, and to compare to data from a similar sampling campaign in the city of Baton Rouge, LA, U.S.A. The isotope compositions of bulk atmospheric sulfate closely reflect those of SAS in Wuhan, with the Δ17O ranging from 0.14‰ to 1.02‰, the δ18O from 8.0‰ to 16.1‰, and the δ34S from 2.1‰ to 7.3‰. The average Δ17O value at 0.53‰-0.59‰ is consistent with model prediction for continental interior, mid-latitude sites. The Asian monsoon-influenced meteorological condition in Wuhan appears to produce a weak but discernible seasonal pattern for Δ17O and δ18O of the SAS. The average rainwater pH value is higher in Wuhan than in Baton Rouge (5.47 versus 4.78) while the two cities have a statistically identical average SAS Δ17O value. We suggest that the higher pH does result in a higher fraction of SAS generated by aqueous O3 oxidation, but the resulted higher Δ17O value for SAS is diluted by the 17O-normal SAS generated from an enhanced transition-metal-catalyzed O2 oxidation pathway. The enhancement is corroborated with the much higher content of atmospheric particulate matter

  2. Comparing orthomagmatic and hydrothermal mineralization models for komatiite-hosted nickel deposits in Zimbabwe using multiple-sulfur, iron, and nickel isotope data

    NASA Astrophysics Data System (ADS)

    Hofmann, Axel; Bekker, Andrey; Dirks, Paul; Gueguen, Bleuenn; Rumble, Doug; Rouxel, Olivier J.

    2014-01-01

    Trojan and Shangani mines are low-grade (<0.8 % Ni), komatiite-hosted nickel sulfide deposits associated with ca. 2.7 Ga volcano-sedimentary sequences of the Zimbabwe craton. At both mines, nickel sulfide mineralization is present in strongly deformed serpentinite bodies that are enveloped by a complex network of highly sheared, silicified, and sulfide-bearing metasedimentary rocks. Strong, polyphase structural-metamorphic-metasomatic overprints in both the Trojan and Shangani deposits make it difficult to ascertain if sulfide mineralization was derived from orthomagmatic or hydrothermal processes, or by a combination of both. Multiple S, Fe, and Ni isotope analyses were applied to test these competing models. Massive ores at Shangani Mine show mass-dependent fractionation of sulfur isotopes consistent with a mantle sulfur source, whereas S-isotope systematics of net-textured ore and disseminated ore in talcose serpentinite indicates mixing of magmatic and sedimentary sulfur sources, potentially via post-magmatic hydrothermal processes. A restricted range of strongly mass-independent Δ33S values in ore samples from Trojan Mine likely reflects high-temperature assimilation of sulfur from supracrustal rocks and later superimposed low-temperature hydrothermal remobilization. Iron isotope values for most Ni-bearing sulfides show a narrow range suggesting that, in contrast to sulfur, nearly all of iron was derived from an igneous source. Negative Ni isotope values also agree with derivation of Ni from ultramafic melt and a significant high-temperature fractionation of Ni isotopes. Fe isotope values of some samples from Shangani Mine are more fractionated than expected to occur in high-temperature magmatic systems, further suggesting that hydrothermal processes were involved in either low-grade ore formation (liberation of Ni from olivine by sulfur-bearing hydrothermal fluids) or remobilization of existing sulfides potentially inducing secondary Ni

  3. Multiple oxygen and sulfur isotope compositions of secondary atmospheric sulfate in the city of Wuhan, central China

    NASA Astrophysics Data System (ADS)

    Li, X.; Bao, H.; Zhou, A.; Wang, D.

    2012-12-01

    Secondary atmospheric sulfate (SAS) is the oxidation product and sink for sulfur gases of biological, volcanic, and anthropogenic origins on Earth. SAS can be produced from gas-phase OH-radical oxidation and five aqueous-phase chemical reactions including aqueous-phase S (IV) oxidation reactions by H2O2, O3, oxygen catalyzed by Fe3+ and Mn2+, and methyle hydrogen peroxide and peroxyacetic acid. The tropospheric sulfur oxidation pathway is therefore determined by cloud-water pH, dissolved [Fe2+] or [Mn2+] content, S emission rate, meteorological condition, and other factors. The S isotope composition is a good tracer for the source while the O isotopes, especially the triple O isotope compositions are a good tracer for S oxidation pathway. Jerkins and Bao (2006) provided the first set of multiple stable isotope compositions (δ34S, δ18O and Δ17O) for SAS collected from bulk atmosphere in Baton Rouge in the relatively rural southern USA. Their study revealed a long-tern average Δ17O value of ~+0.7‰ for SAS, and speculated that much of the Earth mid-latitudes may have a similar average SAS Δ17O value. Additional sampling campaign at different sites is necessarily for constructing and testing models on sulfur oxidation and transport in the troposphere. A total of 33 sulfate samples were collected from bulk atmospheric deposition over a 950-day period from May 2009 to December 2011 in the city of Wuhan, Hubei Province, China. Differing from Baton Rouge, Wuhan is an industrial metropolis with a population of 9.8 million and a high particulate matter content (115 μg/m3). It also has a subtropical monsoon climate, with rainwater pH at ~5.3 year-around. The rainwater ion concentrations have seasonal variations, typically low in summer and high in winter. The anions are dominated by SO42-, at an average concentration of 8.5 mg/L. There is little sulfate contribution from sea-salt (SS) sulfate or dusts in Wuhan. The isotopic compositions for bulk atmospheric sulfate

  4. Multiple oxygen and sulfur isotopic analyses on water-soluble sulfate in bulk atmospheric deposition from the southwestern United States

    NASA Astrophysics Data System (ADS)

    Bao, Huiming; Reheis, Marith C.

    2003-07-01

    Sulfate is a major component of bulk atmospheric deposition (including dust, aerosol, fog, and rain). We analyzed sulfur and oxygen isotopic compositions of water-soluble sulfate from 40 sites where year-round dust traps collect bulk atmospheric deposition in the southwestern United States. Average sulfur and oxygen isotopic compositions (δ34S and δ18O) are 5.8 ± 1.4 (CDT) and 11.2 ± 1.9 (SMOW) (n = 47), respectively. Samples have an oxygen 17 anomaly (Δ17O), with an average value of 1.0 ± 0.6‰. Except for a weak positive correlation between δ18O and Δ17O values (r2 ≈ 0.4), no correlation exists for δ18O versus δ34S, Δ17O versus δ34S, or any of the three isotopic compositions versus elevation of the sample site. Exceptional positive Δ17O values (up to 4.23‰) are found in samples from sites in the vicinity of large cities or major highways, and near-zero Δ17O values are found in samples close to dry lakes. Comparison of isotopic values of dust trap sulfate and desert varnish sulfate from the region reveals that varnish sulfate has average isotopic values that are ˜4.8‰ lower for δ18O, ˜2.1‰ higher for δ34S, and ˜0.3‰ lower for Δ17O than those of the present-day bulk deposition sulfate. Although other factors could cause the disparity, this observation suggests a possibility that varnish sulfate may have recorded a long-term atmospheric sulfate deposition during the Holocene or Pleistocene, as well as the differences between sulfur and oxygen isotopic compositions of the preindustrial bulk deposition sulfate and those of the industrial era.

  5. Multiple oxygen and sulfur isotopic analyses on water-soluble sulfate in bulk atmospheric deposition from the southwestern United States

    USGS Publications Warehouse

    Bao, H.; Reheis, M.C.

    2003-01-01

    Sulfate is a major component of bulk atmospheric deposition (including dust, aerosol, fog, and rain). We analyzed sulfur and oxygen isotopic compositions of water-soluble sulfate from 40 sites where year-round dust traps collect bulk atmospheric deposition in the southwestern United States. Average sulfur and oxygen isotopic compositions (??34S and ??18O) are 5.8 ?? 1.4 (CDT) and 11.2 ?? 1.9 (SMOW) (n = 47), respectively. Samples have an oxygen 17 anomaly (?? 17O), with an average value of 1.0 ?? 0.6???. Except for a weak positive correlation between ??18O and ??17O values (r2 ??? 0.4), no correlation exists for ??18O versus ??34S, ?? 17O versus ??34S, or any of the three isotopic compositions versus elevation of the sample site. Exceptional positive ?? 17O values (up to 4.23???) are found in samples from sites in the vicinity of large cities or major highways, and near-zero ?? 17O values are found in samples close to dry lakes. Comparison of isotopic values of dust trap sulfate and desert varnish sulfate from the region reveals that varnish sulfate has average isotopic values that are ???4.8??? lower for ??18O, ???2.1??? higher for ??34S , and ???0.3??? lower for ?? 17O than those of the present-day bulk deposition sulfate. Although other factors could cause the disparity, this observation suggests a possibility that varnish sulfate may have recorded a long-term atmospheric sulfate deposition during the Holocene or Pleistocene, as well as the differences between sulfur and oxygen isotopic compositions of the preindustrial bulk deposition sulfate and those of the industrial era.

  6. Hydrogen Sulfide Sequestration and Storage in Geothermal System: New Mitigation Strategy to Reduce H2S from the Atmosphere and Detect its Mineralization with Multiple Sulfur Isotopic Systematics

    NASA Astrophysics Data System (ADS)

    Marieni, C.; Stefansson, A.; Gudbrandsson, S.; Gunnarsson, I.; Aradottir, E. S.; Gunnarsson Robin, J.; Ono, S.

    2015-12-01

    Hydrogen sulfide (H2S) is one of the major components in geothermal fluids and is commonly emitted into the atmosphere from geothermal power plants causing potential environmental problems. Among several mitigation methods proposed to reduce the H2S emissions, is H2S sequestration into geothermal systems. Reykjavík Energy is undertaking a pilot project at Hellisheidi geothermal system (SW Iceland) called Sulfix project where H2S is being injected into the geothermal reservoir for permanent sequestration into pyrite. The SulFix project started its operation in June 2014: the soluble geothermal gases are dissolved in geothermal waste water, and injected at 8 bars into the high temperature reservoir (>200˚C) at 750 m below the wellhead. The reactions involving sulfur in the geothermal reservoir may be traced using sulfur fluid chemistry and multiple sulfur isotope systematics (32S, 33S, 34S and 36S), including mixing between the reservoir geothermal fluid and the injection fluid, sulfide mineralization and oxidation of sulfide to sulfate. In this study we investigated the multiple sulfur isotope systematics upon sulfide mineralization under geothermal conditions. High temperature flow through experiments were carried out in basaltic glass at 200-250°C and ~5 mmol/kg H2S to study the fluid-rock interaction. The results indicate that the sulfide mineralization occurs rapidly under geothermal conditions, highlighting the leaching rate of iron from the basaltic glass as the mineralization rate determining factor. Moreover, the formation of sulfide may be traced using the δ34S-Δ33S relationship in the fluids and pyrite formation - for example to determine if non-reactive mixing between the injection fluids and reservoir fluids occurs at Hellisheidi. The experimental results have been further supported by geochemical modeling involving multiple sulfur isotope fractionation between aqueous sulfide species and rocks upon basalt dissolution and secondary pyrite formation.

  7. Multiple sulfur isotope signatures of sulfite and thiosulfate reduction by the model dissimilatory sulfate-reducer, Desulfovibrio alaskensis str. G20

    PubMed Central

    Leavitt, William D.; Cummins, Renata; Schmidt, Marian L.; Sim, Min S.; Ono, Shuhei; Bradley, Alexander S.; Johnston, David T.

    2014-01-01

    Dissimilatory sulfate reduction serves as a key metabolic carbon remineralization process in anoxic marine environments. Sulfate reducing microorganisms can impart a wide range in mass-dependent sulfur isotopic fractionation. As such, the presence and relative activity of these organisms is identifiable from geological materials. By extension, sulfur isotope records are used to infer the redox balance of marine sedimentary environments, and the oxidation state of Earth's oceans and atmosphere. However, recent work suggests that our understanding of microbial sulfate reduction (MSRs) may be missing complexity associated with the presence and role of key chemical intermediates in the reductive process. This study provides a test of proposed metabolic models of sulfate reduction by growing an axenic culture of the well-studied MSRs, Desulfovibrio alaskensis strain G20, under electron donor limited conditions on the terminal electron acceptors sulfate, sulfite or thiosulfate, and tracking the multiple S isotopic consequences of each condition set. The dissimilatory reduction of thiosulfate and sulfite produce unique minor isotope effects, as compared to the reduction of sulfate. Further, these experiments reveal a complex biochemistry associated with sulfite reduction. That is, under high sulfite concentrations, sulfur is shuttled to an intermediate pool of thiosulfate. Site-specific isotope fractionation (within thiosulfate) is very large (34ε ~ 30‰) while terminal product sulfide carries only a small fractionation from the initial sulfite (34ε < 10‰): a signature similar in magnitude to sulfate and thiosulfate reduction. Together these findings show that microbial sulfate reduction (MSR) is highly sensitive to the concentration of environmentally important sulfur-cycle intermediates (sulfite and thiosulfate), especially when thiosulfate and the large site-specific isotope effects are involved. PMID:25505449

  8. Multiple sulfur-isotope signatures in Archean sulfates and their implications for the chemistry and dynamics of the early atmosphere.

    PubMed

    Muller, Élodie; Philippot, Pascal; Rollion-Bard, Claire; Cartigny, Pierre

    2016-07-01

    Sulfur isotopic anomalies (∆(33)S and ∆(36)S) have been used to trace the redox evolution of the Precambrian atmosphere and to document the photochemistry and transport properties of the modern atmosphere. Recently, it was shown that modern sulfate aerosols formed in an oxidizing atmosphere can display important isotopic anomalies, thus questioning the significance of Archean sulfate deposits. Here, we performed in situ 4S-isotope measurements of 3.2- and 3.5-billion-year (Ga)-old sulfates. This in situ approach allows us to investigate the diversity of Archean sulfate texture and mineralogy with unprecedented resolution and from then on to deconvolute the ocean and atmosphere Archean sulfur cycle. A striking feature of our data is a bimodal distribution of δ(34)S values at ∼+5‰ and +9‰, which is matched by modern sulfate aerosols. The peak at +5‰ represents barite of different ages and host-rock lithology showing a wide range of ∆(33)S between -1.77‰ and +0.24‰. These barites are interpreted as primary volcanic emissions formed by SO2 photochemical processes with variable contribution of carbonyl sulfide (OCS) shielding in an evolving volcanic plume. The δ(34)S peak at +9‰ is associated with non-(33)S-anomalous barites displaying negative ∆(36)S values, which are best interpreted as volcanic sulfate aerosols formed from OCS photolysis. Our findings confirm the occurrence of a volcanic photochemical pathway specific to the early reduced atmosphere but identify variability within the Archean sulfate isotope record that suggests persistence throughout Earth history of photochemical reactions characteristic of the present-day stratosphere. PMID:27330111

  9. Multiple sulfur-isotope signatures in Archean sulfates and their implications for the chemistry and dynamics of the early atmosphere

    NASA Astrophysics Data System (ADS)

    Muller, Élodie; Philippot, Pascal; Rollion-Bard, Claire; Cartigny, Pierre

    2016-07-01

    Sulfur isotopic anomalies (∆33S and ∆36S) have been used to trace the redox evolution of the Precambrian atmosphere and to document the photochemistry and transport properties of the modern atmosphere. Recently, it was shown that modern sulfate aerosols formed in an oxidizing atmosphere can display important isotopic anomalies, thus questioning the significance of Archean sulfate deposits. Here, we performed in situ 4S-isotope measurements of 3.2- and 3.5-billion-year (Ga)-old sulfates. This in situ approach allows us to investigate the diversity of Archean sulfate texture and mineralogy with unprecedented resolution and from then on to deconvolute the ocean and atmosphere Archean sulfur cycle. A striking feature of our data is a bimodal distribution of δ34S values at ˜+5‰ and +9‰, which is matched by modern sulfate aerosols. The peak at +5‰ represents barite of different ages and host-rock lithology showing a wide range of ∆33S between ‑1.77‰ and +0.24‰. These barites are interpreted as primary volcanic emissions formed by SO2 photochemical processes with variable contribution of carbonyl sulfide (OCS) shielding in an evolving volcanic plume. The δ34S peak at +9‰ is associated with non–33S-anomalous barites displaying negative ∆36S values, which are best interpreted as volcanic sulfate aerosols formed from OCS photolysis. Our findings confirm the occurrence of a volcanic photochemical pathway specific to the early reduced atmosphere but identify variability within the Archean sulfate isotope record that suggests persistence throughout Earth history of photochemical reactions characteristic of the present-day stratosphere.

  10. Timing the onset of sulfate reduction over multiple subsurface acetate amendments by measurement and modeling of sulfur isotope fractionation.

    PubMed

    Druhan, Jennifer L; Steefel, Carl I; Molins, Sergi; Williams, Kenneth H; Conrad, Mark E; DePaolo, Donald J

    2012-08-21

    Stable isotope fractionations of sulfur are reported for three consecutive years of acetate-enabled uranium bioremediation at the US Department of Energy's Rifle Integrated Field Research Challenge (IFRC) site. The data show a previously undocumented decrease in the time between acetate addition and the onset of sulfate reducing conditions over subsequent amendments, from 20 days in the 2007 experiment to 4 days in the 2009 experiment. Increased sulfide concentrations were observed at the same time as δ(34)S of sulfate enrichment in the first year, but in subsequent years elevated sulfide was detected up to 15 days after increased δ(34)S of sulfate. A biogeochemical reactive transport model is developed which explicitly incorporates the stable isotopes of sulfur to simulate fractionation during the 2007 and 2008 amendments. A model based on an initially low, uniformly distributed population of sulfate reducing bacteria that grow and become spatially variable with time reproduces measured trends in solute concentration and δ(34)S, capturing the change in onset of sulfate reduction in subsequent years. Our results demonstrate a previously unrecognized hysteretic effect in the spatial distribution of biomass growth during stimulated subsurface bioremediation. PMID:22834766

  11. Multiple sulfur isotope fractionation and mass transfer processes during pyrite precipitation and recrystallization: An experimental study at 300 and 350 °C

    NASA Astrophysics Data System (ADS)

    Syverson, Drew D.; Ono, Shuhei; Shanks, Wayne C.; Seyfried, William E.

    2015-09-01

    Equilibrium multiple sulfur isotope fractionation factors (33S/32S and 34S/32S) between aqueous SO4, H2S, and coexisting pyrite under hydrothermal conditions were determined experimentally at 300-350 °C and 500 bars. Two different experimental techniques were used to determine the fractionation factors and the rate of S isotope exchange between pyrite and constituent aqueous species, H2S and SO4; (1) closed system gold capsule pyrite-H2S exchange experiments and (2) complimentary time-series experiments at 300 and 350 °C, 500 bars using flexible gold cell hydrothermal equipment, which allowed monitoring the multiple S isotope composition of dissolved S species during pyrite precipitation and subsequent recrystallization. The three isotope technique was applied to the multiple S isotope data to demonstrate equilibrium S isotope fractionation between pyrite and H2S. Results at 350 °C indicate ln34αPyrite/H2S = -1.9‰ and ln33αPyrite/H2S = -1.0‰. The ln34αPyrite/H2S is not only different in magnitude but also in sign from the commonly used value of 1‰ from Ohmoto and Rye (1979). This experimental study also demonstrated initial S isotope disequilibrium amongst the aqueous S-species and pyrite during rapid precipitation, despite aqueous speciation indicating pyrite saturation at all stages. Textural, crystallographic, and S isotope interpretations suggest that pyrite formed by means of the FeS pathway. The initial S isotope disequilibrium between formed pyrite and dissolved S-species was effectively erased and approached isotopic equilibrium upon recrystallization during the course of 4297 h. Interpretation of seafloor hydrothermal vent sulfides using the revised equilibrium 34S/32S fractionation between pyrite and H2S suggests that pyrite is close to S isotope equilibrium with vent H2S, contrary to previous conclusions. The experimental data reported here broaden the range of pyrite formation mechanisms at seafloor hydrothermal vents, in that mineral

  12. Multiple sulfur isotope and mineralogical constraints on the genesis of Ni-Cu-PGE magmatic sulfide mineralization of the Monchegorsk Igneous Complex, Kola Peninsula, Russia

    NASA Astrophysics Data System (ADS)

    Bekker, A.; Grokhovskaya, T. L.; Hiebert, R.; Sharkov, E. V.; Bui, T. H.; Stadnek, K. R.; Chashchin, V. V.; Wing, B. A.

    2015-08-01

    We present the results of a pilot investigation of multiple sulfur isotopes for the Ni-Cu-PGE sulfide mineralization of the ˜2.5 Ga Monchegorsk Igneous Complex (MIC). Base Metal Sulfide (BMS) compositions, Platinum Group Element (PGE) distributions, and Platinum Group Mineral (PGM) assemblages were also studied for different types of Ni-Cu-PGE mineralization. The uniformly low S content of the country rocks for the MIC as well as variable Sm-Nd isotope systematics and low-sulfide, PGE-rich mineralization of the MIC suggest that S saturation was reached via assimilation of silicates rather than assimilation of sulfur-rich lithologies. R-factor modeling suggests that the mixing ratio for silicate-to-sulfide melt was very high, well above 15,000 for the majority of our mineralized samples, as might be expected for the low-sulfide, PGE-rich mineralization of the MIC. Small, negative Δ33S values (from -0.23 to -0.04 ‰) for sulfides in strongly metamorphosed MIC-host rocks indicate that their sulfur underwent mass-independent sulfur isotope fractionation (MIF) in the oxygen-poor Archean atmosphere before it was incorporated into the protoliths of the host paragneisses and homogenized during metamorphism. Ore minerals from the MIC have similar Δ33S values (from -0.21 to -0.06 ‰) consistent with country rock assimilation contributing to sulfide saturation, but, also importantly, our dataset suggests that Δ33S values decrease from the center to the margin of the MIC as well as from early to late magmatic phases, potentially indicating that both local assimilation of host rocks and S homogenization in the central part of the large intrusion took place.

  13. An experimental investigation of multiple sulfur isotope fractionations during heterogenous reactions between SO2 and activated carbon

    NASA Astrophysics Data System (ADS)

    Hamasaki, H.; Watanabe, Y.; Ohmoto, H.

    2010-12-01

    . We have recognized that the δ34S of SO2 in the system continuously decreased during the experiments from -0.6 to -1.4‰ (relative to the initial value) at 200 °C, and from -1.0 to -1.2 ‰ at 250 °C. The Δ33S of SO2 continued to decrease from 0 to -0.18 ‰ at 200 °C and 0.03 to -0.05 ‰ at 250 °C. Mass balance calculations suggest that the bulk S in activated carbon increased its δ34S value from 1.4 to 12.1 ‰ at 200 °C and 3.2 to 16.7 ‰ at 250 °C; and increased the Δ33S value from 0 to 0.18 ‰ at 200 °C and from 0.07 to 0.32 ‰ at 250 °C. Results of the sequential S extraction from the solid run products (activated C) indicate the total S content of 0.9 wt%, mostly in the forms of Cr-reductive S compounds (e.g., sulfites and polysulfides) and non Cr-reductive S compounds (e.g., organic sulfur, elemental sulfur, and sulfates). Our experimental results indicate that the adsorption of SO2, the reduction of S4+ to S0 (and/or Sx2-), and the oxidation of C0 to C4+ continued to occur during the reaction between SO2 and activated carbon at 200 °C and 250 °C, and that the redox reactions produced larger sulfur isotope effects (both in δ34S and Δ33S) compared to a simple adsorption process under our experimental conditions.

  14. Sulfur isotope homogeneity of lunar mare basalts

    NASA Astrophysics Data System (ADS)

    Wing, Boswell A.; Farquhar, James

    2015-12-01

    We present a new set of high precision measurements of relative 33S/32S, 34S/32S, and 36S/32S values in lunar mare basalts. The measurements are referenced to the Vienna-Canyon Diablo Troilite (V-CDT) scale, on which the international reference material, IAEA-S-1, is characterized by δ33S = -0.061‰, δ34S ≡ -0.3‰ and δ36S = -1.27‰. The present dataset confirms that lunar mare basalts are characterized by a remarkable degree of sulfur isotopic homogeneity, with most new and published SF6-based sulfur isotope measurements consistent with a single mass-dependent mean isotopic composition of δ34S = 0.58 ± 0.05‰, Δ33S = 0.008 ± 0.006‰, and Δ36S = 0.2 ± 0.2‰, relative to V-CDT, where the uncertainties are quoted as 99% confidence intervals on the mean. This homogeneity allows identification of a single sample (12022, 281) with an apparent 33S enrichment, possibly reflecting cosmic-ray-induced spallation reactions. It also reveals that some mare basalts have slightly lower δ34S values than the population mean, which is consistent with sulfur loss from a reduced basaltic melt prior to eruption at the lunar surface. Both the sulfur isotope homogeneity of the lunar mare basalts and the predicted sensitivity of sulfur isotopes to vaporization-driven fractionation suggest that less than ≈1-10% of lunar sulfur was lost after a potential moon-forming impact event.

  15. Sulfur Isotope Effects of Dissimilatory Sulfite Reductase.

    PubMed

    Leavitt, William D; Bradley, Alexander S; Santos, André A; Pereira, Inês A C; Johnston, David T

    2015-01-01

    The precise interpretation of environmental sulfur isotope records requires a quantitative understanding of the biochemical controls on sulfur isotope fractionation by the principle isotope-fractionating process within the S cycle, microbial sulfate reduction (MSR). Here we provide the only direct observation of the major ((34)S/(32)S) and minor ((33)S/(32)S, (36)S/(32)S) sulfur isotope fractionations imparted by a central enzyme in the energy metabolism of sulfate reducers, dissimilatory sulfite reductase (DsrAB). Results from in vitro sulfite reduction experiments allow us to calculate the in vitro DsrAB isotope effect in (34)S/(32)S (hereafter, [Formula: see text]) to be 15.3 ± 2‰, 2σ. The accompanying minor isotope effect in (33)S, described as [Formula: see text], is calculated to be 0.5150 ± 0.0012, 2σ. These observations facilitate a rigorous evaluation of the isotopic fractionation associated with the dissimilatory MSR pathway, as well as of the environmental variables that govern the overall magnitude of fractionation by natural communities of sulfate reducers. The isotope effect induced by DsrAB upon sulfite reduction is a factor of 0.3-0.6 times prior indirect estimates, which have ranged from 25 to 53‰ in (34)εDsrAB. The minor isotope fractionation observed from DsrAB is consistent with a kinetic or equilibrium effect. Our in vitro constraints on the magnitude of [Formula: see text] is similar to the median value of experimental observations compiled from all known published work, where (34)ε r-p = 16.1‰ (r-p indicates reactant vs. product, n = 648). This value closely matches those of MSR operating at high sulfate reduction rates in both laboratory chemostat experiments ([Formula: see text] 17.3 ± 1.5‰, 2σ) and in modern marine sediments ([Formula: see text] 17.3 ± 3.8‰). Targeting the direct isotopic consequences of a specific enzymatic processes is a fundamental step toward a biochemical foundation for reinterpreting the

  16. Sulfur Isotope Effects of Dissimilatory Sulfite Reductase

    PubMed Central

    Leavitt, William D.; Bradley, Alexander S.; Santos, André A.; Pereira, Inês A. C.; Johnston, David T.

    2015-01-01

    The precise interpretation of environmental sulfur isotope records requires a quantitative understanding of the biochemical controls on sulfur isotope fractionation by the principle isotope-fractionating process within the S cycle, microbial sulfate reduction (MSR). Here we provide the only direct observation of the major (34S/32S) and minor (33S/32S, 36S/32S) sulfur isotope fractionations imparted by a central enzyme in the energy metabolism of sulfate reducers, dissimilatory sulfite reductase (DsrAB). Results from in vitro sulfite reduction experiments allow us to calculate the in vitro DsrAB isotope effect in 34S/32S (hereafter, 34εDsrAB) to be 15.3 ± 2‰, 2σ. The accompanying minor isotope effect in 33S, described as 33λDsrAB, is calculated to be 0.5150 ± 0.0012, 2σ. These observations facilitate a rigorous evaluation of the isotopic fractionation associated with the dissimilatory MSR pathway, as well as of the environmental variables that govern the overall magnitude of fractionation by natural communities of sulfate reducers. The isotope effect induced by DsrAB upon sulfite reduction is a factor of 0.3–0.6 times prior indirect estimates, which have ranged from 25 to 53‰ in 34εDsrAB. The minor isotope fractionation observed from DsrAB is consistent with a kinetic or equilibrium effect. Our in vitro constraints on the magnitude of 34εDsrAB is similar to the median value of experimental observations compiled from all known published work, where 34εr−p = 16.1‰ (r–p indicates reactant vs. product, n = 648). This value closely matches those of MSR operating at high sulfate reduction rates in both laboratory chemostat experiments (34εSO4−H2S =  17.3 ± 1.5‰, 2σ) and in modern marine sediments (34εSO4−H2S =  17.3 ± 3.8‰). Targeting the direct isotopic consequences of a specific enzymatic processes is a fundamental step toward a biochemical foundation for reinterpreting the biogeochemical and geobiological sulfur isotope records in

  17. Multiple sulfur isotope characteristics of 3.46-2.7 Ga sedimentary rocks from drill cores of the Archean Biosphere Drilling Project (Invited)

    NASA Astrophysics Data System (ADS)

    Watanabe, Y.; Ohmoto, H.

    2010-12-01

    As part of the Archean Biosphere Drilling Project (ABDP), we have determined the multiple sulfur isotope ratios and examined the mineralogical and geochemical characteristics of the sulfur-bearing minerals (e.g., pyrite, sphalerite, barite) and the host rocks (e.g., major and trace element chemistry; Corg, Ccarb and S contents; δ13Corg and δ13Ccarb) of >100 samples of sedimentary rocks from five ABDP drill cores in the Pilbara Craton, Western Australia. The total ranges of Δ33S and δ34S values of the studied samples are -0.9 to +1.2‰ and -4 to +8‰, respectively. We have found that the Δ33S and δ34S relationships show unique values depending on their depositional environment: (1) Pyrites in the 3.46 Ga Marble Bar Chert Member (ABDP #1), which were formed by submarine hydrothermal fluids, show no AIF-S (anomalously fractionated sulfur isotope) signatures: Δ33S = -0.08 to +0.08‰ and δ34S = -3.3 to +0.6‰ (n = 5). This indicates that the H2S presented in the submarine hydrothermal fluid, which was partly generated through seawater sulfate reduction by Fe2+, did not possess AIF-S signatures. (2) Pyrites in organic C-poor lacustrine shales of the 2.76 Ga Hardey Formation (ABDP #3) also show no or very little AIF-S signatures: Δ33S = -0.38 to +0.25‰ and δ34S = -2.7 to +1.9‰ (n = 18). (3) Pyrites in organic C-poor marine shales of the 2.92 Ga Mosquito Creek Formation (ABDP#5) show no or small negative AIF-S signatures: Δ33S = -0.59 to 0.19 ‰ and all positive δ34S = +1.4 to +7.7‰ (n = 24). (4) Pyrites in organic C-rich (> 1 wt%) and hydrothermally altered marine shales in the 3.46 Ga Panorama Formation (ABDP #2) show constant and small positive AIF-S signatures (+0.44 to +0.61‰) and the smallest variation in δ34S (-1.1 to +1.6‰) (n = 35). In contrast, pyrites in organic C-rich shales in the 2.72 Ga Mt. Roe Basalt show negative Δ33S = -0.50 to -0.10‰ and δ34S = -3.7 to 1.8‰ (n = 10). (5) Pyrites in stromatolitic carbonates of the 2.7 Ga

  18. Effect of electron donors on the fractionation of sulfur isotopes by a marine Desulfovibrio sp.

    NASA Astrophysics Data System (ADS)

    Sim, Min Sub; Ono, Shuhei; Donovan, Katie; Templer, Stefanie P.; Bosak, Tanja

    2011-08-01

    Sulfur isotope effects produced by microbial dissimilatory sulfate reduction are used to reconstruct the coupled cycling of carbon and sulfur through geologic time, to constrain the evolution of sulfur-based metabolisms, and to track the oxygenation of Earth's surface. In this study, we investigate how the coupling of carbon and sulfur metabolisms in batch and continuous cultures of a recently isolated marine sulfate reducing bacterium DMSS-1, a Desulfovibrio sp ., influences the fractionation of sulfur isotopes. DMSS-1 grown in batch culture on seven different electron donors (ethanol, glycerol, fructose, glucose, lactate, malate and pyruvate) fractionates 34S/ 32S ratio from 6‰ to 44‰, demonstrating that the fractionations by an actively growing culture of a single incomplete oxidizing sulfate reducing microbe can span almost the entire range of previously reported values in defined cultures. The magnitude of isotope effect correlates well with cell specific sulfate reduction rates (from 0.7 to 26.1 fmol/cell/day). DMSS-1 grown on lactate in continuous culture produces a larger isotope effect (21-37‰) than the lactate-grown batch culture (6‰), indicating that the isotope effect also depends on the supply rate of the electron donor and microbial growth rate. The largest isotope effect in continuous culture is accompanied by measurable changes in cell length and cellular yield that suggest starvation. The use of multiple sulfur isotopes in the model of metabolic fluxes of sulfur shows that the loss of sulfate from the cell and the intracellular reoxidation of reduced sulfur species contribute to the increase in isotope effects in a correlated manner. Isotope fractionations produced during sulfate reduction in the pure culture of DMSS-1 expand the previously reported range of triple sulfur isotope effects ( 32S, 33S, and 34S) by marine sulfate reducing bacteria, implying that microbial sulfur disproportionation may have a smaller 33S isotopic fingerprint

  19. Mass-dependent sulfur isotope fractionation during reoxidative sulfur cycling: A case study from Mangrove Lake, Bermuda

    NASA Astrophysics Data System (ADS)

    Pellerin, André; Bui, Thi Hao; Rough, Mikaella; Mucci, Alfonso; Canfield, Donald E.; Wing, Boswell A.

    2015-01-01

    The multiple sulfur isotope composition of porewater sulfate from the anoxic marine sapropel of Mangrove Lake, Bermuda was measured in order to establish how multiple sulfur isotopes are fractionated during reoxidative sulfur cycling. The porewater-sulfate δ34S and Δ33S dataset exhibits the distinct isotopic signatures of microbial sulfate reduction and sulfur reoxidation. We reproduced the measurements with a simple diagenetic model that yielded fractionation factors for net sulfate removal of between -29.2‰ and -32.5‰. A new approach to isotopic modeling of the sulfate profiles, informed by the chemistry of sulfur intermediate compounds in Mangrove Lake, reveals that sulfate reduction produces a relatively small intrinsic fractionation and that an active reoxidative sulfur cycle increases the fractionation of the measured values. Based on the model results, the reoxidative cycle of Mangrove Lake appears to include sulfide oxidation to elemental sulfur followed by the disproportionation of the elemental sulfur to sulfate and sulfide. This model also indicates that the reoxidative sulfur cycle of Mangrove Lake turns over from 50 to 80% of the sulfide produced by microbial sulfate reduction. The Mangrove Lake case study shows how sulfur isotope fractionations can be separated into three different "domains" in Δ33S-δ34S space based on their ability to resolve reductive and reoxidative sulfur transformations. The first domain that differentiates reductive and reoxidative sulfur cycling is well illustrated by previous studies and requires 34S-32S fractionations more negative than ≈-70‰, beyond the fractionation limit of microbial sulfate reduction at earth surface temperatures. The second domain that distinguishes reductive and reoxidative processes is between 34S-32S fractionations of -40‰ and 0‰, where the 33S-32S fractionations of sulfate reduction and reoxidation are significantly different. In the remaining domain (between 34S-32S fractionations

  20. Sulfur isotopic ratio of DMS and DMSP from Lake Kinneret

    NASA Astrophysics Data System (ADS)

    Sela-Adler, Michal; Said-Ahmad, Ward; Eckert, Werner; Kamyshny, Alexey; Sivan, Orit; Amrani, Alon

    2014-05-01

    (46):18413-18418. Oduro, H., Kamyshny, A. Jr.,W. Guo, and J. Farquhar. 2011. Multiple sulfur isotopes analysis of volatile organic sulfur compounds and their sulfonium precursors in marine coastal environments. Marine Chemistry 124:78-89.

  1. Geochemical and sulfur isotope signatures of microbial activity in acidic and sulfuric hot springs, northern Taiwan

    NASA Astrophysics Data System (ADS)

    Wang, P.; Chen, K.; Cheng, T.; Hsieh, H.; Lin, L.

    2009-12-01

    Acidic and sulfuric hot springs are natural habitats for thermophilic sulfur-utilizing microorganisms. Integration of bioenergetic evaluation, molecular analysis and stable isotopic signatures may be able to exhibit a full view of microbial activity in such an extreme environment. Widely distributed hot springs hosted by the Tatung volcano group in northern Taiwan provide a chance to evaluate the interplay between geochemical variation and microbial metabolism especially for sulfur. Several hot spring ponds varying in sizes and geochemical characteristics were studied to reveal the possible control of fluid compositions on microbial metabolisms, and vice versa. Sulfate, sulfide, elemental sulfur and dissolved organic carbon were available in spring water and sediments in the ponds. Dominant microbial metabolisms inferred from the bioenergetic evaluation were aerobic oxidations of various reduced compounds, including elemental sulfur, pyrite, ferrous iron and organic carbon. Sulfate and sulfur reductions were thermodynamically favorable but provided less energy flux, while sulfur disproportionation was thermodynamically incapable. The analyses of 16S rRNA genes extracted from the spring water and sediments indicated that aerobic oxidation of sulfur, hydrogen or organic carbon and anaerobic elemental sulfur reduction were possible metabolisms. Since the major portion of 16S rRNA sequences were affiliated with unclassified environmental sequences, their potential metabolisms remained obscure. Sulfur isotopic compositions of dissolved sulfate, pyrite and elemental sulfur exhibited significant variations among the different hot spring ponds. Apparently, the microbial effects on the sulfur isotopic signatures were various. A disproportionation reaction of volcanic gas was required to account for high sulfur isotope difference between sulfate and reduced sulfur in the large hot ponds. In contrary, abiotic or microbial oxidation of reduced sulfur might be dominant in the

  2. Triple sulfur isotope composition of Late Archean seawater sulfate

    NASA Astrophysics Data System (ADS)

    Paris, G.; Fischer, W. W.; Sessions, A. L.; Adkins, J. F.

    2013-12-01

    Multiple sulfur isotope ratios in Archean sedimentary rocks have provided powerful insights into the behavior of the ancient sulfur cycle, the redox state of fluid Earth, and the timing of the rise of atmospheric oxygen [1]. Most processes fractionate sulfur isotopes in proportion to their mass differences, but the Archean sulfur isotope record is marked by pronounced mass-independent fractionation (MIF, Δ33S≠0). The origin of these signatures has been traditionally interpreted as the result of photolysis of SO2 from short wavelength UV light, with positive Δ33S values recorded in pyrite and negative Δ33S values in sulfate-bearing phases [2]. This long-held hypothesis rests on observations of negative Δ33S from enigmatic barite occurrences from mixed volcanic sedimentary strata in Mesoarchean greenstone terrains. Despite forming the framework for understanding Archean sulfur cycle processes [3], it is largely untested [3]. It is largely untested. Consequently, the biggest challenge to our current understanding of the early sulfur cycle is a poor understanding of the isotopic composition of seawater sulfate. Sulfate evaporite minerals are absent from Archean strata and the sulfur isotope record is written entirely by measurements of pyrite. Carbonate associated sulfate (CAS) provides an important archive for assaying the isotopic composition of ancient seawater sulfate It has been exploited in many studies of Phanerozoic and Proterozoic sulfate but have been only marginally used thus far for Archean samples because of the extremely low concentration of CAS in limestones and dolomites from this era. We have developed a novel MC-ICP-MS approach to solve this problem [4]. This new method lowers the detection limit by up to three orders of magnitude for δ34S and Δ33S measurements, enabling to work on a few nmols of sulfate which represent only tens of mg of sample powders micromilled from specific carbonate textures. Two stratigraphic sections from the 2

  3. Sulfur Isotope Composition of Putative Primary Troilite in Chondrules

    NASA Technical Reports Server (NTRS)

    Tachibana, Shogo; Huss, Gary R.

    2002-01-01

    Sulfur isotope compositions of putative primary troilites in chondrules from Bishunpur were measured by ion probe. These primary troilites have the same S isotope compositions as matrix troilites and thus appear to be isotopically unfractionated. Additional information is contained in the original extended abstract.

  4. Large sulfur isotope fractionation does not require disproportionation.

    PubMed

    Sim, Min Sub; Bosak, Tanja; Ono, Shuhei

    2011-07-01

    The composition of sulfur isotopes in sedimentary sulfides and sulfates traces the sulfur cycle throughout Earth's history. In particular, depletions of sulfur-34 ((34)S) in sulfide relative to sulfate exceeding 47 per mil (‰) often serve as a proxy for the disproportionation of intermediate sulfur species in addition to sulfate reduction. Here, we demonstrate that a pure, actively growing culture of a marine sulfate-reducing bacterium can deplete (34)S by up to 66‰ during sulfate reduction alone and in the absence of an extracellular oxidative sulfur cycle. Therefore, similar magnitudes of sulfur isotope fractionation in sedimentary rocks do not unambiguously record the presence of other sulfur-based metabolisms or the stepwise oxygenation of Earth's surface environment during the Proterozoic. PMID:21719675

  5. Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

    NASA Technical Reports Server (NTRS)

    Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

    1983-01-01

    In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

  6. Microbially Mediated Kinetic Sulfur Isotope Fractionation: Reactive Transport Modeling Benchmark

    NASA Astrophysics Data System (ADS)

    Wanner, C.; Druhan, J. L.; Cheng, Y.; Amos, R. T.; Steefel, C. I.; Ajo Franklin, J. B.

    2014-12-01

    Microbially mediated sulfate reduction is a ubiquitous process in many subsurface systems. Isotopic fractionation is characteristic of this anaerobic process, since sulfate reducing bacteria (SRB) favor the reduction of the lighter sulfate isotopologue (S32O42-) over the heavier isotopologue (S34O42-). Detection of isotopic shifts have been utilized as a proxy for the onset of sulfate reduction in subsurface systems such as oil reservoirs and aquifers undergoing uranium bioremediation. Reactive transport modeling (RTM) of kinetic sulfur isotope fractionation has been applied to field and laboratory studies. These RTM approaches employ different mathematical formulations in the representation of kinetic sulfur isotope fractionation. In order to test the various formulations, we propose a benchmark problem set for the simulation of kinetic sulfur isotope fractionation during microbially mediated sulfate reduction. The benchmark problem set is comprised of four problem levels and is based on a recent laboratory column experimental study of sulfur isotope fractionation. Pertinent processes impacting sulfur isotopic composition such as microbial sulfate reduction and dispersion are included in the problem set. To date, participating RTM codes are: CRUNCHTOPE, TOUGHREACT, MIN3P and THE GEOCHEMIST'S WORKBENCH. Preliminary results from various codes show reasonable agreement for the problem levels simulating sulfur isotope fractionation in 1D.

  7. Stratigraphic variation of sulfur isotopes in Colorado Corehole Number 1

    SciTech Connect

    Smith, J.W.; Young, N.B.

    1983-04-01

    Sulfur isotope distribution with stratigraphy is reported for organic and pyritic sulfur of Green River Formation oil shale samples selected to represent the 1600-foot (488 m) Parachute Creek Member in Colorado Corehole No. 1. In the saline zone where nahcolite and dawsonite occur in the oil shale and in the Mahogany zone the /sup 34/ values for organic sulfur and pyrite sulfur match with the pyrite sulfur slightly lighter than the organic sulfur. This is interpreted to demonstrate that organic matter supplied most of the sulfur to the sediment which became oil shale. Little sulfate reached the sediment so no sulfate reduction could occur to enrich the heavy sulfur isotope. No systematic increase in S/sup 34/ was detected in either pyrite or organic sulfur. A remarkably large increase in concentration of /sup 34/S occurring in a short stratigraphic span is demonstrated. This abrupt increase occurs near the middle of the Parachute Creek Member sediments. Above this point both pyrite and organic sulfur remain significantly enriched in /sup 34/S.

  8. Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

    NASA Technical Reports Server (NTRS)

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

    1997-01-01

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

  9. Sulfur isotope ratios as evidence of dissolved sulfur uptake by salt marsh cordgrass. [Spartina alterniflora

    SciTech Connect

    Carlson, P.R. Jr.; Forrest, J.

    1985-06-01

    The difference in stable sulfur isotope ratios of sulfate and sulfide in marsh porewater was used to verify the uptake of hydrogen sulfide by the salt marsh cordgrass, Spartina alterniflora, in North Carlina salt marsh. Most of the plant sulfur derived from porewater sulfide was recovered as sulfate indicating that the sulfide had been oxidized within the plant. The analysis of sulfur isotope ratios of other marsh halophytes is suggested as a technique to determine whether sulfide is taken up by plants. 15 refs., 2 figs., 1 tab.

  10. Sulfur isotope fractionation during the reduction of elemental sulfur and thiosulfate by Dethiosulfovibrio spp.

    NASA Astrophysics Data System (ADS)

    Surkov, A. V.; Böttcher, M. E.; Kuever, J.

    2009-04-01

    Thiosulfate and elemental sulfur are typical by-products of the oxidation of dissolved sulfide and important sulfur intermediates in the biogeochemical sulfur cycle of natural sediments where they can be further transformed by microbial or chemical oxidation, reduction, or disproportionation. Due to the often superimposing reaction pathways of the sulfur intermediates in natural environments specific tracers are needed to better resolve the complex microbial and biogeochemical reactions. An important fingerprint for sulfur cycling is provided by the microbial fractionation of the stable sulfur isotopes S-34 and S-32. Proper interpretation of isotope signals in nature, however, is only possible by the calibration with results obtained with pure cultures under defined experimental conditions. In addition, sulfur isotope discrimination may provide informations about specific encymatic biochemical pathways within the bacterial cells. In this study, we report the results for the discrimination of stable sulfur isotopes S-32 and S-34 during reduction of thiosulfate and elemental sulfur by non-sulfate, but sulfur- and thiosulfate-reducing bacteria which are phylogenetically not related to sulfate-reducing bacteria. Experiments with were conducted at known cell-specific thiosulfate reduction rates. Stable sulfur isotope fractionation was investigated during reduction of thiosulfate and elemental sulfur at 28°C by growing batch cultures of Dethiosulfovibrio marinus WS100 (type strain DSM 12537) and Dethiosulfovibrio russensis (type strain DSM 12538) using citrate as carbon and energy source. The cell-specific reduction rates were 0.3 to 2.4 fmol cell-1 d-1 (thiosulfate) and 31 to 38 fmol cell-1 d-1 (elemental sulphur), respectively. The sulfide produced was depleted in S-34 by 12 per mil compared to total thiosulfate sulfur, close to previous results observed for sulfate-reducing bacteria, indicating that the thiosulfate-reducing mechanism of sulfate reducers is similar to

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

    PubMed Central

    Canfield, Donald E.

    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 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 on interpretations of the isotope record of seawater sulfates and sedimentary pyrites. The isotope record, however, does not give a complete picture of the ancient sulfur cycle. This is because, in standard isotope mass balance models, there are more variables than constraints. Typically, in interpretations of the isotope record and in the absence of better information, one assumes that the isotopic composition of the input sulfate to the oceans has remained constant through time. It is argued here that this assumption has a constraint over the last 390 Ma from the isotopic composition of sulfur in coal. Indeed, 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 the Phanerozoic Eon. PMID:23650346

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

    PubMed

    Canfield, Donald E

    2013-05-21

    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 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 on interpretations of the isotope record of seawater sulfates and sedimentary pyrites. The isotope record, however, does not give a complete picture of the ancient sulfur cycle. This is because, in standard isotope mass balance models, there are more variables than constraints. Typically, in interpretations of the isotope record and in the absence of better information, one assumes that the isotopic composition of the input sulfate to the oceans has remained constant through time. It is argued here that this assumption has a constraint over the last 390 Ma from the isotopic composition of sulfur in coal. Indeed, 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 the Phanerozoic Eon. PMID:23650346

  13. Sulfur and oxygen isotope studies of sulfate reduction

    NASA Astrophysics Data System (ADS)

    Farquhar, J.; Canfield, D. E.; Bao, H.; Masterson, A.; Johnston, D. T.; Wing, B. A.

    2007-12-01

    I will discuss insights into sulfur and oxygen isotope fractionations of dissimilatory sulfate reduction and specifically insight provided by experiments with natural populations of sulfate-reducing bacteria from Faellestrand, Denmark. The experiments yielded relatively large magnitude sulfur isotope fractionations for dissimilatory sulfate reduction (up to approximately 45 ‰ for 34S/32S), with higher δ18O accompanying higher δ34S, similar to that observed in previous studies. The seawater used in the experiments was spiked by addition of 17O-labelled water and the 17O content of residual sulfate was found to depend on the fraction of sulfate reduced in the experiments. The 17O data provides evidence for recycling of sulfur from metabolic intermediates and for an 18O/16O fractionation of ~25-30 ‰ for dissimilatory sulfate reduction, a magnitude that is consistent with isotopic exchange between a sulfite species and cell water. The molar ratio of oxygen exchange to sulfate reduction was found to be about 2.5. Using recent models of sulfur isotope fractionations we find that our combined sulfur and oxygen isotopic data places constraints on the proportion of sulfate recycled to the medium (78-96 %), the proportion of sulfur intermediate sulfite that was recycled by way of APS to sulfate and released back to the external sulfate pool (~70%) and also that a fraction of the sulfur intermediates between sulfite and sulfide were recycled to sulfate. These parameters can be constrained because of the independent information provided by δ18O, δ34S, 17O labels, and Δ33S.

  14. Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

    USGS Publications Warehouse

    Yaofa, Jiang; Elswick, E.R.; Mastalerz, Maria

    2008-01-01

    Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur ( 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in ??34S for sulfur species within and between the low-sulfur and high-sulfur coal. The ??34S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the ??34S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the ??34S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of ??34S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in ??34S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition. The ??34S values for fly ash from the high-sulfur Springfield coal (averaging 9.7???) are greatly enriched in 34S relative to those in the parent coal (averaging 2.2???). This indicates a fractionation of sulfur isotopes

  15. Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes

    USGS Publications Warehouse

    Hackley, Keith C.; Buchanan, D.H.; Coombs, K.; Chaven, C.; Kruse, C.W.

    1990-01-01

    Hot tetrachloroethene (perchloroethylene, PCE) extracts significant amounts of elemental sulfur (So) from weathered coals but not from pristine coals. The objective of this study was to determine whether So extracted by PCE is an oxidation product of pyrite or whether it originates in some way from unstable, organically-bound sulfur. The isotopic composition of the PCE-extracted So was compared to the isotopic compositions of the pyritic and the organic sulfur in a coal. The So was shown to have an isotopic signature similar to the pyritic sulfur. Additionally, the isotopic differences observed between the pyritic, So and sulfatic sulfur were consistent with bacterial mediated oxidation of sulfide sulfur (pyrite) as the source of both the sulfatic and elemental sulfur. ?? 1990.

  16. Diversity of Sulfur Isotope Fractionations by Sulfate-Reducing Prokaryotes†

    PubMed Central

    Detmers, Jan; Brüchert, Volker; Habicht, Kirsten S.; Kuever, Jan

    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‰. 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. Sulfate reducers that oxidized the carbon source completely to CO2 showed greater fractionations than sulfate reducers that released acetate as the final product of carbon oxidation. Different metabolic pathways and variable regulation of sulfate transport across the cell membrane all potentially affect isotope fractionation. Previous models that explained fractionation only in terms of sulfate reduction rates appear to be oversimplified. The species-specific physiology of each sulfate reducer thus needs to be taken into account to understand the regulation of sulfur isotope fractionation during dissimilatory sulfate reduction. PMID:11157259

  17. Large sulfur isotope fractionations associated with Neoarchean microbial sulfate reduction.

    PubMed

    Zhelezinskaia, Iadviga; Kaufman, Alan J; Farquhar, James; Cliff, John

    2014-11-01

    The minor extent of sulfur isotope fractionation preserved in many Neoarchean sedimentary successions suggests that sulfate-reducing microorganisms played an insignificant role in ancient marine environments, despite evidence that these organisms evolved much earlier. We present bulk, microdrilled, and ion probe sulfur isotope data from carbonate-associated pyrite in the ~2.5-billion-year-old Batatal Formation of Brazil, revealing large mass-dependent fractionations (approaching 50 per mil) associated with microbial sulfate reduction, as well as consistently negative Δ(33)S values (~ -2 per mil) indicative of atmospheric photochemical reactions. Persistent (33)S depletion through ~60 meters of shallow marine carbonate implies long-term stability of seawater sulfate abundance and isotope composition. In contrast, a negative Δ(33)S excursion in lower Batatal strata indicates a response time of ~40,000 to 150,000 years, suggesting Neoarchean sulfate concentrations between ~1 and 10 μM. PMID:25378623

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

    USGS Publications Warehouse

    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.

  19. Multiple heteroatom containing sulfur compounds in coals

    SciTech Connect

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

    1989-01-01

    Flash vacuum pyrolysis of a high sulfur coal has been combined with high resolution mass spectrometry 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 identified 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 extracted and liquefaction products. 25 refs., 5 figs., 4 tabs.

  20. Isotopic insights into microbial sulfur cycling in oil reservoirs

    PubMed Central

    Hubbard, Christopher G.; Cheng, Yiwei; Engelbrekston, Anna; Druhan, Jennifer L.; Li, Li; Ajo-Franklin, Jonathan B.; Coates, John D.; Conrad, Mark E.

    2014-01-01

    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 (FW) containing elevated concentrations of volatile fatty acids (VFAs) and injection water (IW) 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. PMID:25285094

  1. Humic sulfur in eutrophic bay sediments: Characterization by sulfur stable isotopes and K-edge XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhu, Mao-Xu; Chen, Liang-Jin; Yang, Gui-Peng; Huang, Xiang-Li; Ma, Chen-Yan

    2014-02-01

    Organic sulfur (OS) is an important sedimentary sulfur pool in marine sediments and chemical extractions are often used for quantification of various OS pools, however, OS sources and mechanisms of OS formation are not well understood. In this study, sulfur stable isotope and sulfur X-ray absorption near edge structure (XANES) spectroscopy were combined to investigate the sources and speciation of humic-acid sulfur (HA-S) and fulvic-acid sulfur (FA-S) in sediments of eutrophic Jiaozhou Bay. Whilst there may be some indication that eutrophication has enhanced FA-S burial in the sediment, this has not substantially modified the characteristically low humic sulfur (i.e., HA-S + FA-S) contents of the sediments. Sulfur isotopic compositions indicate that both HA-S and FA-S are mixtures of diagenetic and biosynthetic OS in origin; HA-S is dominated by biosynthetic sulfur and FA-S by diagenetic source. Sulfur isotopic compositions and contents of pyrite and diagenetic OS indicate that inhibition of sulfurization by pyrite formation, if any, appears insignificant. XANES analysis suggests that the contents of high oxidized OS (i.e., sulfones and ester-sulfates) and strongly reduced OS species are comparable in the HA-S, whereas the FA-S is dominated by strongly reduced OS as a result of enhanced sulfurization.

  2. On-line Sulfur Isotope Determination by Hydride Generation coupled to MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Callac, Nolwenn; Rouxel, Olivier; Ponzevera, Emmanuel; Godfroy, Anne

    2010-05-01

    In seafloor hydrothermal systems, Sulfur is an important element present in various forms such as sulfate, elemental sulfur or sulfide in hydrothermal fluids and pore waters. Sulfur, as either electron donor or acceptor, is one element that enables support for microbial life in the deep biosphere. Traditionally, measurements of 34S/32S ratios (δ34S) are performed using gas-source mass spectrometry (GS-MS) in which sulfur is introduced as gaseous SO2 or SF6 species. We recently developed an alternate technique for the accurate and precise determination of 34S/32S ratios in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) (Craddock et al, 2008; Chemical Geology 253 p102-113). We examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. In particular, the use of high resolution sector-field mass spectrometry has been shown to remove major isobaric interferences from O2+ while standard-sample bracketing allowed the correcting instrumental mass bias of unknown samples. Here, we evaluate a new method for the direct determination of S isotope in environmental samples using on-line generation of hydrogen sulfide coupled to MC-ICPMS. It is expected that the introduction of volatile S-species in the plasma torch will lower the minimum amounts of S required per analysis by more than 1 order of magnitude while permitting matrix-free isotope analysis. An important aim of this study was to determine optimal procedures to overcome analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and isotope fractionation induced during hydrogen sulfide generation. We initially applied this method to investigate the diversity of sulfur isotope fractionations during microbial sulfur-reducing or sulfate-reducing at

  3. Mechanisms of Mass-independent Fractionation of Sulfur Isotopes

    NASA Astrophysics Data System (ADS)

    Lyons, J. R.

    2006-05-01

    Sulfur mass-independent fractionation (MIF) is believed to arise from gas-phase atmospheric reactions involving SO2 and H2S [1]. However, a quantitative understanding of the mechanisms remains elusive. Here I will discuss two MIF mechanisms for sulfur isotopes, and use existing laboratory data to place constraints on these mechanisms. The relevant laboratory data includes the following: 1) Photolysis of H2S [2]; 2) spark discharge of SO2 [3]; 3) SO2 photolysis from 190-210 nm [3]; 4) SO2 photolysis at wavelengths > 220 nm [4]. Experiments 1 and 2 yielded elemental sulfur (Sel) that exhibited primarily mass-dependent fractionation, while experiment 3 produced Sel with a large MIF signature, and experiment 4 yielded sulfate with a smaller MIF signature. One likely MIF mechanism is intramolecular disequilibrium (or non-RRKM) effects, as proposed for O + O2 -- > O3 [5]. The isoelectronic sulfur reaction, S + S2 --> S3, may also exhibit non-RRKM effects, but for several reasons that I will discuss such effects may either be reduced in magnitude or of negligible importance. A second possible source of MIF is isotope-selective photodissociation during predissociation. This process is likely in SO and SH, may occur in SO2, and unlikely in H2S, but in all cases depends on wavelength. SO2 dissociation is also likely to depend on the oxygen isotopes present, because an O isotope substitution will change SO2 symmetry. Although this may produce a MIF signature in oxygen isotopes, it's not clear that this would be accompanied by a MIF effect in S. I will present kinetics simulations of the above H2S and SO2 photolysis experiments, and show how it is possible to use the results of these experiments to constrain the mechanism of MIF for atmospheric sulfur species. For example, simulations of Sel formation by H2S photolysis predict little MIF in experiments, but possible MIF in the atmosphere. [1] J. Farquhar et al. (2000) Science 289 756-758. [2] J. Farquhar et al. (2000) Nature

  4. The Fractionation of Sulfur Isotopes during Arc Initiation - Preliminary Data

    NASA Astrophysics Data System (ADS)

    Brandl, P. A.; Ireland, T. R.; O'Neill, H. S.

    2014-12-01

    The "Stable Isotope Sensitive High-Resolution Ion Microprobe" (SHRIMP-SI) at the ANU in Canberra provides a powerful tool for in-situ analyses of light isotopes. Recently, we developed a technique to analyze the sulfur isotope composition (δ34S) of volcanic glasses. Since no interlaboratory reference material is available for this purpose, we carried out piston cylinder experiments to create artificial glasses of known sulfur isotope composition. We used natural sulfides mixed with CaO-Al2O3-SiO2 (with PtO2 in 5 mm Pt capsule) and high-Ti Mare basalt powder (graphite capsule inside the Pt capsule). Experimental conditions were set to 1400°C, 5 kbar and 4 hours. We used these artificial glasses to survey sulfur isotope fractionation during our experimental runs and for use as standard material with calibrated δ34S. Additionally, natural standards Juan de Fuca basalt (VG-2), Makaopuhi basalt (VG-A99; Hawai'i), SEIR MORB (NMNH 113716), and one rhyolite (VG-568) were analyzed repeatedly to provide sulfur isotope data of commonly used natural glass standards. IODP expedition 351 to the Amami-Sankaku Basin adjacent to the Kyushu-Palau Ridge in June-July 2014 recovered a variety of rocks related to the history of the Izu-Bonin Mariana (IBM) Arc. Basalts of the oceanic igneous crust underlying the IBM arc give us information of the basement prior to arc initiation and volcaniclastic rocks eroded from active volcanoes of the IBM arc record its evolution from inception in the Eocene through Oligocene and Miocene. Ash layers intercalated in hemipelagic sediments record the evolution of the IBM and Ryukyu arcs during the Neogene. The aim of this study is to track changes in the oxidation state of island arc magmas and the mantle wedge during the time of arc initiation. Experimental results as well as preliminary data from IODP Exp. 351 will be presented by the time of the conference.

  5. Are sulfur isotope ratios sufficient to determine the antiquity of sulfate reduction. [implications for chemical evolution

    NASA Technical Reports Server (NTRS)

    Ashendorf, D.

    1980-01-01

    Possible limitations on the use of sulfur isotope ratios in sedimentary sulfides to infer the evolution of microbial sulfate reduction are discussed. Current knowledge of the ways in which stable sulfur isotope ratios are altered by chemical and biological processes is examined, with attention given to the marine sulfur cycle involving various microbial populations, and sulfur reduction processes, and it is noted that satisfactory explanations of sulfur isotope ratios observed in live organisms and in sediments are not yet available. It is furthermore pointed out that all members of the same genus of sulfate reducing bacteria do not always fractionate sulfur to the same extent, that the extent of sulfur fractionation by many sulfate-reducing organisms has not yet been determined, and that inorganic processes can also affect sulfur isotope fractionation values. The information currently available is thus concluded to be insufficient to determine the time of initial appearance of biological sulfate reduction.

  6. Sulfur isotope systematics of basaltic lavas from Indonesia: implications for the sulfur cycle in subduction zones

    NASA Astrophysics Data System (ADS)

    de Hoog, J. C. M.; Taylor, B. E.; van Bergen, M. J.

    2001-07-01

    We report sulfur isotope compositions of basaltic and basaltic andesite lavas from selected volcanoes in the Indonesian arc system covering the spectrum from low-K tholeiitic to high-K calc-alkaline compositions. The results of 25 samples from seven volcanoes, which are associated with different subduction regimes, show a range in δ34S values of +2.0-+7.8‰ (VCDT) with an average of +4.7±1.4‰ (1σ). Averages and within-suite variations of two larger sets of samples from Batur and Soputan volcanoes (+4.2±1.3‰ with n=9 and +5.7±1.4‰ with n=7, respectively) are comparable to those of the entire sample set. Sulfur concentrations are low (mostly between 2 and 74 ppm, average=19 ppm) and do not show correlations with sulfur isotope composition and whole-rock chemistry, or systematic changes with time in any of the lava suites. From model calculations we infer that basaltic magmas will undergo sulfur isotope fractionation during degassing, most commonly towards lower δ34S values, but that the extent is limited at P-T conditions and oxidation states of interest. Hence, δ34S signatures of basaltic lavas will generally be within a few permil from primary magmatic values, even in cases of extensive sulfur loss. Consequently, magmas in the Indonesian arc system originate from mantle sources that are enriched in 34S relative to MORB and OIB sources and are likely to have δ34S values of about +5-+7‰. The enrichment in 34S is considered to reflect addition of slab-derived material, presumably from sediments rather than altered oceanic crust, with fluids being the most likely transport medium. Absence of correlation between δ34S values of Indonesian basalts and chemical proxies for source components or processes at the slab-wedge interface suggests that sulfur isotopes are relatively insensitive to variations in subduction setting and dynamics. This is supported by the modest range in δ34S of the Indonesian volcanoes studied despite significant variations in the

  7. Measuring sulfur isotopes by multicollector ICP-MS

    NASA Astrophysics Data System (ADS)

    Sessions, A. L.; Adkins, J. F.

    2011-12-01

    The stable isotopes of sulfur have traditionally been measured by converting analytes to SO2, which is then introduced to a gas-source isotope ratio mass spectrometer (IRMS). Recently, we and several other groups have begun measuring S isotopes using a multicollector inductively-coupled plasma mass spectrometer (MC-ICP-MS). The approach offers several advantages, including decreased reliance on preparatory chemical conversion (including combustion) of analytes, greater flexibility of sample introduction, and increased sensitivity. Sulfur is measured as monoatomic S+ ions produced in the plasma source, and can be introduced in a variety of forms including dissolved sulfate or sulfide, or as organosulfur compounds either in solution or in the gas phase. A primary requirement for accurate measurements is resolving isobaric interferences from O2+, which requires a mass analyzer with resolution > 4000. Using a Thermo Neptune system, we document accuracy and precision for δ34S near the shot-noise limit (ie, counting statistics) for both aqueous solutions and gas streams. For samples containing 50 pmol S (as gaseous SF6), this corresponds to ~0.3%; for 50 nmol S (as aqueous SO4) this is ~0.02%. One important application of this new analytical approach is the measurement of S isotopes in volatile and semivolatile organic compounds. No IRMS-based methods for measuring compound-specific S isotopes currently exist. We have demonstrated this capability by coupling a capillary gas chromatograph (GC) directly to the ICP-MS via a heated transfer line. Isotope ratios (δ34S values) are calculated relative to co-injected peaks of SF6 reference gas, in the same manner as is used by GC-combustion-IRMS approaches. As a demonstration of this capability, we measured the δ34S values of individual thiophene isomers separated by GC from a crude oil, which range over 20% for compounds from the same oil. A second application of ICP-MS to sulfur isotopes is the measurement of dissolved

  8. Sulfur isotope homogeneity of oceanic DMSP and DMS

    PubMed Central

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

    2013-01-01

    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 (34S/32S ratio, δ34S) 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 δ34S at the picomole level in individual compounds. Surface water DMSP collected from six different ocean provinces revealed a remarkable consistency in δ34S values ranging between +18.9 and +20.3‰. Sulfur isotope composition of DMS analyzed in freshly collected seawater was similar to δ34S of DMSP, showing that the in situ fractionation between these species is small (<+1‰). Based on volatilization experiments, emission of DMS to the atmosphere results in a relatively small fractionation (−0.5 ± 0.2‰) compared with the seawater DMS pool. Because δ34S values of oceanic DMS closely reflect that of DMSP, we conclude that the homogenous δ34S of DMSP at the ocean surface represents the δ34S of DMS emitted to the atmosphere, within +1‰. The δ34S 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. PMID:24167289

  9. Calibrated sulfur isotope abundance ratios of three IAEA sulfur isotope reference materials and V-CDT with a reassessment of the atomic weight of sulfur

    NASA Astrophysics Data System (ADS)

    Ding, T.; Valkiers, S.; Kipphardt, H.; De Bièvre, P.; Taylor, P. D. P.; Gonfiantini, R.; Krouse, R.

    2001-09-01

    Calibrated values have been obtained for sulfur isotope abundance ratios of sulfur isotope reference materials distributed by the IAEA (Vienna). For the calibration of the measurements, a set of synthetic isotope mixtures were prepared gravimetrically from high purity Ag 2S materials enriched in 32S, 33S, and 34S. All materials were converted into SF 6 gas and subsequently, their sulfur isotope ratios were measured on the SF 5+ species using a special gas source mass spectrometer equipped with a molecular flow inlet system (IRMM's Avogadro II amount comparator). Values for the 32S/ 34S abundance ratios are 22.650 4(20), 22.142 4(20), and 23.393 3(17) for IAEA-S-1, IAEA-S-2, and IAEA-S-3, respectively. The calculated 32S/ 34S abundance ratio for V-CDT is 22.643 6(20), which is very close to the calibrated ratio obtained by Ding et al. (1999). In this way, the zero point of the VCDT scale is anchored firmly to the international system of units SI. The 32S/ 33S abundance ratios are 126.942(47), 125.473(55), 129.072(32), and 126.948(47) for IAEA-S-1, IAEA-S-2, IAEA-S-3, and V-CDT, respectively. In this way, the linearity of the V-CDT scale is improved over this range. The values of the sulfur molar mass for IAEA-S-1 and V-CDT were calculated to be 32.063 877(56) and 32.063 911(56), respectively, the values with the smallest combined uncertainty ever reported for the sulfur molar masses (atomic weights).

  10. Evaluation of the sulfur isotopic composition and homogeneity of the Soufre de Lacq reference material

    USGS Publications Warehouse

    Carmody, R.W.; Seal, R.R., II

    1999-01-01

    Sulfur isotopic analysis of the elemental sulfur reference material Soufre de Lacq, prepared as silver sulfide by chromous chloride reduction and as copper sulfide by sealed-tube synthesis, indicates that Soufre de Lacq is isotopically homogeneous across different size fractions to within analytical uncertainty (??0.15???). The sulfur isotopic composition of aliquots of Soufre de Lacq prepared by these two techniques are identical to within analytical uncertainty. The mean sulfur isotopic composition for Soufre de Lacq prepared as silver sulfide and copper sulfide (relative to VCDT) is +16.20 ?? 0.15??? (1??).

  11. Sulfur and oxygen isotope insights into sulfur cycling in shallow-sea hydrothermal vents, Milos, Greece

    PubMed Central

    2014-01-01

    Shallow-sea (5 m depth) hydrothermal venting off Milos Island provides an ideal opportunity to target transitions between igneous abiogenic sulfide inputs and biogenic sulfide production during microbial sulfate reduction. Seafloor vent features include large (>1 m2) white patches containing hydrothermal minerals (elemental sulfur and orange/yellow patches of arsenic-sulfides) and cells of sulfur oxidizing and reducing microorganisms. Sulfide-sensitive film deployed in the vent and non-vent sediments captured strong geochemical spatial patterns that varied from advective to diffusive sulfide transport from the subsurface. Despite clear visual evidence for the close association of vent organisms and hydrothermalism, the sulfur and oxygen isotope composition of pore fluids did not permit delineation of a biotic signal separate from an abiotic signal. Hydrogen sulfide (H2S) in the free gas had uniform δ34S values (2.5 ± 0.28‰, n = 4) that were nearly identical to pore water H2S (2.7 ± 0.36‰, n = 21). In pore water sulfate, there were no paired increases in δ34SSO4 and δ18OSO4 as expected of microbial sulfate reduction. Instead, pore water δ34SSO4 values decreased (from approximately 21‰ to 17‰) as temperature increased (up to 97.4°C) across each hydrothermal feature. We interpret the inverse relationship between temperature and δ34SSO4 as a mixing process between oxic seawater and 34S-depleted hydrothermal inputs that are oxidized during seawater entrainment. An isotope mass balance model suggests secondary sulfate from sulfide oxidation provides at least 15% of the bulk sulfate pool. Coincident with this trend in δ34SSO4, the oxygen isotope composition of sulfate tended to be 18O-enriched in low pH (<5), high temperature (>75°C) pore waters. The shift toward high δ18OSO4 is consistent with equilibrium isotope exchange under acidic and high temperature conditions. The source of H2S contained in hydrothermal fluids could not be

  12. Sulfur and oxygen isotope insights into sulfur cycling in shallow-sea hydrothermal vents, Milos, Greece.

    PubMed

    Gilhooly, William P; Fike, David A; Druschel, Gregory K; Kafantaris, Fotios-Christos A; Price, Roy E; Amend, Jan P

    2014-01-01

    Shallow-sea (5 m depth) hydrothermal venting off Milos Island provides an ideal opportunity to target transitions between igneous abiogenic sulfide inputs and biogenic sulfide production during microbial sulfate reduction. Seafloor vent features include large (>1 m(2)) white patches containing hydrothermal minerals (elemental sulfur and orange/yellow patches of arsenic-sulfides) and cells of sulfur oxidizing and reducing microorganisms. Sulfide-sensitive film deployed in the vent and non-vent sediments captured strong geochemical spatial patterns that varied from advective to diffusive sulfide transport from the subsurface. Despite clear visual evidence for the close association of vent organisms and hydrothermalism, the sulfur and oxygen isotope composition of pore fluids did not permit delineation of a biotic signal separate from an abiotic signal. Hydrogen sulfide (H2S) in the free gas had uniform δ(34)S values (2.5 ± 0.28‰, n = 4) that were nearly identical to pore water H2S (2.7 ± 0.36‰, n = 21). In pore water sulfate, there were no paired increases in δ(34)SSO4 and δ(18)OSO4 as expected of microbial sulfate reduction. Instead, pore water δ(34)SSO4 values decreased (from approximately 21‰ to 17‰) as temperature increased (up to 97.4°C) across each hydrothermal feature. We interpret the inverse relationship between temperature and δ(34)SSO4 as a mixing process between oxic seawater and (34)S-depleted hydrothermal inputs that are oxidized during seawater entrainment. An isotope mass balance model suggests secondary sulfate from sulfide oxidation provides at least 15% of the bulk sulfate pool. Coincident with this trend in δ(34)SSO4, the oxygen isotope composition of sulfate tended to be (18)O-enriched in low pH (<5), high temperature (>75°C) pore waters. The shift toward high δ(18)OSO4 is consistent with equilibrium isotope exchange under acidic and high temperature conditions. The source of H2S contained in hydrothermal

  13. Multiple linear regression for isotopic measurements

    NASA Astrophysics Data System (ADS)

    Garcia Alonso, J. I.

    2012-04-01

    There are two typical applications of isotopic measurements: the detection of natural variations in isotopic systems and the detection man-made variations using enriched isotopes as indicators. For both type of measurements accurate and precise isotope ratio measurements are required. For the so-called non-traditional stable isotopes, multicollector ICP-MS instruments are usually applied. In many cases, chemical separation procedures are required before accurate isotope measurements can be performed. The off-line separation of Rb and Sr or Nd and Sm is the classical procedure employed to eliminate isobaric interferences before multicollector ICP-MS measurement of Sr and Nd isotope ratios. Also, this procedure allows matrix separation for precise and accurate Sr and Nd isotope ratios to be obtained. In our laboratory we have evaluated the separation of Rb-Sr and Nd-Sm isobars by liquid chromatography and on-line multicollector ICP-MS detection. The combination of this chromatographic procedure with multiple linear regression of the raw chromatographic data resulted in Sr and Nd isotope ratios with precisions and accuracies typical of off-line sample preparation procedures. On the other hand, methods for the labelling of individual organisms (such as a given plant, fish or animal) are required for population studies. We have developed a dual isotope labelling procedure which can be unique for a given individual, can be inherited in living organisms and it is stable. The detection of the isotopic signature is based also on multiple linear regression. The labelling of fish and its detection in otoliths by Laser Ablation ICP-MS will be discussed using trout and salmon as examples. As a conclusion, isotope measurement procedures based on multiple linear regression can be a viable alternative in multicollector ICP-MS measurements.

  14. Relationship between microbial sulfate reduction rates and sulfur isotopic fractionation

    NASA Astrophysics Data System (ADS)

    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 < -30 ‰, around hydrothermal vents or beneath the sea-floor is speculated to be the products of sulfate reducers. But laboratory experiments using sulfate reducers fail to produce such light sulfur, and many models were proposed to explain the discrepancy. Canfield et al. (2006) proposed so-called "standard model" based on previous studies. The standard model explained the reason for the large fractionation by temperature dependence of sulfur isotopic fractionation factor and rate of sulfate reduction, which indicated the growth conditions of microbes. However, they failed to prove their model by their other experiments (Canfield et al., 2006). In this study, I performed laboratory culture experiment of sulfate reducing bacteria (SRB) to explain the 34S-depleted sulfide sulfur. [Experiments] To compare the result with Canfield et al. (2006), I used Desulfovibrio desulfuricans for my laboratory culture experiment. D. desulfuricans was inoculated into glass 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

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

    PubMed

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

    2012-06-01

    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. PMID:22586117

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

    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-SO42-) 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 (δ34S) of DMSP are depleted in 34S 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 δ34S is transferred to atmospheric geochemical products of DMSP degradation (DMS, MSA, and NSS-SO42-), carrying implications for the interpretation of variability in δ34S of MSA and NSS-SO42- that links them to changes in growth conditions and populations of DMSP producers rather than to the contributions of DMS and non-DMS sources.

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

    PubMed Central

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

    2012-01-01

    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-SO42−) 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 (δ34S) of DMSP are depleted in 34S 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 δ34S is transferred to atmospheric geochemical products of DMSP degradation (DMS, MSA, and NSS-SO42−), carrying implications for the interpretation of variability in δ34S of MSA and NSS-SO42− that links them to changes in growth conditions and populations of DMSP producers rather than to the contributions of DMS and non-DMS sources. PMID:22586117

  18. Sulfur isotope and porewater geochemistry of Florida escarpment seep sediments

    USGS Publications Warehouse

    Chanton, J.P.; Martens, C.S.; Paull, C.K.; Coston, J.A.

    1993-01-01

    Distributions of porewater constituents, SO4=, NH4+, Cl-, ???CO2, and H2S, solid phase iron, and sulfur concentrations, and the sulfur isotopic composition of dissolved and solid phases were investigated in sediments from abyssal seeps at the base of the Florida escarpment. Despite the apparent similarity of seep sediment porewater chemistry to that of typical marine sediments undergoing early diagenesis, relationships between chemical distributions and isotopic measurements revealed that the distribution of pore fluid constituents was dominated by processes occurring within the platform rather than by in situ microbial processes. Ammonium and sulfate concentrations were linearly correlated with chloride concentrations, indicating that variations in porewater chemistry were controlled by the admixture of seawater and a sulfate depleted brine with a chlorinity of 27.5 ?? 1.9%. and 2.2 ?? 1.3 mM ammonium concentration. At sites dominated by seepage, dissolved sulfate isotopic composition remained near seawater values despite depletion in porewater concentrations. Porewater ???CO2 concentrations were found to be elevated relative to seawater, but not to the extent predicted from the observed sulfate depletion. Sediment solid phase sulfur was predominantly pyrite, at concentrations as high as 20% S by weight. In contrast to typical marine deposits, pyrite concentrations were not related to the quantity of sedimentary organic matter. Pyrite ??34S values ranged from -29%. to + 21%. (CDT). However, only positive ??34S values were observed at sites associated with high pyrite concentrations. Isotopically heavy pyrite was observed at sites with porewater sulfate of seawater-like isotopic composition. Isotopically light pyrite was associated with sites where porewater sulfate exhibited ??34S values greater than those in seawater, indicating the activity of in situ microbial sulfate reduction. Thus, dual sulfide sources are suggested to explain the range in sediment pyrite

  19. Sulfur Isotopic Fractionation During Dissimilatory Sulfate Reduction from the Perspective of an Entire Microbial Metabolism

    NASA Astrophysics Data System (ADS)

    Webber, B.; Lau, L.; Wing, B.

    2009-05-01

    Whether in the investigation of the most ancient life on Earth, examination of surface oxidation properties across geological timescales, or the estimation of microbial metabolism in inaccessible environments, dissimilatory sulfate reduction (DSR) constrains biogeochemical processes in a variety of spatial and temporal scales. Pioneering work in the 1970s established the importance of DSR to biogeochemical processes and its potential as a geochemical tracer, and models for biological controls of DSR were published from empirical results of in vitro microbial cultures. Recent efforts have expanded upon this body of work and further extended toward multiple sulfur isotopes and through the more precise definition of the biological processes themselves. Resulting from these recent efforts is an rigorous description of DSR of the sulfur metabolism of sulfate-reducing bacteria. However, despite these efforts, the exact mechanisms of DSR within the scope of a complex system such as microbial metabolism remain incomplete and obscure. We will be presenting ongoing work coupling together recent mathematical models of isotopic fractionation with a flux-oriented, genomically-derived software model of the metabolism of Desulfovibrio vulgaris, a patent sulfate-reducing bacterium. Our presentation will explore the effects on isotopic fractionation throughout the sulfate reduction pathway of D. vulgaris by a multitude of separate and distinct biological pathways within the bacterial metabolism. Further, we will be discussing both the pitfalls and promise of such an approach and its implications for future research.

  20. Oxygen isotope composition of sulfate produced during microbial sulfur oxidation: A pathway-specific fingerprint?

    NASA Astrophysics Data System (ADS)

    Pjevac, P.; Brunner, B.; Mußmann, M.

    2012-04-01

    The oxidation of zero-valent sulfur such as elemental sulfur (S0) is an important energy source in many marine habitats including deep-sea vents, pelagic redox-clines and coastal surface sediments. Many microorganisms oxidize elemental sulfur to sulfate to gain reducing power. This transformation is catalyzed by a few known enzymatic pathways such as the reverse dissimilatory sulfite reductase (rDSR)-aprAB/Sor pathway or the Sox multienzyme pathway. The isotopic composition of oxygen and sulfur in produced sulfate (δ34S and δ18O) is determined by the isotope composition of the reactants, the ratio between forward and backward fluxes of enzymatically catalyzed reaction steps, and by kinetic and equilibrium isotopic fractionation. We hypothesize that the activity of distinct oxidation pathways is reflected in different δ34S and particularly, in unique δ18O isotopic fingerprints in the produced sulfate. To test our hypothesis we grew pure cultures of photo- and chemoautotrophic sulfur-oxidizing microorganisms of different phylogenetic origin with S0 as sole source of reducing power and determined the sulfur and oxygen isotope composition of the produced sulfate. The identification of characteristic isotope fingerprints for each sulfur oxidation pathway could serve as a tool to estimate and deduce the importance of certain enzymatic pathways and sulfur-oxidizing microorganisms in the environment.

  1. Influence of Purple Sulfur Bacteria on the biogeochemistry of Carbon and Sulfur Isotopes in Crystal Lake, OH

    NASA Astrophysics Data System (ADS)

    Meyer, A.; Nichols, D. L.; Cheng, S.

    2013-12-01

    Crystal Lakes are a series of four interconnected mesotrophic, moulin-induced glacial lakes in west-central Ohio. The study site, Main Lake (a.k.a. Crystal Lake), is the largest and deepest lake among them. It is about 5 ha with a maximum depth of 11.9 meters and a mean depth of 3.8 meters. Thermal stratification develops during the warmer months. Photosynthesis, which preferentially uptakes lighter isotopes, is the primary pathway for carbon and sulfur isotope fractionation in natural waters. Photosynthesizers present at Crystal Lake include green algae, diatoms, cyanobacteria, and purple sulfur bacteria (PSB). Phytoplankton growth is limited by nutrient availability, influencing the extent of fractionation. Purple sulfur bacteria (PSB) utilize sulfide as an electron donor instead of water. The layer of concentrated PSB population exists between oxic and anoxic water in lakes where sufficient light and sulfide are present. These bacteria impact the levels of several sulfur compounds and isotopic composition within lake systems by oxidizing sulfide to sulfate. Field parameters collected in warmer months show turbidity and chlorophyll peaks around 6 m with variations caused by temperature, light, and nutrient availability. The dissolved oxygen minimum and the redox and sulfate maxima generally correspond with the turbidity and chlorophyll peaks, indicating the presence of a PSB layer. This layer occurs at the boundary between the metalimnion and hypolimnion. Sulfide concentrations increased from a maximum of 0.02 mg/L in May to a maximum of 9.25 mg/L in August. In May sulfide was only found at 10.4 m and below while in August it was present at 6 m and below. Sulfate values remain relatively constant with a maximum at the layer of PSB, then decline with depth where Sulfide is abundant. δ13C-DIC values peak at 6 m corresponding with the layer of PSB. This peak may be due to the influence of PSB on carbon isotope fractionation. The carbon isotope composition of

  2. Influence of sulfate reduction rates on the Phanerozoic sulfur isotope record.

    PubMed

    Leavitt, William D; Halevy, Itay; Bradley, Alexander S; Johnston, David T

    2013-07-01

    Phanerozoic levels of atmospheric oxygen relate to the burial histories of organic carbon and pyrite sulfur. The sulfur cycle remains poorly constrained, however, leading to concomitant uncertainties in O2 budgets. Here we present experiments linking the magnitude of fractionations of the multiple sulfur isotopes to the rate of microbial sulfate reduction. The data demonstrate that such fractionations are controlled by the availability of electron donor (organic matter), rather than by the concentration of electron acceptor (sulfate), an environmental constraint that varies among sedimentary burial environments. By coupling these results with a sediment biogeochemical model of pyrite burial, we find a strong relationship between observed sulfur isotope fractionations over the last 200 Ma and the areal extent of shallow seafloor environments. We interpret this as a global dependency of the rate of microbial sulfate reduction on the availability of organic-rich sea-floor settings. However, fractionation during the early/mid-Paleozoic fails to correlate with shelf area. We suggest that this decoupling reflects a shallower paleoredox boundary, primarily confined to the water column in the early Phanerozoic. The transition between these two states begins during the Carboniferous and concludes approximately around the Triassic-Jurassic boundary, indicating a prolonged response to a Carboniferous rise in O2. Together, these results lay the foundation for decoupling changes in sulfate reduction rates from the global average record of pyrite burial, highlighting how the local nature of sedimentary processes affects global records. This distinction greatly refines our understanding of the S cycle and its relationship to the history of atmospheric oxygen. PMID:23733944

  3. Influence of sulfate reduction rates on the Phanerozoic sulfur isotope record

    PubMed Central

    Leavitt, William D.; Halevy, Itay; Bradley, Alexander S.; Johnston, David T.

    2013-01-01

    Phanerozoic levels of atmospheric oxygen relate to the burial histories of organic carbon and pyrite sulfur. The sulfur cycle remains poorly constrained, however, leading to concomitant uncertainties in O2 budgets. Here we present experiments linking the magnitude of fractionations of the multiple sulfur isotopes to the rate of microbial sulfate reduction. The data demonstrate that such fractionations are controlled by the availability of electron donor (organic matter), rather than by the concentration of electron acceptor (sulfate), an environmental constraint that varies among sedimentary burial environments. By coupling these results with a sediment biogeochemical model of pyrite burial, we find a strong relationship between observed sulfur isotope fractionations over the last 200 Ma and the areal extent of shallow seafloor environments. We interpret this as a global dependency of the rate of microbial sulfate reduction on the availability of organic-rich sea-floor settings. However, fractionation during the early/mid-Paleozoic fails to correlate with shelf area. We suggest that this decoupling reflects a shallower paleoredox boundary, primarily confined to the water column in the early Phanerozoic. The transition between these two states begins during the Carboniferous and concludes approximately around the Triassic–Jurassic boundary, indicating a prolonged response to a Carboniferous rise in O2. Together, these results lay the foundation for decoupling changes in sulfate reduction rates from the global average record of pyrite burial, highlighting how the local nature of sedimentary processes affects global records. This distinction greatly refines our understanding of the S cycle and its relationship to the history of atmospheric oxygen. PMID:23733944

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

    USGS Publications Warehouse

    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.

  5. Laser isotope separation by multiple photon absorption

    DOEpatents

    Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

    1987-01-01

    Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

  6. Laser isotope separation by multiple photon absorption

    DOEpatents

    Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

    1977-01-01

    Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, in the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

  7. Laser isotope separation by multiple photon absorption

    DOEpatents

    Robinson, C.P.; Rockwood, S.D.; Jensen, R.J.; Lyman, J.L.; Aldridge, J.P. III.

    1987-04-07

    Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO[sub 2] laser light may be used to highly enrich [sup 34]S in natural SF[sub 6] and [sup 11]B in natural BCl[sub 3]. 8 figs.

  8. Sulfur isotopic characteristics of volcanic products from the September 2014 Mount Ontake eruption, Japan

    NASA Astrophysics Data System (ADS)

    Ikehata, Kei; Maruoka, Teruyuki

    2016-07-01

    Components and sulfur isotopic compositions of pyroclastic materials from the 2014 Mt. Ontake eruption were investigated. The volcanic ash samples were found to be composed of altered volcanic fragments, alunite, anhydrite, biotite, cristobalite, gypsum, ilmenite, kaolin minerals, native sulfur, orthopyroxene, plagioclase, potassium feldspar, pyrite, pyrophyllite, quartz, rutile, and smectite, and most of these minerals were likely derived from the acidic alteration zones of Mt. Ontake. The absence of juvenile material in the eruptive products indicates that the eruption was phreatic. The sulfur isotopic compositions of the water-leached sulfate, hydrochloric acid-leached sulfate, acetone-leached native sulfur, and pyrite of the samples indicate that these sulfur species were produced by disproportionation of magmatic SO2 in the hydrothermal system at temperatures of 270-281 °C. This temperature range is consistent with that inferred from the hydrothermal mineral assemblage (e.g., pyrophyllite and rutile) in the 2014 pyroclastic materials (200-300 °C). Except for the sulfur isotopic compositions of anhydrite, which may have been altered by incorporation of sulfate minerals in a fumarolic area with lower sulfur isotopic values into the underground materials during the 1979 eruption, no significant differences in the mineral assemblages and sulfur isotopic compositions of the pyroclastic materials were identified between the products of the 2014 and 1979 Ontake phreatic eruptions, which suggests geochemical similarities in the underlying hydrothermal systems before the 2014 and 1979 eruptions.

  9. A sulfur isotope perspective of fluid transport across subduction zones

    NASA Astrophysics Data System (ADS)

    Shimizu, N.; Mandeville, C. W.

    2011-12-01

    While there is a broad consensus that mantle melting in subduction zones occurs as a result of transport of aqueous fluid (or H2O-rich components) from the subducting slab to the mantle wedge, how and where the transport occurs is still one of the outstanding questions. We report recent SIMS-based sulfur isotope data of input to (pyrites in eclogites) and output from (un-degassed olivine-hosted primitive melt inclusions from arcs) subduction zones, and argue, on the basis of sulfur isotope mass balance, that our results do not support a widely held view of deep fluid transfer from slab to wedge. We suggest, instead, that hydration of the mantle wedge occurs at shallow levels with subsequent subduction and dehydration as the likely source of H2O-rich components for magma generation. Our data from olivine-hosted un-degassed primitive melt inclusions from Galunggung (δ34S ranging from -3 to +10 %, average = +2.9% with 1000 - 2000 ppm S), Krakatau (+1.6 - +8.7 %, av = +4.2%, 1200 - 2400 ppm S), and Augustine (+11 - +17%, 2500 - 5200 ppm S) clearly show that mantle wedge (δ34S ~0%, ~250 ppm S) has been significantly modified by slab-derived fluid (e.g., seawater with +21%, ~900 ppm S). On the other hand, eclogitic pyrites from the Western Gneiss Region, Norway (2 - 2.5 GPa, 700 - 850°C: Kylander-Clark et al., 2007) range in δ34S from -3.4 to +2.8%, similar to that for altered oceanic crust (e.g., Alt, 1995). Fluid in equilibrium with the eclogitic pyrites could have δ34S up to +10% (Ohmoto and Rye, 1979) and could contain up to ~1000 ppm S, based on the solubility data of Newton and Manning (2005). Mass balance calculations show that more than 10 wt.% of this fluid would be needed for modifying δ34S of the mantle wedge with ~250 ppm S from 0% to +5%, at least an order of magnitude greater than predicted by trace element-based arguments. For fluids with more seawater-like salinity, much more would be necessary for modifying the sulfur isotopic composition of the

  10. Intracellular metabolite levels shape sulfur isotope fractionation during microbial sulfate respiration

    PubMed Central

    Wing, Boswell A.; Halevy, Itay

    2014-01-01

    We present a quantitative model for sulfur isotope fractionation accompanying bacterial and archaeal dissimilatory sulfate respiration. By incorporating independently available biochemical data, the model can reproduce a large number of recent experimental fractionation measurements with only three free parameters: (i) the sulfur isotope selectivity of sulfate uptake into the cytoplasm, (ii) the ratio of reduced to oxidized electron carriers supporting the respiration pathway, and (iii) the ratio of in vitro to in vivo levels of respiratory enzyme activity. Fractionation is influenced by all steps in the dissimilatory pathway, which means that environmental sulfate and sulfide levels control sulfur isotope fractionation through the proximate influence of intracellular metabolites. Although sulfur isotope fractionation is a phenotypic trait that appears to be strain specific, we show that it converges on near-thermodynamic behavior, even at micromolar sulfate levels, as long as intracellular sulfate reduction rates are low enough (<<1 fmol H2S⋅cell−1⋅d−1). PMID:25362045

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Advances in the measurement of sulfur isotopes using laser ablation MC-ICP- MS

    NASA Astrophysics Data System (ADS)

    Ridley, W. I.; Pribil, M. J.; Koenig, A. E.; Fayek, M.; Slack, J. F.

    2008-05-01

    Although sulfur is poorly ionized in an argon plasma, there are many applications for sulfur isotope analysis using an ICP source. Studies using a desolvation system (DSN) and an aqueous source of sulfur, where the sulfur is complexed with a cation to form a sulfur salt, e.g., calcium or sodium to provide a stable delivery of sulfur through the sample introduction system indicate that precision (~ 0.3 per mil) and accuracy are maintained at sulfur concentrations as low as 1 mg/L. Based on this data, solid sampling of sulfides and sulfates can provide an adequate amount supply of sulfur to an ICP source, even allowing for the relatively poor transport efficiency of laser ablation systems. The main limitations on accuracy and precision are the initial sampling volume, principally a function of spot size and laser fluence and the decreased instrument sensitivity resulting from the pseudo- medium or high resolution mode of analysis required to eliminate polyatomic isobaric interferences. These factors, in turn, determine the minimal grain size necessary for analysis. There are also fit-for-purpose considerations. For instance, many base metal sulfide systems have large variations in sulfur isotope composition, so that precision as poor as one per mil can still provide useful information. Here, we describe the methodology used at the USGS for laser ablation analysis of sulfides and sulfates using a second generation MC-ICP-MS and demonstrate the accuracy of the method based upon a grain-by-grain comparison of laser ablation and ion microprobe sulfur isotope data. A laser ablation MC-ICP-MS study of base metal mineralization at Dry Creek deposit, east-central Alaska demonstrates that the range in sulfur isotope composition of pyrite, sphalerite and galena, based on analysis of individual grains, is almost twice that reported for any other individual VMS deposit. Analysis on the microscopic scale thus provides additional insights into the potential sources of sulfur for

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Uptake of dissolved sulfide by Spartina alterniflora: evidence from natural sulfur isotope abundance ratios

    SciTech Connect

    Carlson, P.R. Jr.; Forrest, J.

    1982-05-07

    The difference in the stable sulfur isotope ratios of sulfate and sulfide in marsh pore water was used to verify the uptake of hydrogen sulfide by the salt marsh cordgrass Spartina alterniflora in a North Carolina salt marsh. Most of the plant sulfur derived from pore-water sulfide was recovered as sulfate, an indication that the sulfide had been oxidized within the plant. The anaysis of the sulfur isotope ratios of other coastal halophytes may be a useful technique for determining whether sulfide is taken up by plants in saline wetlands.

  15. Ecologically and geologically relevant isotope signatures of C, N, and S: okenone producing purple sulfur bacteria Part I.

    PubMed

    Smith, D A; Steele, A; Bowden, R; Fogel, M L

    2015-05-01

    Purple sulfur bacteria (PSB) are known to couple the carbon, nitrogen, and sulfur cycling in euxinic environments. This is the first study with multiple strains and species of okenone-producing PSB to examine the carbon (C), nitrogen (N), and sulfur (S) metabolisms and isotopic signatures in controlled laboratory conditions, investigating what isotopic fractionations might be recorded in modern environments and the geologic record. PSB play an integral role in the ecology of euxinic environments and produce the unique molecular fossil okenane, derived from the diagenetic alteration of the carotenoid pigment okenone. Cultures of Marichromatium purpuratum 1591 (Mpurp1591) were observed to have carbon isotope fractionations ((13)ε biomass - CO2), via RuBisCO, ranging from -16.1 to -23.2‰ during exponential and stationary phases of growth. Cultures of Thiocapsa marina 5653 (Tmar5653) and Mpurp1591 had a nitrogen isotope fractionation ((15)ε biomass - NH 4) of -15‰, via glutamate dehydrogenase, measured and recorded for the first time in PSB. The δ(34) SVCDT values and amount of stored elemental sulfur for Mpurp1591 cells grown autotrophically and photoheterotrophically were dependent upon their carbon metabolic pathways. We show that PSB may contribute to the isotopic enrichments observed in modern and ancient anoxic basins. In a photoheterotrophic culture of Mpurp1591 that switched to autotrophy once the organic substrate was consumed, there were bulk biomass δ(13)C values that span a broader range than recorded across the Late Devonian, Permian-Triassic, Triassic-Jurassic, and OAE2 mass extinction boundaries. This finding stresses the complexities in interpreting and assigning δ(13)C values to bulk organic matter preserved in the geologic record. PMID:25857753

  16. Pathways for Neoarchean pyrite formation constrained by mass-independent sulfur isotopes

    PubMed Central

    Farquhar, James; Cliff, John; Zerkle, Aubrey L.; Kamyshny, Alexey; Poulton, Simon W.; Claire, Mark; Adams, David; Harms, Brian

    2013-01-01

    It is generally thought that the sulfate reduction metabolism is ancient and would have been established well before the Neoarchean. It is puzzling, therefore, that the sulfur isotope record of the Neoarchean is characterized by a signal of atmospheric mass-independent chemistry rather than a strong overprint by sulfate reducers. Here, we present a study of the four sulfur isotopes obtained using secondary ion MS that seeks to reconcile a number of features seen in the Neoarchean sulfur isotope record. We suggest that Neoarchean ocean basins had two coexisting, significantly sized sulfur pools and that the pathways forming pyrite precursors played an important role in establishing how the isotopic characteristics of each of these pools was transferred to the sedimentary rock record. One of these pools is suggested to be a soluble (sulfate) pool, and the other pool (atmospherically derived elemental sulfur) is suggested to be largely insoluble and unreactive until it reacts with hydrogen sulfide. We suggest that the relative contributions of these pools to the formation of pyrite depend on both the accumulation of the insoluble pool and the rate of sulfide production in the pyrite-forming environments. We also suggest that the existence of a significant nonsulfate pool of reactive sulfur has masked isotopic evidence for the widespread activity of sulfate reducers in the rock record. PMID:23407162

  17. Sulfur isotopic composition of surface snow along a latitudinal transect in East Antarctica

    NASA Astrophysics Data System (ADS)

    Uemura, Ryu; Masaka, Kosuke; Fukui, Kotaro; Iizuka, Yoshinori; Hirabayashi, Motohiro; Motoyama, Hideaki

    2016-06-01

    The sulfur stable isotopic values (δ34S) of sulfate aerosols can be used to assess oxidation pathways and contributions from various sources, such as marine biogenic sulfur, volcanoes, and sea salt. However, because of a lack of observations, the spatial distribution of δ34S values in Antarctic sulfate aerosols remains unclear. Here we present the first sulfur isotopic values from surface snow samples along a latitudinal transect in eastern Dronning Maud Land, East Antarctica. The δ34S values of sulfate showed remarkably uniform values, in the range of 14.8-16.9‰, and no significant decrease toward the inland part of the transect was noted. These results suggest that net isotopic fractionation during long-range transport is insignificant. Thus, the δ34S values can be used to infer source contributions. The δ34S values suggest that marine biogenic sulfur is the dominant source of sulfate aerosols, with a fractional contribution of 84 ± 16%.

  18. Chemical and sulfur isotopic composition of precipitation in Beijing, China.

    PubMed

    Zhu, Guangxu; Guo, Qingjun; Chen, Tongbin; Lang, Yunchao; Peters, Marc; Tian, Liyan; Zhang, Hanzhi; Wang, Chunyu

    2016-03-01

    China is experiencing serious acid rain contamination, with Beijing among the worst-hit areas. To understand the chemical feature and the origin of inorganic ions in precipitation of Beijing, 128 precipitation samples were collected and analyzed for major water-soluble ions and δ(34)S. The pH values ranged from 3.68 to 7.81 and showed a volume weighted average value (VWA) of 5.02, with a frequency of acid rain of 26.8 %. The VWA value of electrical conductivity (EC) was 68.6 μS/cm, which was nearly 4 times higher than the background value of northern China. Ca(2+) represented the main cation; SO4 (2-) and NO3 (-) were the dominant anion in precipitation. Our study showed that SO4 (2-) and NO3 (-) originated from coal and fossil fuel combustion; Ca(2+), Mg(2+), and K(+) were from the continental sources. The δ(34)S value of SO4 (2-) in precipitation ranged from +2.1 to +12.8‰ with an average value of +4.7‰. The δ(34)S value showed a winter maximum and a summer minimum tendency, which was mainly associated with temperature-dependent isotope equilibrium fractionation as well as combustion of coal with relatively positive δ(34)S values in winter. Moreover, the δ(34)S values revealed that atmospheric sulfur in Beijing are mainly correlated to coal burning and traffic emission; coal combustion constituted a significant fraction of the SO4 (2-) in winter precipitation. PMID:26573310

  19. Isotope evidence for sulfur sources for the Viburnum Trend of lead-zinc mineralization, southeast Missouri

    SciTech Connect

    Goldhaber, M.B.; Viets, J.G.

    1985-01-01

    The ore minerals of the Pb-Zn deposits of the Viburnum Trend in southeast Missouri, hosted by the Cambrian Bonneterre Formation have a wide range of sulfur isotope delta values. We report a similar range for pyrite and marcasite in unmineralized samples of the Bonneterre from a core fence oriented perpendicular to the mineralized trend. The Bonneterre has been variably altered by warm, saline fluid. The portion considered least affected is the brown rock, an early diagenetic alteration facies. This brown rock has systematically heavier sulfur isotopes than other rock facies. Petrographic examination suggests that FeS/sub 2/ minerals in the brown rock predate mineralization. The FeS/sub 2/ in the highly porous, vuggy white rock facies characteristically has lower isotope ratios than brown rock. White rock FeS/sub 2/ formed during or after mineralization. Some cores show a progression from brown to white rock which coincides with decreasing sulfur and carbon-oxygen isotope ratios and with increasing vuggy porosity. The authors data suggests that a source of isotopically heavy sulfur was available locally in the Bonneterre in the brown rock, and that this local sulfur was remobilized and combined with an extrinsic, isotopically light S component during mineralization to produce ore sulfide.

  20. Sulfur Isotope Fractionation during the Evolutionary Adaptation of a Sulfate-Reducing Bacterium

    PubMed Central

    Anderson-Trocmé, Luke; Whyte, Lyle G.; Zane, Grant M.; Wall, Judy D.; Wing, Boswell A.

    2015-01-01

    Dissimilatory sulfate reduction is a microbial catabolic pathway that preferentially processes less massive sulfur isotopes relative to their heavier counterparts. This sulfur isotope fractionation is recorded in ancient sedimentary rocks and generally is considered to reflect a phenotypic response to environmental variations rather than to evolutionary adaptation. Modern sulfate-reducing microorganisms isolated from similar environments can exhibit a wide range of sulfur isotope fractionations, suggesting that adaptive processes influence the sulfur isotope phenotype. To date, the relationship between evolutionary adaptation and isotopic phenotypes has not been explored. We addressed this by studying the covariation of fitness, sulfur isotope fractionation, and growth characteristics in Desulfovibrio vulgaris Hildenborough in a microbial evolution experiment. After 560 generations, the mean fitness of the evolved lineages relative to the starting isogenic population had increased by ∼17%. After 927 generations, the mean fitness relative to the initial ancestral population had increased by ∼20%. Growth rate in exponential phase increased during the course of the experiment, suggesting that this was a primary influence behind the fitness increases. Consistent changes were observed within different selection intervals between fractionation and fitness. Fitness changes were associated with changes in exponential growth rate but changes in fractionation were not. Instead, they appeared to be a response to changes in the parameters that govern growth rate: yield and cell-specific sulfate respiration rate. We hypothesize that cell-specific sulfate respiration rate, in particular, provides a bridge that allows physiological controls on fractionation to cross over to the adaptive realm. PMID:25662968

  1. Sulfur isotope fractionation during the evolutionary adaptation of a sulfate-reducing bacterium.

    PubMed

    Pellerin, André; Anderson-Trocmé, Luke; Whyte, Lyle G; Zane, Grant M; Wall, Judy D; Wing, Boswell A

    2015-04-01

    Dissimilatory sulfate reduction is a microbial catabolic pathway that preferentially processes less massive sulfur isotopes relative to their heavier counterparts. This sulfur isotope fractionation is recorded in ancient sedimentary rocks and generally is considered to reflect a phenotypic response to environmental variations rather than to evolutionary adaptation. Modern sulfate-reducing microorganisms isolated from similar environments can exhibit a wide range of sulfur isotope fractionations, suggesting that adaptive processes influence the sulfur isotope phenotype. To date, the relationship between evolutionary adaptation and isotopic phenotypes has not been explored. We addressed this by studying the covariation of fitness, sulfur isotope fractionation, and growth characteristics in Desulfovibrio vulgaris Hildenborough in a microbial evolution experiment. After 560 generations, the mean fitness of the evolved lineages relative to the starting isogenic population had increased by ∼ 17%. After 927 generations, the mean fitness relative to the initial ancestral population had increased by ∼ 20%. Growth rate in exponential phase increased during the course of the experiment, suggesting that this was a primary influence behind the fitness increases. Consistent changes were observed within different selection intervals between fractionation and fitness. Fitness changes were associated with changes in exponential growth rate but changes in fractionation were not. Instead, they appeared to be a response to changes in the parameters that govern growth rate: yield and cell-specific sulfate respiration rate. We hypothesize that cell-specific sulfate respiration rate, in particular, provides a bridge that allows physiological controls on fractionation to cross over to the adaptive realm. PMID:25662968

  2. Sulfur isotope effects associated with oxidation of sulfide by O2 in aqueous solution

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

    Normal sulfur isotope effects averaging epsilon = -5.2 +/- 1.4% (s.d.) were consistently observed for the oxidation of sulfide in aqueous solution. Reaction products were sulfate, thiosulfate and sulfite at pH 10.8-11 in distilled water; S0 was formed in two experiments with synthetic seawater at pH 8-9.5. Because the -5.2% normal isotope effect differs significantly from the previously measured +2% inverse effect associated with anaerobic oxidation of sulfide by photosynthetic bacteria, stable sulfur isotopic measurements are potentially useful for distinguishing aerobic vs. anaerobic sulfide oxidation in marine and freshwater sulfureta.

  3. Insights into Paleogene biogeochemistry from coupled carbon and sulfur isotopes in foraminiferal calcite.

    NASA Astrophysics Data System (ADS)

    Rennie, V.; Paris, G.; Abramovitch, S.; Sessions, A. L.; Adkins, J. F.; Turchyn, A. V.

    2014-12-01

    The Paleogene witnessed large-scale environmental changes, including the beginning of long-term Cenozoic cooling. The carbon isotope composition of foraminiferal calcite suggests a major reorganization of the carbon cycle over the Paleogene, with enhanced organic carbon burial in the Paleocene, and subsequent oxidation of this organic carbon or increased volcanism throughout the Eocene. The sulfur cycle is linked to the carbon cycle via the breakdown of organic carbon during bacterial sulfate reduction. Over geological time, carbon and sulfur isotopic shifts are often coupled due to enhanced pyrite burial being coupled to enhanced organic carbon burial, and enhanced pyrite weathering being coupled to enhanced organic carbon weathering. However, over the Paleogene, carbon and sulfur isotopes are fully decoupled, with the sulfur isotope record showing only one major shift in the early Eocene, after most of the carbon isotope variability is complete. One complication of interpreting the evolution of the sulfur cycle over the Cenozoic, is the fact that the mineral proxies used (typically barite) may not be temporally coincident with those used to reconstruct the carbon cycle (typically carbonate). Furthermore, these minerals are preserved in different locations, and therefore often must be extracted from different sediment cores in different ocean basins, leading to age-model uncertainty when the records are merged. To properly ascertain the phasing between early Cenozoic changes in the carbon cycle and the sulfur cycle, we would ideally measure all isotope records on the same mineral. A new sulfur isotope analytical technique [1] has been optimised for foraminiferal calcite as a proxy for seawater δ34SSO4. The δ34SSO4 in foraminiferal calcite can then be tied to records of carbon isotopes from stratigraphically identical samples, resolving previous age model uncertainties. We present coupled carbon and sulfur isotope records from the same core over the early

  4. Combined S-33 and O-18 Isotope Tracing of Intracellular Sulfur Metabolism during Microbial Sulfate Reduction

    NASA Astrophysics Data System (ADS)

    Antler, Gilad; Bosak, Tanja; Ono, Shuhei; Sivan, Orit; Turchyn, Alexandra V.

    2014-05-01

    Microbial sulfate reduction is a key player in the global carbon cycle, oxidizing nearly 50% of organic matter in marine sediments. The biochemical pathway of microbial sulfate reduction fractionates sulfur and oxygen isotopes and these fractionations can be used to reconstruct S cycling in sediments. Sulfur isotope fractionation during microbial sulfate reduction, which partitions lighter sulfur (32S) into sulfide and heavier sulfur (33S and 34S) into the residual sulfate, can be as high as 72o for 34S/32S. The availability and type of organic substrate control the magnitude of sulfur isotope fractionation by influencing the fluxes of and the transfer of electrons to different S species. The partitioning of oxygen in sulfate during microbial sulfate reduction appears to be strongly influenced by the oxygen isotopic composition of water in which the bacteria grow, but its magnitude also seems to correlate with the magnitude of 34S/32S isotope fractionation. In addition, the fractionation of 33S/32S is thought to reflect the reversibility of some intercellular fluxes. We wanted to investigate whether the 18O/16O, 34S/32S and 33S/32S isotope fractionations in sulfate are controlled by the same intracellular processes and conditions. This was done by investigating the combined sulfur and oxygen isotope partitioning by a marine Desulfovibrio sp. grown in pure culture on different organic substrates and in water with different isotopic composition of oxygen. The isotope fractionations of oxygen and sulfur correlated with the cell specific sulfate reduction rates (csSRR), where slower rates yielded higher sulfur fractionation (as high as 60) and higher oxygen isotope fractionation. The trends in 33S/32S and 34S/32S with the changing csSRR was similar to the trends in 18O/16O with the csSRR, suggesting that the same intercellular pathways controlled both oxygen and sulfur isotope signatures during microbial sulfate reduction. The use of water with different isotopic

  5. Sulfur isotope fractionation during bacterial reduction and disproportionation of thiosulfate and sulfite

    SciTech Connect

    Habicht, K.S.; Canfield, D.E.; Rethmeier, J.

    1998-08-01

    In bacterial cultures the authors measured sulfur isotope fractionation during transformations of thiosulfate and sulfite, pathways which may be of considerable importance in the cycling of sulfur in marine sediments and euxinic waters. They documented isotope fractionations during the reduction and disproportionation of thiosulfate and sulfite by bacterial enrichments and pure bacterial cultures from marine and freshwater environments. They also measured the isotope fractionation associated with the anoxygenic phototrophic oxidation of H{sub 2}S to thiosulfate by cyanobacteria. Except for sulfite reduction, isotope fractionations for these processes have not been previously reported. During the dissimilatory reduction of sulfite, H{sub 2}S was depleted in {sup 34}S by 6%, and during the reduction of thiosulfate to H{sub 2}S, depletions were between 7% and 11%. The largest observed isotope fractionation was associated with the bacterial disproportionation of sulfite which caused a {sup 34}S depletion in H{sub 2}S of 20--37% and a {sup 34}S enrichment in sulfate of 7--12%. During the bacterial disproportionation of thiosulfate, isotope fractionations between the outer sulfane sulfur and H{sub 2}S and between the inner sulfonate sulfur and sulfate were <4%. The authors observed isotope exchange between the two sulfur atoms of thiosulfate leading to a depletion of {sup 34}S in H{sub 2}S by up to 12% with a comparable enrichment of {sup 34}S in sulfate. No isotope fractionation was associated with the anoxygenic phototrophic oxidation of H{sub 2}S to thiosulfate. The depletion of {sup 34}S into H{sub 2}S during the bacterial reduction and disproportionation of thiosulfate and sulfite may, in addition to sulfate reduction and the bacterial disproportionation of elemental sulfur, contribute to the generation of {sup 34}S-depleted sedimentary sulfides.

  6. Sulfur and carbon isotope biogeochemistry of a rewetted brackish fen

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    Balter, Vincent; Nogueira da Costa, Andre; Bondanese, Victor Paky; 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. PMID:25583489

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Concentration and isotope ratio of sulfur species in snow along the route to Dome Fuji, Antarctica

    NASA Astrophysics Data System (ADS)

    Hirabayashi, M.; Motoyama, H.

    2014-12-01

    Snow ice sample in Antarctica contains particulate matter. Particulates originate from continent, volcano, sea, space, and organism. Methanesulfonate ion and sulfate ion are major sulfur compounds packed in snow ice in Antarctica. The isotopic ratio of an element reflects the origin and the history of the particle matter. Since the isotopic ratio of sulfur species depends on the source, the information about the source contribution of particulate matter can be estimated by analyzing the isotopic ratios of sulfur species. In this research, concentrations of sulfur species and isotopic ratios of sulfur species in snow collected on the route form coastal area to Dome Fuji station in Antarctica were analyzed. The snow samples were collected along ca. 1000 km traverse route from Mikaeridai (S16; 69°01'S, 40°03'E, 590 m) to Dome Fuji station (77°19'S, 39°42'E, 3810 m) by the Japan Antarctica research expedition. The snow samples were also collected from a pit dug at Dome Fuji station. Those samples were collected in the 2009/2010 austral summer. The samples were transported to Japan without thawing. Quantitative analyses of sulfur species were performed using ion chromatograph and quadrupole type mass spectrometer. The isotopic ratios of isolated sulfur species were measured using elemental analyzer and the magnetic field type mass spectrometer. Average concentrations and maximum concentration of methanesulfonate ion in the snow samples were 17 ng/ml and 123 ng/ml, respectively. Average concentrations and maximum concentration of sulfate ion were ng/ml 63 and 419 ng/ml, respectively. Further results and discussion about the behavior and origin of sulfur species in the snow will be presented.

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

    PubMed

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

    2015-01-27

    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 ((65)Cu/(63)Cu) and sulfur ((34)S/(32)S) 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 (63)Cu-enriched by ∼0.4‰ and sulfur is (32)S-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 (32)S-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. PMID:25583489

  11. Sulfur Isotope Composition of Volcanic Sulfate in Polar Ice Cores (Invited)

    NASA Astrophysics Data System (ADS)

    Cole-Dai, J.; Savarino, J.; Thiemens, M. H.

    2011-12-01

    Explosive volcanic eruptions often emit copious amounts of sulfur gases into the atmosphere. Similar to that of anthropogenic aerosols, volcanic aerosols can influence climate by altering the atmosphere's radiative properties. Traces of sulfate aerosols from past explosive eruptions are preserved in the snow strata of polar ice sheets and can be retrieved with ice cores. We have been measuring sulfur isotope composition of volcanic sulfate in Antarctica and Greenland ice cores to investigate the kinetics of atmospheric oxidation chemistry and to determine the climatic impact of the eruptions. We have found that the chemical conversion process of volcanic sulfur dioxide into sulfuric acid and sulfate aerosols in the stratosphere proceeds through oxidation reaction pathways different from those for sulfur dioxide in the troposphere. Recent laboratory experiments and modeling efforts by other investigators support the hypothesis that short wavelength ultra-violet radiation above the stratospheric ozone layer plays a key role in the chemical conversion or oxidation and can cause mass independent fractionation (MIF) of sulfur isotopes (33S, 34S, 36S). The discovery of the sulfur MIF isotope signatures in the volcanic sulfate offers a unique and dependable way to distinguish the signals of large, stratospheric eruptions in the ice core volcanic records from those of eruptions with little or no climate impact. Identification of the climate-impacting eruptions helps to improve our understanding of the volcano-climate connection.

  12. Sulfur Isotope Composition of Volcanic Sulfate in Polar Ice Cores (Invited)

    NASA Astrophysics Data System (ADS)

    Cole-Dai, J.; Savarino, J.; Thiemens, M. H.

    2013-12-01

    Explosive volcanic eruptions often emit copious amounts of sulfur gases into the atmosphere. Similar to that of anthropogenic aerosols, volcanic aerosols can influence climate by altering the atmosphere's radiative properties. Traces of sulfate aerosols from past explosive eruptions are preserved in the snow strata of polar ice sheets and can be retrieved with ice cores. We have been measuring sulfur isotope composition of volcanic sulfate in Antarctica and Greenland ice cores to investigate the kinetics of atmospheric oxidation chemistry and to determine the climatic impact of the eruptions. We have found that the chemical conversion process of volcanic sulfur dioxide into sulfuric acid and sulfate aerosols in the stratosphere proceeds through oxidation reaction pathways different from those for sulfur dioxide in the troposphere. Recent laboratory experiments and modeling efforts by other investigators support the hypothesis that short wavelength ultra-violet radiation above the stratospheric ozone layer plays a key role in the chemical conversion or oxidation and can cause mass independent fractionation (MIF) of sulfur isotopes (33S, 34S, 36S). The discovery of the sulfur MIF isotope signatures in the volcanic sulfate offers a unique and dependable way to distinguish the signals of large, stratospheric eruptions in the ice core volcanic records from those of eruptions with little or no climate impact. Identification of the climate-impacting eruptions helps to improve our understanding of the volcano-climate connection.

  13. Isotope evidence for the microbially mediated formation of elemental sulfur: A case study from Lake Peten Itza, Guatemala

    NASA Astrophysics Data System (ADS)

    Turchyn, A. V.; Bennett, V. A.; Hodell, D. A.

    2013-12-01

    Elemental, or native, sulfur nodules or veins can be formed during aqueous diagenesis and have been found in a range of natural environments, including lake sediments. What governs the formation of elemental sulfur remains enigmatic, although it is widely thought to be microbially-mediated. While most of the literature suggests elemental sulfur is formed by partial re-oxidation of hydrogen sulphide, elemental sulfur can also form during incomplete bacterial sulfate reduction or during aborted sulfur disproportionation. Lake Peten Itza, in Northern Guatemala, which was cored during the International Continental Drilling program in 2006, is one of the few places where elemental sulfur nodules are forming during microbial diagenesis today. Sulfur isotopes are strongly partitioned during bacterial sulfate reduction and the magnitude of the partitioning yields insight into the microbial reactions and environmental conditions. For example, sulfate reduction that terminates at elemental sulfur likely requires the use of the intracellular trithonite pathway, which may drive larger overall sulfur isotope fractionation between the precursor sulfate and the elemental sulfur product. Sulfur isotopes combined with oxygen isotopes in the precursor sulfate may provide even more information about microbial mechanisms. We present coupled pore fluid sulfate concentrations and sulfur and oxygen isotope measurements, as well as co-existing nodule sulfur isotopes from the Lake Peten Itza sediments. The δ34S of the nodules in the lake sediments ranges from +12 to -13‰, often within a single nodule. This suggests formation from an open system where sulfate is replenished by diffusion, as might be expected during pore fluid diagenesis. The δ34S of the pore fluid sulfate at the depth of nodule formation is between 50 and 60‰ (versus the precursor gypsum which is 17 to 18‰) suggesting a large sulfur isotope fractionation between sulfate and elemental sulfur (38 to 73‰). Pyrite was

  14. Microbial sulfur metabolism evidenced from pore fluid isotope geochemistry at Site U1385

    NASA Astrophysics Data System (ADS)

    Turchyn, Alexandra V.; Antler, Gilad; Byrne, David; Miller, Madeline; Hodell, David A.

    2016-06-01

    At Site U1385, drilled during IODP Expedition 339 off the coast of Portugal on the continental slope, high-resolution sulfate concentration measurements in the pore fluids display non-steady-state behavior. At this site there is a zone of sulfate reduction in the uppermost seven meters of sediment, followed by a 38-meter interval where sulfate concentrations do not change, and finally sulfate concentrations are depleted to zero between 45 and 55 meters below seafloor. Below the sulfate minimum zone, there is abundant methane, suggesting that the lower sulfate consumption zone is coupled to anaerobic methane oxidation. We analyze pore water samples from IODP Site U1385 for sulfur and oxygen isotope ratios of dissolved sulfate, as well as the sulfur isotope composition of sedimentary pyrite. The sulfur isotopes in pore fluid sulfate display similar non-steady-state behavior similar to that of the sulfate concentrations, increasing over the uppermost zone of sulfate reduction and again over the lower zone of sulfate-driven anaerobic methane oxidation. The oxygen isotopes in sulfate increase to the 'apparent equilibrium' value in the uppermost zone of sulfate reduction and do not change further. Our calculations support the idea that sulfite to sulfide reduction is the limiting step in microbial sulfate reduction, and that the isotope fractionation expressed in the residual pore water sulfate pool is inversely proportional to the net sulfate reduction rate. The sulfur isotope composition of pyrite acquires one value in the uppermost sediments, which may be overprinted by a second value in the deeper sediments, possibly due to iron release during anaerobic methane oxidation or iron diffusion from a higher zone of bacterial iron reduction. Our results have implications for modeling the sulfur isotope composition of the pyrite burial flux in the global biogeochemical sulfur cycle.

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

    PubMed Central

    Ono, Shuhei; Bosak, Tanja

    2012-01-01

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

  16. Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere.

    PubMed

    Shaheen, Robina; Abaunza, Mariana M; Jackson, Teresa L; McCabe, Justin; Savarino, Joël; Thiemens, Mark H

    2014-08-19

    Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984-2001) showed the highest S-isotopic anomalies (Δ(33)S = +1.66‰ and Δ(36)S = +2‰) in a nonvolcanic (1998-1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997-1998)-induced changes in troposphere-stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ(36)S = -0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere. PMID:25092338

  17. Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere

    PubMed Central

    Shaheen, Robina; Abaunza, Mariana M.; Jackson, Teresa L.; McCabe, Justin; Savarino, Joël; Thiemens, Mark H.

    2014-01-01

    Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984–2001) showed the highest S-isotopic anomalies (Δ33S = +1.66‰ and Δ36S = +2‰) in a nonvolcanic (1998–1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997–1998)-induced changes in troposphere–stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ36S = −0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere. PMID:25092338

  18. Fractionation of sulfur isotopes by Desulfovibrio vulgaris mutants lacking hydrogenases or type I tetraheme cytochrome c3

    PubMed Central

    Sim, Min Sub; Wang, David T.; Zane, Grant M.; Wall, Judy D.; Bosak, Tanja; Ono, Shuhei

    2013-01-01

    The sulfur isotope effect produced by sulfate reducing microbes is commonly used to trace biogeochemical cycles of sulfur and carbon in aquatic and sedimentary environments. To test the contribution of intracellular coupling between carbon and sulfur metabolisms to the overall magnitude of the sulfur isotope effect, this study compared sulfur isotope fractionations by mutants of Desulfovibrio vulgaris Hildenborough. We tested mutant strains lacking one or two periplasmic (Hyd, Hyn-1, Hyn-2, and Hys) or cytoplasmic hydrogenases (Ech and CooL), and a mutant lacking type I tetraheme cytochrome (TpI-c3). In batch culture, wild-type D. vulgaris and its hydrogenase mutants had comparable growth kinetics and produced the same sulfur isotope effects. This is consistent with the reported redundancy of hydrogenases in D. vulgaris. However, the TpI-c3 mutant (ΔcycA) exhibited slower growth and sulfate reduction rates in batch culture, and produced more H2 and an approximately 50% larger sulfur isotope effect, compared to the wild type. The magnitude of sulfur isotope fractionation in the CycA deletion strain, thus, increased due to the disrupted coupling of the carbon oxidation and sulfate reduction pathways. In continuous culture, wild-type D. vulgaris and the CycA mutant produced similar sulfur isotope effects, underscoring the influence of environmental conditions on the relative contribution of hydrogen cycling to the electron transport. The large sulfur isotope effects associated with the non-ideal stoichiometry of sulfate reduction in this study imply that simultaneous fermentation and sulfate reduction may be responsible for some of the large naturally-occurring sulfur isotope effects. Overall, mutant strains provide a powerful tool to test the effect of specific redox proteins and pathways on sulfur isotope fractionation. PMID:23805134

  19. Speciation and isotopic composition of sulfur in sediments from Jellyfish Lake, Palau

    USGS Publications Warehouse

    Bates, A.L.; Spiker, E. C.; Orem, W.H.; Burnett, W.C.

    1993-01-01

    Jellyfish Lake, Palau, is a meromictic marine lake with high organic productivity, low reactive Fe content, and anoxic bottom waters. Sediment samples from Jellyfish Lake were examined for the distribution of sulfur species and their isotopic signatures in order to gain a better understanding of sedimentary sulfur incorporation in Fe-poor environments. Surface samples were taken along a transect from a near-shore site to the center of the lake, and include a sample below oxic water, a sample below the chemocline layer, and samples below anoxic waters. Three additional samples were taken from a core, 2 m long, collected near the lake center. Sulfur to organic carbon weight ratios in all samples were lower than the expected value of 0.36 for normal marine sediment, probably because the lake water is deficient in reactive Fe to form iron sulfides. Total sulfur contents in the surface sediments indicated no changes with distance from shore; however, the sulfur content of the surface sample at the chemocline layer may be slightly higher. Total sulfur content increased with depth in the core and is inversely related to organic carbon content. Organic sulfur is the major sulfur species in the samples, followed in descending order by sulfate, disulfides and monosulfides. Sulfate sulfur isotope ??34S-values are positive (from +20.56 to +12.04???), reflecting the marine source of sulfate in Jellyfish Lake. Disulfide and monosulfide ??34S-values are negative (from -25.07 to -7.60???), because of fractionation during bacterial reduction of sulfate. Monosulfide ??34S-values are somewhat higher than those of disulfides, and they are close to the ??34S-values of organic sulfur. These results indicate that most of the organic sulfur is formed by reaction of bacteriogenic monosulfides, or possibly monosulfide-derived polysulfides, with organic matter in the sediment. ?? 1993.

  20. Oxygen and Sulfur Isotope Composition of Dissolved Sulfate in Interstitial Waters of the Great Australian Bight, ODP Leg 182.

    NASA Astrophysics Data System (ADS)

    Bernasconi, S. M.; Böttcher, M. E.; Wormann, U. G.

    2005-12-01

    We measured the sulfur and oxygen isotope composition of dissolved sulfides and sulfate at ODP Sites 1129, 1130, 1131 and 1132 in the Great Australian Bight (GAB). At all Sites, a saline brine is present in the subsurface as indicated by increasing chloride concentrations with depth to reach contents up to 3 times seawater. Sulfate also increases with depth but the concentrations are reduced by intense microbial sulfate reduction. The sulfur isotope fractionation between coexisting dissolved sulfate and sulfide is very large and reaches up to 70 ‰ at all studied Sites. Due to the high sulfide concentrations and the lack of a significant source of oxidants we consider that the large sulfur isotope fractionations are induced by sulfate reducing bacteria alone without a significant contribution of elemental sulfur disproportionation and sulfide oxidation processes. The oxygen isotope composition of dissolved sulfate reaches maximum values of approximately +27 ‰ vs. VSMOW at all sites, close to the equilibrium isotope fractionation between sulfate and water. The oxygen isotope composition of dissolved sulfate positively correlates with the sulfur isotope fractionation between sulfate and sulfide. These oxygen isotope data thus support the hypothesis that that the high sulfur isotope fractionation are related to a single step fractionation by sulfate reducing bacteria and do not involve significant sulfide oxidation reactions and/or elemental sulfur disproportionation. Sulfide oxidation processes would lead to a lowering of the oxygen isotope composition of residual sulfate. Elemental sulfur disproportionation has been shown to increase the oxygen isotope composition of sulfate but to a smaller extent than that that observed in the GAB. The patterns of the oxygen isotope increase with progressive sulfate reduction indicate a predominant influence of isotope exchange rather than a kinetic isotope fractionation controlling the oxygen isotope composition of sulfate

  1. Chemistry and isotope ratios of sulfur in basalts and volcanic gases at Kilauea volcano, Hawaii

    USGS Publications Warehouse

    Sakai, H.; Casadevall, T.J.; Moore, J.G.

    1982-01-01

    Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ?? 100 ppm total sulfur with ??34S??s of 0.7 ?? 0.1 ???. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is +7.5 ?? 1.5???. On the other hand, the concentration and ??34S??s values of the total sulfur in the subaerial basalt are reduced to 150 ?? 50 ppm and -0.8 ?? 0.2???, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0???, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the f{hook}o2 and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO2 from basalt thereby depleting sulfate and 34S in basalt. The volcanic sulfur gases, predominantly SO2, from the 1971 and 1974 fissures in Kilauea Crater have ??34S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the ??34S value of sulfur gases (largely SO2) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The ??34S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high

  2. Stable carbon and sulfur isotopes as records of the early biosphere

    NASA Technical Reports Server (NTRS)

    Desmarais, David J.

    1989-01-01

    The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

  3. The Sulfur Isotope Composition of the Pyrite Burial Flux in the Modern Ocean

    NASA Astrophysics Data System (ADS)

    Turchyn, A. V.; Antler, G.; Byrne, D. J.; Sun, X.

    2014-12-01

    Microbial sulfate reduction followed by sulfide mineral burial, typically as pyrite, represents the largest removal pathway for sulfur from the exogenic sulfur reservoir. During microbial sulfate reduction, sulfur isotopes are partitioned such that the lighter 32S isotope is preferentially reduced; the magnitude of this partitioning has a large range (0 to 72‰), and therefore the average sulfur isotope composition of the global pyrite burial flux remains enigmatic. Recent work has mapped the global spatial distribution of microbial sulfate reduction rates in the modern ocean, which allows conclusions to be drawn concerning the conditions and controls on where sulfate respiration occurs (Bowles et al., 2014). The local rate of sulfate reduction in a particular sediment column can be calculated by the change in sulfate concentrations in pore fluids below the surface, which yields the net flux of sulfate into marine sediments. A flux of sulfate into the sediment is assumed to be due to diffusion along a concentration gradient set up by the consumption of sulfate at depth. We have calculated the deep-sea rates of microbial sulfate reduction using over 700 drilling sites and arrive at a similar estimate of the global modern rate of sulfate respiration. Rates of sulfate reduction are not, however, the same as the rates of pyrite burial, which is likely limited to the uppermost sediments where reactive iron may be available, or in the most nearshore environments where the terrestrial supply of iron is high and rates of sulfate reduction are orders of magnitude higher than those in the deep-sea. Sulfur isotope fractionation during microbial sulfate reduction is a function of several environmental factors, including the rate of sulfate reduction. We use a new compilation of the link between sulfate reduction rate and sulfur isotope fractionation with a model of pyrite burial in a range of modern marine sediments to derive an estimate of the global pyrite burial flux and

  4. Stable isotope ratio mass spectrometry of nanogram quantities of boron and sulfur

    NASA Astrophysics Data System (ADS)

    Wieser, Michael Eugene

    1998-09-01

    Instrumentation and analytical techniques were developed to measure isotope abundances from nanograms of sulfur and boron. Sulfur isotope compositions were determined employing continuous flow isotope ratio mass spectroscopy (CF-IRMS) procedures and AsS+ thermal ionization mass spectrometry techniques (AsS+-TIMS). Boron isotope abundances were determined by BO2/sp--TIMS. CF-IRMS measurements realized δ34S values from 10 μg sulfur with precisions of ±0.3/perthous. To extend sulfur isotope measurements to much smaller samples, a TIMS procedure was developed to measure 75As32S+ and 75As34S+ at masses 108 and 109 from 200 ng S on a Finnigan MAT 262 with an ion counter. This is possibly the smallest amount of sulfur which has been successfully analyzed isotopically. The internal precision of 32S/34S ratios measured by AsS+-TIMS was better than ±0.15 percent. δ34S-values calculated relative to the measured 32S/34S value of an IAEA AG2S standard (S-1) agreed with those determined by CF-IRMS to within ±3/perthous. The increasing sensitivity of S-isotope analyses permits hiterto impossible investigations e.g. sulfur in tree rings and ice cores. Boron isotope abundances were measured as BO2/sp- from 50 ng B using an older thermal ionization mass spectrometer which had been extensively upgraded including the addition of computer control electronics, sensitive ion current amplification and fiber optic data bus. The internal precisions of the measured 11B/10B ratios were ±0.15 percent and the precisions of δ11B values calculated relative to the accepted international standard (SRM-951) were ±3/perthous. Two applications of boron isotope abundance variations were initiated (1) ground waters of Northern Alberta and (2) coffee beans in different regions of the world. In the first it was demonstrated that boron isotopes could be used to trace boron released during steam injection of oil sands into the surrounding environment. Data from the second study suggest that boron

  5. High sulfur isotope fractionation associated with anaerobic oxidation of methane in a low sulfate, iron rich environment

    NASA Astrophysics Data System (ADS)

    Weber, Hannah; Thamdrup, Bo; Habicht, Kirsten

    2016-06-01

    Sulfur isotope signatures provide key information for the study of microbial activity in modern systems and the evolution of the Earth surface redox system. Microbial sulfate reducers shift sulfur isotope distributions by discriminating against heavier isotopes. This discrimination is strain-specific and often suppressed at sulfate concentrations in the lower micromolar range that are typical to freshwater systems and inferred for ancient oceans. Anaerobic oxidation of methane (AOM) is a sulfate-reducing microbial process with a strong impact on global sulfur cycling in modern habitats and potentially in the geological past, but its impact on sulfur isotope signatures is poorly understood, especially in low sulfate environments. We investigated sulfur cycling and 34S fractionation in a low-sulfate freshwater sediment with biogeochemical conditions analogous to Early Earth environments. The zone of highest AOM activity was associated in situ with a zone of strong 34S depletions in the pool of reduced sulfur species, indicating a coupling of sulfate reduction and AOM at sulfate concentrations < 50 µmol L-1. In slurry incubations of AOM-active sediment, the addition of methane stimulated sulfate reduction and induced a bulk sulfur isotope effect of ~29 ‰. Our results imply that sulfur isotope signatures may be strongly impacted by AOM even at sulfate concentrations two orders of magnitude lower than at present oceanic levels. Therefore, we suggest that sulfur isotope fractionation during AOM must be considered when interpreting 34S signatures in modern and ancient environment.

  6. Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, Sherwood

    1996-01-01

    Isotopic measurements have been made on organic sulfur and phosphorus compounds recently discovered in the Murchison meteorite. Carbon, hydrogen and sulfur measurements were performed on individual members of the organic sulfur compounds, alkyl sulfonates; and carbon and hydrogen measurements were made on bulk alkyl phosphonates. Cooper and Chang reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into the potential synthetic mechanisms of these and, possibly, other organic species. Hydrogen isotopic measurements of the sulforiates now reveal deuterium excesses ranging from +660 to +2730 %. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurements of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson have shown that some bulk ureilites possess excess S-33 and Thiemens et al. have reported excess S-33 in an oldhamite separate from the Norton County meteorite. Rees and Thode reported a large S-33 excess in an Allende acid residue, however, attempts to verify this measurements have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect chemistry in the protosolar nebula or the precursor molecular cloud, identification of potential carriers is of considerable interest. In the present study, the stable isotopes of sulfur were measured in methane sulfonic acid extracted from the Murchison meteorite. The isotopic composition was found to be: (delta)S-33 = 2.48 %, (delta)S-34 = 2.49 % and (delta)S-36 = 6.76 %. Based upon analysis of more than 60 meteoritic and numerous terrestrial samples, the mass fractionation lines are

  7. Stable sulfur and nitrogen isotopic compositions of crude oil fractions from Southern Germany

    NASA Astrophysics Data System (ADS)

    Hirner, A. V.; Graf, W.; Treibs, R.; Melzer, A. N.; Hahn-Weinheimer, P.

    1984-11-01

    Eleven samples of crude oil from the Molasse Basin of Southern Germany were fractionated and their contents of sulfur and nitrogen as well as the stable isotope compositions of these elements ( 34S /32S and 15N /14N , resp.) investigated. According to the δ34S determinations, all crude oils from the Tertiary base of the Western and Eastern Molasse belong to one oil family and differ significantly from the Triassic and Liassic oils in the Western Molasse. An enrichment of 34S was observed with increasing polarity of crude oil fractions. The isotope distributions of sulfur in the polar constituents of the biodegraded oils from the sandstones of Ampfing, however, approach a homogeneous distribution. The nitrogen isotope distribution is rather uniform in Southern German oils. A regional differentiation can be recognized, although the overall isotopic variation is small. The δ15N values of the crudes and asphaltenes do not correlate.

  8. The minor sulfur isotope composition of Cretaceous and Cenozoic seawater sulfate

    NASA Astrophysics Data System (ADS)

    Masterson, A. L.; Wing, Boswell A.; Paytan, Adina; Farquhar, James; Johnston, David T.

    2016-06-01

    The last 125 Myr capture major changes in the chemical composition of the ocean and associated geochemical and biogeochemical cycling. The sulfur isotopic composition of seawater sulfate, as proxied in marine barite, is one of the more perplexing geochemical records through this interval. Numerous analytical and geochemical modeling approaches have targeted this record. In this study we extend the empirical isotope record of seawater sulfate to therefore include the two minor sulfur isotopes, 33S and 36S. These data record a distribution of values around means of Δ33S and Δ36S of 0.043 ± 0.016‰ and -0.39 ± 0.15‰, which regardless of δ34S-based binning strategy is consistent with a signal population of values throughout this interval. We demonstrate with simple box modeling that substantial changes in pyrite burial and evaporite sulfate weathering can be accommodated within the range of our observed isotopic values.

  9. Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

    NASA Astrophysics Data System (ADS)

    Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, S.

    1995-09-01

    Carbon, hydrogen and sulfur isotopic measurements have been made on individual members of a recently discovered class of organic sulfur compounds, alkyl sulfonates, in the Murchison meteorite. Cooper and Chang (1) reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into potential synthetic mechanisms of these, and possibly other, organic species. Hydrogen isotopic measurements of the sulfonates now reveal deuterium excesses ranging from +660 to +2730 per mil. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurement of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson (2) have shown that some bulk ureilites possess excess 33S and Thiemens et al. (3) have reported excess 33S in an oldhamite separate from Norton County. Rees and Thode (4) reported a large 33S excess in an Allende acid residue, however, attempts to verify this measurement have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect nebular chemistry, identification of potential carriers is of considerable interest. In the present study the three stable isotopes of sulfur were measured in methane sulfonate extracted from the Murchison meteorite. The isotopic composition was found to be delta 33S=2.48, delta 34S=2.49 and delta 36S = 6.76 per mil. Based upon analysis of more than 60 meteoritic, and numerous terrestrial samples, the mass fractionation lines are defined by 33Delta = delta 33S-0.50 delta 34S and 36Delta = delta 36S -1.97 delta 34S. From these relations a 33Delta = 1.24 per mil and 36Delta = 0.89 per mil is observed. These anomalies

  10. High-resolution quadruple sulfur isotope analyses of 3.2 Ga pyrite from the Barberton Greenstone Belt in South Africa reveal distinct environmental controls on sulfide isotopic arrays

    NASA Astrophysics Data System (ADS)

    Roerdink, Desiree L.; Mason, Paul R. D.; Whitehouse, Martin J.; Reimer, Thomas

    2013-09-01

    Multiple sulfur isotopes in Paleoarchean pyrite record valuable information on atmospheric processes and emerging microbial activity in the early sulfur cycle. Here, we report quadruple sulfur isotope data (32S, 33S, 34S, 36S) analyzed by secondary ion mass spectrometry from pyrite in a 3.26-3.23 Ga sedimentary barite deposit in the Barberton Greenstone Belt, South Africa. Our results demonstrate the presence of distinct pyrite populations and reproducible isotopic arrays in barite-free and barite-rich samples. The most 34S-depleted signatures with weakly positive Δ33S/δ34S were found in disseminated pyrite in barite, whereas positive Δ33S-values with negative Δ33S/δ34S and Δ36S/Δ33S = -0.9 ± 0.2 were exclusively observed in pyrite hosted by chert, dolomite, conglomerate and breccia. We interpret these variations to be related to local redox reactions and mixing in the sulfide phase, rather than representing primary atmospheric variability alone. The strong correlation between lithology and isotopic composition indicates distinct environments of sulfide formation linked to local sulfate concentrations and fluctuating inputs from different sulfur metabolisms. Strongly 34S-depleted sulfide was formed by microbial sulfate reduction at [SO42-] > 200 μM during deposition of barite-rich sediments, whereas isotope effects were suppressed when sulfate levels decreased during deposition of terrigeneous clastic rocks. Positive Δ33S-values indicate an increased input of sulfide derived from elemental sulfur metabolisms when sulfate concentrations fell below 200 μM. Our results support an important role for local sulfate concentrations on the expression of biogenic sulfur isotope signatures in some of the oldest rocks on Earth.

  11. A mass-independent sulfur isotope effect in the nonthermal formation

    NASA Technical Reports Server (NTRS)

    Bains-Sahota, Swroop K.; Thiemens, Mark H.

    1989-01-01

    A nonmass-dependent sulfur isotope effect is present in the rotationally symmetric S2F10 molecule, produced in an electrical discharge through sulfur tetrafluoride. A similar isotopic fractionation was observed in the product S2F10 from the electrodissociation of SF5Cl and in the reaction between fluorine atoms produced by F2 photolysis and SF2, collectively ruling out the SF5 formation process as the source of the mass-independent fractionation. The secondary dissociation of S2F10 as a source of the mass-independent fractionation is ruled out by control S2F10 dissociation experiments which are shown to produce small mass-dependent fractionations. Mass-dependent effects such as sulfur isotopic exchange and secondary dissociation reactions are significant processes for the system under study, and have been quantitatively accounted for. The role of symmetry in nonmass-dependent isotope effects is strengthened by the present experiments, and the search and characterization of mass-independent effects is extended to sulfur-containing molecules.

  12. Anomalous sulfur isotope compositions of volcanic sulfate over the last millennium in Antarctic ice cores

    NASA Astrophysics Data System (ADS)

    Baroni, MéLanie; Savarino, JoëL.; Cole-Dai, Jihong; Rai, Vinai K.; Thiemens, Mark H.

    2008-10-01

    The reconstruction of past volcanism from glaciological archives is based on the measurement of sulfate concentrations in ice. This method does not allow a proper evaluation of the climatic impact of an eruption owing to the uncertainty in classifying an event between stratospheric or tropospheric. This work develops a new method, using anomalous sulfur isotope composition of volcanic sulfate in order to identify stratospheric eruptions over the last millennium. The advantages and limits of this new method are established with the examination of the 10 largest volcanic signals in ice cores from Dome C and South Pole, Antarctica. Of the 10, seven are identified as stratospheric eruptions. Among them, three have been known to be stratospheric (Tambora, Kuwae, the 1259 Unknown Event) and they exhibit anomalous sulfur isotope compositions. Three unknown events (circa 1277, 1230, 1170 A.D.) and the Serua eruption have been identified as stratospheric eruptions, which suggests for the first time that they could have had significant climatic impact. However, the Kuwae and the 1259 Unknown Event stratospheric eruptions exhibit different anomalous sulfur isotope compositions between South Pole and Dome C samples. Differences in sulfate deposition and preservation patterns between the two sites can help explain these discrepancies. This study shows that the presence of an anomalous sulfur isotope composition of volcanic sulfate in ice core indicates a stratospheric eruption, but the absence of such composition does not necessarily lead to the conclusion of a tropospheric process because of differences in the sulfate deposition on the ice sheet.

  13. OXYGEN ISOTOPES IN ATMOSPHERIC SULFATES, SULFUR DIOXIDE, AND WATER VAPORS FIELD MEASUREMENTS, JULY 1975

    EPA Science Inventory

    Oxygen isotope ratios were determined for atmospheric samples of sulfate aerosols, sulfur dioxide, and water vapor collected simultaneously during a six-day period in July, 1975, at St. Louis, MO; Auburn, IL; and Glasgow, IL. The collection sites were located about 100km apart. C...

  14. Dynamic changes in sulfate sulfur isotopes preceding the Ediacaran Shuram Excursion

    NASA Astrophysics Data System (ADS)

    Osburn, Magdalena R.; Owens, Jeremy; Bergmann, Kristin D.; Lyons, Timothy W.; Grotzinger, John P.

    2015-12-01

    Large excursions in δ13C and δ34S are found in sedimentary rocks from the Ediacaran Period that may provide detailed mechanistic information about oxidation of Earth's surface. However, poor stratigraphic resolution and diagenetic concerns have thus far limited the interpretation of these records. Here, we present a high-resolution record of carbon and sulfur isotopes from the Khufai Formation, leading up to and including the onset of the Shuram carbon isotope excursion. We document large coherent excursions in the sulfur isotope composition and concentration of carbonate-associated sulfate (CAS) that occur both independently and synchronously with the carbon isotope excursion. Isotopic changes appear decoupled from major stratigraphic surfaces and facies changes, suggesting regional or global processes rather than local controls. Our data suggest that very low marine sulfate concentrations are maintained at least through the middle-Khufai Formation and require that the burial fraction of pyrite and the fractionation factor between sulfate and pyrite necessarily change through deposition. Reconciliation of simultaneous, up-section increases in marine sulfate concentration and δ34SCAS requires the introduction of strongly 34S-enriched sulfate, possibly from weathering of Cryogenian and earlier Ediacaran 34S-enriched pyrite. Our analysis of the onset of the Shuram carbon isotope excursion, observed in stratigraphic and lithologic context, is not consistent with diagenetic or authigenic formation mechanisms. Instead, we observe a contemporaneous negative excursion in sulfate δ34S suggesting linked primary perturbations to the carbon and sulfur isotope systems. This work further constrains the size, isotopic composition, and potential input fluxes of the Ediacaran marine sulfate reservoir, placing mechanistic constraints on possible drivers of extreme isotopic perturbations during this critical period in Earth history.

  15. Contrasting sulfur isotope records during the Late Devonian punctata and Upper Kellwasser events

    NASA Astrophysics Data System (ADS)

    Sim, M.; Ono, S.; Hurtgen, M. T.

    2013-12-01

    The Late Devonian was a period of intense biological and environmental changes, including terrestrial afforestation, a series of asteroid impacts, and active orogeny due to the accretion of continental blocks. High amplitude positive carbon isotope excursions, the punctata and Kellwasser events, reflect major perturbations in the global carbon cycle during this period, which have been attributed to increased continental weathering and subsequent ocean eutrophication. Despite the comparable carbon isotope anomalies, however, a global biological crisis has been reported only for the Kellwasser events, while very low extinction intensity characterizes the punctata Event. We will present sulfur isotope records of carbonate associated sulfate (CAS) and pyrite from Frasnian-Famennian sections in the Great Basin, USA, and evaluate the role of sulfur during the punctata and Upper Kellwasser events. A positive sulfur isotope shift in both CAS and pyrite accompanies the onset of the punctata Event, but with a larger extent in the latter. As a result, the sulfur isotope offset between CAS and pyrite (Δ34SCAS-py) plummeted to less than 10‰. In the middle of the punctata Event, a sharp negative δ34SCAS excursion occurred just after the Alamo Impact, leading to the negative Δ34SCAS-py values. Unlike the rapid oscillations of δ34Spy and δ34SCAS during the punctata Event, the Upper Kellwasser was a period of stability, except for a brief drop of δ34SCAS before the event. Paired sulfur isotope data, aided by a simple box model, suggests that geochemical cycle of sulfur might be responsible for the contrasting biological responses to these two events. Superheavy pyrite and high stratigraphic variability of δ34Spy and δ34SCAS demonstrate a relatively small oceanic sulfate pool during the punctata Event, and the Alamo Impact likely triggered to the rapid oxidation of microbially-produced sulfide. The expansion of sulfidic bottom water thus may have been impeded, thereby

  16. Sulfate sulfur isotope stratigraphy reveals a record of ocean ventilation during the Latest Ordovician

    NASA Astrophysics Data System (ADS)

    Gill, B. C.; Lyons, T. W.; Young, S.; Kaljo, D.; Saltzman, M.

    2012-12-01

    The Hirnantian (445 to 443 Ma)—the last stage of the Ordovician—is marked by several important historical events, including large-scale continental glaciation; a large perturbation to the global carbon cycle; and, most notably, the second largest extinction interval in Earth history. Several recent models for Late Ordovician extinction have invoked the expansion of euxinia (anoxic, H2S-containing marine waters) as a kill mechanism. A positive sulfur isotope excursion found in sedimentary pyrite that parallels the well-known Hirnantian positive carbon isotope excursion or HICE is cited as one of the main lines of evidence for enhanced marine euxinia. Following this line of argument, the pyrite-S and organic-C excursions should track changes in the isotopic compositions of the marine sulfate and dissolved inorganic carbon pools attributed to enhanced burial rates for both pyrite and organic carbon during a global expansion of euxinia in the oceans. Our data for marine sulfate, however, suggest something different. Specifically, to further constrain the changes to the global sulfur cycle over the late Ordovician, we present sulfur isotope data from both carbonate-associated sulfate (δ34SCAS) and pyrite (δ34Spyrite) paired with carbon isotope data from successions from the paleo-contintents of Laurentia and Baltica. δ34SCAS data from both successions show little variation during the Hirnantian. The lack a positive sulfate-S isotope excursion parallel to the HICE suggests a driver other than organic carbon burial for the carbon isotope excursion, such as enhanced weathering of carbonate rocks as proposed by others. Consistent with this alternative, we argue that the positive sulfur isotope excursion seen in pyrite in the Hirnantian successions, including our section from Baltica, reflects changes in local sedimentary environments. Specifically, eustatic shallowing of sedimentary environments and ventilation of the oceans pushed the local zone of microbial sulfate

  17. High-resolution sulfur isotopes in ice cores identify large stratospheric volcanic eruptions

    NASA Astrophysics Data System (ADS)

    Burke, Andrea; Sigl, Michael; Adkins, Jess; Paris, Guillaume; McConnell, Joe

    2016-04-01

    The record of the volcanic forcing of climate over the past 2500 years is reconstructed primarily from sulfate concentrations in ice cores. Of particular interest are stratospheric eruptions, as these afford sulfate aerosols the longest residence time and largest dispersion in the atmosphere, and thus the greatest impact on radiative forcing. Identification of stratospheric eruptions currently relies on the successful matching of the same volcanic sulphate peak in ice cores from both the Northern and Southern hemispheres (a "bipolar event"). These are interpreted to reflect the global distribution of sulfur aerosols by the stratospheric winds. Despite its recent success, this method relies on precise and accurate dating of ice cores, in order to distinguish between a true 'bipolar event' and two separate eruptions that occurred in close temporal succession. Sulfur isotopes can been used to distinguish between these two scenarios since stratospheric sulfur aerosols are exposed to UV radiation which imparts a mass independent fractionation (Baroni et al., 2007). Mass independent fractionation of sulfate in ice cores thus offers a novel method of fingerprinting stratospheric eruptions, and thus refining the historic record of explosive volcanism and its forcing of climate. Here we present new high-resolution (sub-annual) sulfur isotope data from the Tunu Ice core in Greenland over seven eruptions. Sulfur isotopes were measured by MC-ICP-MS, which substantially reduces sample size requirements and allows high temporal resolution from a single ice core. We demonstrate the efficacy of the method on recent, well-known eruptions (including Pinatubo and Katmai/Novarupta), and then apply it to unidentified sulfate peaks, allowing us to identify new stratospheric eruptions. Baroni, M., Thiemens, M. H., Delmas, R. J., & Savarino, J. (2007). Mass-independent sulfur isotopic compositions in stratospheric volcanic eruptions. Science, 315(5808), 84-87. http://doi.org/10

  18. Sulfur isotope values in the sulfidic Frasassi cave system, central Italy: A case study of a chemolithotrophic S-based ecosystem

    NASA Astrophysics Data System (ADS)

    Zerkle, Aubrey L.; Jones, Daniel S.; Farquhar, James; Macalady, Jennifer L.

    2016-01-01

    Sulfide oxidation forms a critical step in the global sulfur cycle, although this process is notoriously difficult to constrain due to the multiple pathways and highly reactive intermediates involved. Multiple sulfur isotopes (δ34S and Δ33S) can provide a powerful tool for unravelling sulfur cycling processes in modern (and ancient) environments, although they have had limited application to systems with well-resolved oxidative S cycling. In this study, we report the major (δ34S) and minor (Δ33S) isotope values of sulfur compounds in streams and sediments from the sulfidic Frasassi cave system, Marche Region, Italy. These microaerophilic cave streams host prominent white biofilms dominated by chemolithotrophic organisms that oxidize sulfide to S0, allowing us to estimate S isotope fractionations associated with in situ sulfide oxidation and to evaluate any resulting isotope biosignatures. Our results demonstrate that chemolithotrophic sulfide oxidation produces 34S enrichments in the S0 products that are larger than those previously measured in laboratory experiments, with 34εS0-H2S of up to 8‰ calculated. These small reverse isotope effects are similar to those produced during phototrophic sulfide oxidation (⩽7‰), but distinct from the small normal isotope effects previously calculated for abiotic oxidation of sulfide with O2 (∼-5‰). An inverse correlation between the magnitude of 34εS0-H2S effects and sulfide availability, along with substantial differences in Δ33S, both support complex sulfide oxidation pathways and intracellular recycling of S intermediates by organisms inhabiting the biofilms. At the ecosystem level, we calculate fractionations of less than 40‰ between sulfide and sulfate in the water column and in the sediments. These fractionations are smaller than those typically calculated for systems dominated by sulfate reduction (>50‰), and contrast with the commonly held assumption that oxidative recycling of sulfide generally

  19. Fractionation of sulfur isotopes during heterogeneous oxidation of SO2 in the atmosphere

    NASA Astrophysics Data System (ADS)

    Harris, E. J.; Sinha, B.; Hoppe, P.; Crowley, J.; Borrmann, S.; Foley, S. F.; Gnauk, T.; Van Pinxteren, D.; Herrmann, H.

    2011-12-01

    Sulfate and sulfur dioxide play an important role in environmental chemistry and climate, particularly through their effect on aerosols. Processing of aerosol through sulfate addition in clouds, which causes both hygroscopicity changes and mass increases, has been shown to modify the cloud condensation nucleus spectrum, leading to important climatological effects (Bower et al. 1997, Hegg et al. 2004). However, the uptake of sulfate and SO2 to aerosol in clouds is not well constrained, nor is it resolved for different particle types and sizes (Kasper-Giebl et al. 2000, Barrie et al. 2001). Measurements of stable sulfur isotopes can be used to investigate the chemistry of SO2 in the environment, providing insight into sources, sinks and oxidation pathways. Typical isotopic compositions for many sources have been measured, and the major current limitation is the lack of reliable fractionation factors - characteristic changes in isotopic composition caused by chemical reactions - with which to interpret the data. Laboratory values of fractionation factors for the major oxidation reactions have been measured in previous work, however there are no measurements or models to represent isotopic fractionation during heterogeneous oxidation on complex atmospheric surfaces. In this work the sulfur isotopic fractionation factors for SO2 oxidation have been measured on Sahara dust, obtained from the Cape Verde Islands, and sea salt aerosol, which was synthesised in the laboratory according to Millero (1974), modified to contain no sulfate. Sulfur dioxide with a known isotopic composition was oxidised on these surfaces under a variety of conditions including irradiation and ozonation, and the sulfur isotopic composition of the product sulfate was measured with the Cameca NanoSIMS 50. These laboratory results were then used to investigate the uptake of sulfur to particles in an orographic cloud during the HCCT campaign. The campaign took place at the Schmücke mountain in Germany

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

    SciTech Connect

    Janecky, D.R.

    1988-09-21

    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.

  1. Rare Isotope Insights into Supereruptions: Rare Sulfur and Triple Oxygen Isotope Geochemistry of Stratospheric Sulfate Aerosols Absorbed on Volcanic Ash Particles

    NASA Astrophysics Data System (ADS)

    Bindeman, I. N.; Eiler, J.; Wing, B.; Farquhar, J.

    2006-12-01

    isotopes, possibly through gas-phase reaction of volcanic SO2 with OH, or a multi-step Rayleigh-type process of atmospheric oxidation of sulfur dioxide; equilibrium fractionation cannot be ruled out during or moreof these multiple steps. We observe a positive correlation between Δ17O and δ18O values in this work that are similar to those recently obtained by Bao et al. (2003) and Savarino et al (2003). This correlation likely results from oxidation by high-δ18O and high-Δ17O compounds such as ozone and radicals that result from ozone break down, such as OH (Lyons, 2001). Large caldera-forming eruptions have the highest values, and the highest range of δ18O and Δ17O, which may be due to stratospheric reaction with ozone- derived OH following exhaustion of troposphere-derived OH radicals. These results imply that massive eruptions are capable of drying out the stratosphere from water and OH, and cause the temporal depletion of the ozone layer. Such depletion may be many times that of the measured three to eight percent depletion following 1991 Pinatubo eruption, if the amount of sulfur dioxide released is scaled with the amount of ozone depletion.

  2. Sulfur fluxes and isotopic compositions of the major rivers in China

    NASA Astrophysics Data System (ADS)

    Liu, C.; Lang, Y.; Tian, L.; Ding, H.; Strauss, H.; Zhao, Z.; Li, S.; Li, X.; Hu, J.

    2012-12-01

    Sulfur is widely distributed in the environment by volcanism, volatile emissions, precipitation, acid mine drainage and anthropogenic activity. Since the industrial revolution, the atmospheric sulfur cycle has been dominated by anthropogenic sources. Combustion of sulfur-containing fossil fuels release large quantities of sulfur dioxide into Earth's atmosphere annually. The cycling of sulfur, among those of many elements, is seriously disturbed by human activities at the earth's surface. Therefore, it is important to obtain a better understanding of sources and cycling processes of sulfur in river basins. For this purpose, we have measured the sulfur isotope composition of sulfate and its concentration for Changjiang (Yangtze River), Huanghe (Yellow River), Liaohe (Liao River), and Songhuajiang (Songhua River) in China. The sulfate fluxes of the major rivers in southern China are significantly larger as compared with the rivers in northern China. Sulfur isotopic compositions (δ34S) of sulfate in the rivers do not show a variation trend from southern to northern China. The sulfate δ34S values are 4.3‰~9.8‰ for Changjiang, 5.0‰~10.0‰ for most of river waters of Huanghe, and 2.0‰~27.0‰ for Songhuajiang. For Zhujiang (Pearl River), three sulfate δ34S values are from 1.0‰~6.9‰. The coal produced in southern China is generally of lower δ34S values as compared with that in northern China. The distributions of the sulfate δ34S values of the river waters of are generally lower in southern China, showing the contribution of atmospheric deposition of sulfur into the river water. Three main sources, atmospheric deposition (mostly anthropogenic), dissolution of sulfate evaporate, oxidation of sulfide minerals and/or sulfur-containing organic matter in soil, have been recognized for the sulfate in the rivers. Relative contributions of the different sulfur sources into the sulfate of the rivers are different, suggesting that sulfur cycling in the different

  3. A comprehensive sulfur and oxygen isotope study of sulfur cycling in a shallow, hyper-euxinic meromictic lake

    NASA Astrophysics Data System (ADS)

    Gilhooly, William P.; Reinhard, Christopher T.; Lyons, Timothy W.

    2016-09-01

    Mahoney Lake is a permanently anoxic and sulfidic (euxinic) lake that has a dense plate of purple sulfur bacteria positioned at mid-water depth (∼7 m) where free sulfide intercepts the photic zone. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and the water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within an aquatic environment with extremely high sulfide concentrations (>30 mM). Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S > 50‰) are consistent with sulfate reduction in both the sediments and the anoxic water column. Given the high sulfide concentrations of the lake, sulfur disproportionation is likely inoperable or limited to a very narrow zone in the chemocline, and therefore the large instantaneous fractionations are best explained by the microbial process of sulfate reduction. Pyrite extracted from the sediments reflects the isotopic composition of water column sulfide, suggesting that pyrite buried in the euxinic depocenter of the lake formed in the water column. The offset between sulfate and dissolved sulfide decreases at the chemocline (δ34SSO4-H2S = 37‰), a trend possibly explained by elevated sulfate reduction rates and inconsistent with appreciable disproportionation within this interval. Water column sulfate exhibits a linear response in δ18OSO4-δ34SSO4 and the slope of this relationship suggests relatively high sulfate reduction rates that appear to respond to seasonal changes in the productivity of purple sulfur bacteria. Although photosynthetic activity within the microbial plate influences the δ18OSO4-δ34SSO4 relationship, the biosignature for photosynthetic sulfur bacteria is restricted to the oxic/anoxic transition zone and is apparently minor relative to the more prevalent process of

  4. Source of arsenic-bearing pyrite in southwestern Vermont, USA: sulfur isotope evidence.

    PubMed

    Mango, Helen; Ryan, Peter

    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(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. PMID:24726513

  5. Regional source identification of atmospheric aerosols in Beijing based on sulfur isotopic compositions

    NASA Astrophysics Data System (ADS)

    Lianfang, Wei; Pingqing, Fu; Xiaokun, Han; Qingjun, Guo; Yele, Sun; Zifa, Wang

    2016-04-01

    65 daily PM2.5 (aerosol particle with aerodynamic diameter less than 2.5 μm) samples were collected from an urban site in Beijing in four months representing the four seasons between September 2013 and July 2014. Inorganic ions, organic/elemental carbon and stable sulfur isotopes of sulfate aerosols were analyzed systematically. The "fingerprint" characteristics of the stable sulfur isotopic composition, together with trajectory clustering modeled by HYSPLIT-4 and potential source contribution function (PSCF), were employed for identifying potential regional sources. Results obviously exhibited the distinctive seasonality for various aerosol speciation associated with PM2.5 in Beijing with sulfate, nitrate, ammonium, organic matter, and element carbon being the dominant species. Elevated chloride associated with higher concentration of organics were found in autumn and winter, due to enhanced coal combustion emissions. The δ34S values of Beijing aerosol samples ranged from 2.94‰ to 10.2‰ with an average value of 6.18±1.87‰ indicating that the major sulfur source is direct fossil fuel burning-related emissions. Owning to a temperature-dependent fractionation and elevated biogenic sources of isotopically light sulfur in summer, the δ34S values had significant seasonal variations with a winter maximum ( 8.6‰)and a summer minimum ( 5.0‰). The results of trajectory clustering and the PSCF method demonstrated that higher concentrations of sulfate with lower sulfur isotope ratios ( 4.83‰) were associated with air masses from the south, southeast or east, whereas lower sulfate concentrations with higher δ34S values ( 6.69‰) when the air masses were mainly from north or northwest. These results suggested two main different kinds of regional coal combustion sources contributed to the pollution in Beijing.

  6. Sulfur isotopes track the global extent and dynamics of euxinia during Cretaceous Oceanic Anoxic Event 2.

    PubMed

    Owens, Jeremy D; Gill, Benjamin C; Jenkyns, Hugh C; Bates, Steven M; Severmann, Silke; Kuypers, Marcel M M; Woodfine, Richard G; Lyons, Timothy W

    2013-11-12

    The Mesozoic Era is characterized by numerous oceanic anoxic events (OAEs) that are diagnostically expressed by widespread marine organic-carbon burial and coeval carbon-isotope excursions. Here we present coupled high-resolution carbon- and sulfur-isotope data from four European OAE 2 sections spanning the Cenomanian-Turonian boundary that show roughly parallel positive excursions. Significantly, however, the interval of peak magnitude for carbon isotopes precedes that of sulfur isotopes with an estimated offset of a few hundred thousand years. Based on geochemical box modeling of organic-carbon and pyrite burial, the sulfur-isotope excursion can be generated by transiently increasing the marine burial rate of pyrite precipitated under euxinic (i.e., anoxic and sulfidic) water-column conditions. To replicate the observed isotopic offset, the model requires that enhanced levels of organic-carbon and pyrite burial continued a few hundred thousand years after peak organic-carbon burial, but that their isotope records responded differently due to dramatically different residence times for dissolved inorganic carbon and sulfate in seawater. The significant inference is that euxinia persisted post-OAE, but with its global extent dwindling over this time period. The model further suggests that only ~5% of the global seafloor area was overlain by euxinic bottom waters during OAE 2. Although this figure is ~30× greater than the small euxinic fraction present today (~0.15%), the result challenges previous suggestions that one of the best-documented OAEs was defined by globally pervasive euxinic deep waters. Our results place important controls instead on local conditions and point to the difficulty in sustaining whole-ocean euxinia. PMID:24170863

  7. Evaporation and Accompanying Isotopic Fractionation of Sulfur from FE-S Melt During Shock Wave Heating

    NASA Technical Reports Server (NTRS)

    Tachibana, S.; Huss, G. R.; Miura, H.; Nakamoto, T.

    2004-01-01

    Chondrules probably formed by melting and subsequent cooling of solid precursors. Evaporation during chondrule melting may have resulted in depletion of volatile elements in chondrules. It is known that kinetic evaporation, especially evaporation from a melt, often leads to enrichment of heavy isotopes in an evaporation residue. However, no evidence for a large degree of heavy-isotope enrichment has been reported in chondrules for K, Mg, Si, and Fe (as FeO). The lack of isotopic fractionation has also been found for sulfur in troilites (FeS) within Bishunpur (LL3.1) and Semarkona (LL3.0) chondrules by an ion microprobe study. The largest fractionation, found in only one grain, was 2.7 +/- 1.4 %/amu, while all other troilite grains showed isotopic fractionations of <1 %/amu. The suppressed isotopic fractionation has been interpreted as results of (i) rapid heating of precursors at temperatures below the silicate solidus and (ii) diffusion-controlled evaporation through a surrounding silicate melt at temperatures above the silicate solidus. The kinetic evaporation model suggests that a rapid heating rate of >10(exp 4)-10(exp 6) K/h for a temperature range of 1000-1300 C is required to explain observed isotopic fractionations. Such a rapid heating rate seems to be difficult to be achieved in the X-wind model, but can be achieved in shock wave heating models. In this study, we have applied the sulfur evaporation model to the shock wave heating conditions of to evaluate evaporation of sulfur and accompanying isotopic fractionation during shock wave heating at temperatures below the silicate solidus.

  8. Sulfur isotopes track the global extent and dynamics of euxinia during Cretaceous Oceanic Anoxic Event 2

    PubMed Central

    Owens, Jeremy D.; Gill, Benjamin C.; Jenkyns, Hugh C.; Bates, Steven M.; Severmann, Silke; Kuypers, Marcel M. M.; Woodfine, Richard G.; Lyons, Timothy W.

    2013-01-01

    The Mesozoic Era is characterized by numerous oceanic anoxic events (OAEs) that are diagnostically expressed by widespread marine organic-carbon burial and coeval carbon-isotope excursions. Here we present coupled high-resolution carbon- and sulfur-isotope data from four European OAE 2 sections spanning the Cenomanian–Turonian boundary that show roughly parallel positive excursions. Significantly, however, the interval of peak magnitude for carbon isotopes precedes that of sulfur isotopes with an estimated offset of a few hundred thousand years. Based on geochemical box modeling of organic-carbon and pyrite burial, the sulfur-isotope excursion can be generated by transiently increasing the marine burial rate of pyrite precipitated under euxinic (i.e., anoxic and sulfidic) water-column conditions. To replicate the observed isotopic offset, the model requires that enhanced levels of organic-carbon and pyrite burial continued a few hundred thousand years after peak organic-carbon burial, but that their isotope records responded differently due to dramatically different residence times for dissolved inorganic carbon and sulfate in seawater. The significant inference is that euxinia persisted post-OAE, but with its global extent dwindling over this time period. The model further suggests that only ∼5% of the global seafloor area was overlain by euxinic bottom waters during OAE 2. Although this figure is ∼30× greater than the small euxinic fraction present today (∼0.15%), the result challenges previous suggestions that one of the best-documented OAEs was defined by globally pervasive euxinic deep waters. Our results place important controls instead on local conditions and point to the difficulty in sustaining whole-ocean euxinia. PMID:24170863

  9. Mass independent fractionation of sulfur isotopes during thermochemical reduction of native sulfur, sulfite and sulfate by amino acids

    NASA Astrophysics Data System (ADS)

    Watanabe, Y.; Naraoka, H.; Ohmoto, H.

    2006-05-01

    Mass independent fractionation of sulfur isotopes (MIF-S) is recognized when the Δ33S value (= δ33S-0.515xδ34S) of a sample falls outside the range of 0±0.2 permil and the 33-34θ value (= ln33α/ ln34α) lies outside the range of 0.515±.005 (Farquhar and Wing, 2003). Previous investigators have concluded that the only mechanisms to create MIF-S are photochemical reactions between sulfur-bearing gases (SO2, H2S) and UV. Based on comparisons of the geochemical characteristics of Archean sedimentary rocks between those with large MIF-S values (e.g., the 2.5 Ga McRae and 2.7 Ga Jeerinah shales) and those with no (or very small) MIF- S values (e.g., 2.76 Ga Hardey shales and 2.92 Ga Mosquito Creek shales), we have developed a hypothesis that MIF-S in sedimentary rocks may have been created by reactions among organic-rich sediments, sulfur- bearing solid compounds, and sulfur-bearing hydrothermal fluids at T = 100-200°C during the early diagenetic stage of sediments. Most abundant organic compounds in immature sediments are amino acids. For these reasons, we have conducted series of laboratory experiments to investigate sulfur isotope fractionations during reactions between a variety of amino acids (alanine, glycine, hystidine, etc.) and native sulfur, sodium sulfite or sodium sulfate at 150-200°C. Previous researchers used a variety of organic compounds (sugars, methane, xylene, etc) and/or ferrous- bearing minerals to investigate non-bacterial sulfate reduction, but they failed to demonstrate thermochemical sulfate reduction at temperatures below 230°C. However, we were able to reduce sulfate (S6+), as well as sulfite (S4+) and native sulfur (S0), to hydrogen sulfide (S2-) even at 150°C using simple and common amino acids (e.g., alanine and glycine). The reduction rates generally decreased: (a) from native sulfur, to sulfite, and to sulfate; (b) from simple amino acids to more complex amino acids (e.g., histidine); and (c) with decreasing temperatures. The

  10. Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

    NASA Astrophysics Data System (ADS)

    Johnson, Craig A.; Emsbo, Poul; Poole, Forrest G.; Rye, Robert O.

    2009-01-01

    Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a δ 34S versus δ 18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The δ 34S versus δ 18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H 2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.

  11. Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

    USGS Publications Warehouse

    Johnson, C.A.; Emsbo, P.; Poole, F.G.; Rye, R.O.

    2009-01-01

    Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a ??34S versus ??18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The ??34S versus ??18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.

  12. Precise isotope-ratio determination by CGC hyphenated to ICP-MCMS for speciation of trace amounts of gaseous sulfur, with SF6 as example compound.

    PubMed

    Krupp, Eva M; Pécheyran, Christophe; Meffan-Main, Simon; Donard, Olivier F X

    2004-01-01

    Capillary gas chromatography coupled to an inductively coupled plasma mass spectrometer with multiple-collector detection (GC-ICP-MCMS) has been used to assess the precision and instrumental mass bias in sulfur isotope-ratio determination for the gaseous sulfur species SF6. The isotopic composition of the compound was certified by the institute for reference materials and measurements (IRMM, Belgium) and is available as PIGS 2010. Integration of the peaks (peak half-width 1.4 s) was performed using a special peak-integration method based on definition of the integration area by assessment of a uniform isotope-ratio area within the chromatographic peak. Instrumental mass bias was determined to be approximately 12% per mass unit and proved to be stable in the concentration range measured. Replicate injections of 2, 10, 20, and 30 ng (as S) SF6 diluted in argon gave precision for the 32S/34S ratio from 0.6% RSD for 2-ng injections to 0.03% RSD for 30-ng injections. The 32S/33S and 33S/34S isotope-ratio precision was better than 0.4% RSD for injections of 10 ng (as S) and higher. Detection limits were in the absolute pg range for all measured sulfur isotopes. PMID:14618293

  13. Coupled sulfur and oxygen isotope insight into bacterial sulfate reduction in the natural environment

    NASA Astrophysics Data System (ADS)

    Antler, Gilad; Turchyn, Alexandra V.; Rennie, Victoria; Herut, Barak; Sivan, Orit

    2013-10-01

    We present new sulfur and oxygen isotope data in sulfate (δ34SSO4 and δ18OSO4, respectively), from globally distributed marine and estuary pore fluids. We use this data with a model of the biochemical steps involved in bacterial sulfate reduction (BSR) to explore how the slope on a δ18OSO4 vs. δ34SSO4 plot relates to the net sulfate reduction rate (nSRR) across a diverse range of natural environments. Our data demonstrate a correlation between the nSRR and the slope of the relative evolution of oxygen and sulfur isotopes (δ18OSO4 vs. δ34SSO4) in the residual sulfate pool, such that higher nSRR results in a lower slope (sulfur isotopes increase faster relative to oxygen isotopes). We combine these results with previously published literature data to show that this correlation scales over many orders of magnitude of nSRR. Our model of the mechanism of BSR indicates that the critical parameter for the relative evolution of oxygen and sulfur isotopes in sulfate during BSR in natural environments is the rate of intracellular sulfite oxidation. In environments where sulfate reduction is fast, such as estuaries and marginal marine environments, this sulfite reoxidation is minimal, and the δ18OSO4 increases more slowly relative to the δ34SSO4. In contrast, in environments where sulfate reduction is very slow, such as deep sea sediments, our model suggests sulfite reoxidation is far more extensive, with as much as 99% of the sulfate being thus recycled; in these environments the δ18OSO4 increases much more rapidly relative to the δ34SSO4. We speculate that the recycling of sulfite plays a physiological role during BSR, helping maintain microbial activity where the availability of the electron donor (e.g. available organic matter) is low.

  14. Sulfur Isotope Analysis of Minerals and Fluids in a Natural CO2 Reservoir, Green River, Utah

    NASA Astrophysics Data System (ADS)

    Chen, F.; Kampman, N.; Bickle, M. J.; Busch, A.; Turchyn, A. V.

    2013-12-01

    Predicting the security of geological CO2 storage sites requires an understanding of the geochemical behavior of the stored CO2, especially of fluid-rock reactions in reservoirs, caprocks and fault zones. Factors that may influence geochemical behavior include co-injection of sulfur gases along with the CO2, either in acid-gas disposal or as contaminants in CO2 storage sites, and microbial activity, such as bacterial sulfate reduction. The latter may play an important role in buffering the redox chemistry of subsurface fluids, which could affect toxic trace metal mobilization and transport in acidic CO2-rich fluids. These processes involving sulfur are poorly understood. Natural CO2-reservoirs provide natural laboratories, where the flow and reactions of the CO2-charged fluids and the activity of microbial communities are integrated over sufficient time-scales to aid prediction of long-term CO2 storage. This study reports on sulfur isotope analyses of sulfate and sulfide minerals in rock core and in CO2-charged fluids collected from a stacked sequence of natural CO2 reservoirs at Green River, Utah. Scientific drilling adjacent to a CO2-degassing normal fault to a depth of 325m retrieved core and fluid samples from two CO2 reservoirs in the Entrada and Navajo Sandstones and from the intervening Carmel Formation caprock. Fluid samples were collected from CO2-charged springs that discharge through the faults. Sulfur exists as sulfate in the fluids, as sedimentary gypsum beds in the Carmel Formation, as remobilized gypsum veins within a fault damage zone in the Carmel Fm. and in the Entrada Sandstone, and as disseminated pyrite and pyrite-mineralized open fractures throughout the cored interval. We use the stable sulfur (δ34S) and oxygen (δ18OSO4) isotopes of the sulfate, gypsum, and pyrite to understand the source of sulfur in the reservoir as well as the timing of gypsum vein and pyrite formation. The hydration water of the gypsum is also reported to explore the

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

    NASA Astrophysics Data System (ADS)

    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

  16. Stable sulfur isotope partitioning during simulated petroleum formation as determined by hydrous pyrolysis of Ghareb Limestone, Israel

    USGS Publications Warehouse

    Amrani, A.; Lewan, M.D.; Aizenshtat, Zeev

    2005-01-01

    Hydrous pyrolysis experiments at 200 to 365??C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2 S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2??? in 34S during thermal maturation compared with the initial ??34S values. The ??34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1??? of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21??? lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the ??34S-enriched secondary pyrite decomposes above 300??C resulting in a corresponding decrease in the ??34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen ??34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The

  17. Biogeochemistry of sulfur in the Vienna Woods: Study of sulfur stable isotope ratios by MC-ICP-MS as indicator of biogeochemical S cycling

    NASA Astrophysics Data System (ADS)

    Hanousek, Ondrej; Berger, Torsten W.; Prohaska, Thomas

    2014-05-01

    Sulfur entering forest ecosystems originates mainly from combustion of fossil fuels. This source of sulfur has been strongly (by more than 95 %) reduced in last decades and recently, higher sulfur output (in soil solution or stream water) than sulfur input (in rain water) in an ecosystem was registered in many monitored forest ecosystems. This unbalance may be caused by weathering of sulfur-bearing rocks, desorption of sulfur adsorbed in soil in the past or (re)mineralization of organic sulfur compounds. This 'negative' balance leads to mobilization of base cations along with SO42- and as such to an acidification of soils. As hypothesis, δ34S/32S depletion in stream water will be observed if a considerable proportion of atmospherically deposited sulfate is cycled through the organic S pool. Rain water and soil solutions samples were collected for this study at 3 sites (beech stands) in the Vienna Woods, Austria twice a month from May 2010 to April 2012. Due to the expected sulfate concentration gradient with respect to the distance from a tree, sampling was carried out at 5 intervals from a stem. The sulfur concentration in the samples was determined by ion chromatography. Sulfur isotope ratios (δ34S/32SV CDT) were analyzed by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in edge-resolution mode. The method was validated using IAEA-S-1 and IAEA-S-2 isotopic certified reference materials. The combined standard uncertainty of the measurement (uc = 0.10 %, k = 1) proves the suitability of the developed method. The concentration of sulfur in rain water showed expected behavior, with a seasonal maximum in winter months, in contrast to the corresponding δ34S/32SV CDT isotope ratios, where no or low seasonal trends were observed. The sulfur isotope ratios in soil solution samples show a dependence on the distance from a tree stem and the sampling depth with lower δ34S/32SV CDT ratios as compared to the precipitation. The measured isotopic

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

    PubMed

    Popov, L

    2016-09-01

    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. PMID:27451111

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

    EPA Science Inventory

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

  20. Carbon, nitrogen and sulfur in lunar fines 15012 and 15013 - Abundances, distributions and isotopic compositions

    NASA Technical Reports Server (NTRS)

    Chang, S.; Lawless, J.; Romiez, M.; Kaplan, I. R.; Petrowski, C.; Sakai, H.; Smith, J. W.

    1974-01-01

    Lunar fines 15012,16 and 15013,3 were analyzed by stepwise pyrolysis and acid hydrolysis as well as complete combustion in oxygen to determine carbon, nitrogen and sulfur. In addition, hydrogen was analysed during pyrolysis as well as during hydrolysis. By comparison of the distribution frequencies of C, N, S, H2 and Fe with He-4, considered to have arisen from solar wind contribution, it is concluded that nitrogen and hydrogen have largely a solar origin. Carbon has a significant solar contribution, and metallic iron may have resulted from solar wind interaction with ferrous minerals on the lunar surface. Sulfur probably has a predominantly lunar origin. There is no direct evidence for meteorotic contribution to these samples. Solar wind interaction also has a marked effect on the stable isotope distribution of C-13/C-12, N-15/N-14, and S-34/S-32. In all cases, the heavy isotope was most enriched in the smallest grain-size fraction.

  1. Isotopic Approaches to Allying Productivity and Sulfur Metabolism in Three Symbiotic Hydrothermal Vent Molluscs

    NASA Astrophysics Data System (ADS)

    Beinart, R.; Gartman, A.; Sanders, J. G.; Luther, G. W.; Girguis, P. R.

    2012-12-01

    Symbioses between animals and chemosynthetic bacteria predominate at hydrothermal vents. In these associations, the endosymbiotic bacteria utilize chemical reductants for the energy to support autotrophy, providing primary nutrition for the host. Despite their ubiquity at vents worldwide, little is known about the rates of productivity of these symbioses under different physico-chemical regimes or how their metabolism effects the local geochemical environment. To address this matter, we used high-pressure flow through incubations and stable isotopic tracers to maintain three genera of symbiotic mollusc - the gastropods Alviniconcha and Ifremeria, and the mussel Bathymodiolus - at vent-like conditions. Via the incorporation of isotopically labeled compounds, we assessed their productivity when using different reduced sulfur species as reductants. Using cyclic voltammetry, mass spectrometry and discrete geochemical analyses, we concurrently measured their effect on sulfur flux from the vessels. We found that the symbionts of all three genera can support autotrophy with hydrogen sulfide and thiosulfate, though at different rates. Additionally, by examining the rate of isotopic incorporation into biomass, we revealed intra-generic variability in productivity among the individuals in our experimental assemblages that are likely related to differences in the geochemical regime along the length of reactor. These geochemical gradients are due to the activity of other individuals within the vessel, since those organisms closest to the influent of the vent-like water had the highest measured carbon incorporation. Finally, we measured the uptake and excretion of sulfur species, which illustrate the degree to which these symbioses might impact local sulfur chemistry in situ. These experiments show that A) access to particular sulfur species differentially affects the productivity of vent symbioses, suggesting that competition for these substrates, both within and between host

  2. Coupled Changes in Sulfur and Carbon Isotopes Preceding the Sturtian Glaciation of the Neoproterozoic

    NASA Astrophysics Data System (ADS)

    Gouldey, J.; Hurtgen, M.

    2014-12-01

    The relationship between the carbon and sulfur cycles in the Neoproterozoic has proven to be complex. Unusually high δ13Ccarbonate persists throughout this period, however large negative excursions precede both the Sturtian (~710 Ma) and the Marinoan (635 Ma) glaciations, the mechanisms of which are still debated. Previous data shows that during the interglacial interval, sulfate concentrations were very low and abnormally enriched δ34Spyrite values inversely correlate with shifts in δ13Ccarbonate. However, very little carbonate-associated sulfate (CAS) could be extracted from these sections. To better understand the relationship between the global carbon and sulfur cycles during this tumultuous time, high-resolution coupled records of δ13Ccarbonate and δ34Ssulfate are needed. Here we present paired δ34Ssulfate and δ34Spyrite data from carbonates of the Coates Lake Group (Mackenzie Mountains, Canada), which represent deposition preceding the Sturtian glaciation, to further explore the connection between the Neoproterozoic sulfur and carbon cycles, and to gain insight into the possible mechanisms driving major perturbations in the carbon isotope record. Leading into the glaciation, δ13Ccarbonate increases from -9.5‰ to 8‰ over approximately 200 meters of section, then abruptly drops to ~2‰ over 30 meters. Both sulfate and pyrite isotopes track these changes, indicating that as organic carbon burial is steadily increasing and driving δ13Ccarbonate more positive, pyrite burial is increasing as well. Δ34S decreases as δ13Ccarbonate and δ34S increase, providing further evidence that more organic carbon and pyrite are being buried, leading to a decrease in oceanic sulfate concentrations. Δ34S then increases as δ13Ccarbonate decreases, indicating a positive flux to the sulfate reservoir prior to the Sturtian glaciation. This relationship between carbon and sulfur differs significantly from what is seen during the interglacial interval, and represents

  3. Sulfur and oxygen isotope fractionation during sulfate reduction coupled to anaerobic oxidation of methane is dependent on methane concentration

    NASA Astrophysics Data System (ADS)

    Deusner, Christian; Holler, Thomas; Arnold, Gail L.; Bernasconi, Stefano M.; Formolo, Michael J.; Brunner, Benjamin

    2014-08-01

    Isotope signatures of sulfur compounds are key tools for studying sulfur cycling in the modern environment and throughout earth's history. However, for meaningful interpretations, the isotope effects of the processes involved must be known. Sulfate reduction coupled to the anaerobic oxidation of methane (AOM-SR) plays a pivotal role in sedimentary sulfur cycling and is the main process responsible for the consumption of methane in marine sediments - thereby efficiently limiting the escape of this potent greenhouse gas from the seabed to the overlying water column and atmosphere. In contrast to classical dissimilatory sulfate reduction (DSR), where sulfur and oxygen isotope effects have been measured in culture studies and a wide range of isotope effects has been observed, the sulfur and oxygen isotope effects by AOM-SR are unknown. This gap in knowledge severely hampers the interpretation of sulfur cycling in methane-bearing sediments, especially because, unlike DSR which is carried out by a single organism, AOM-SR is presumably catalyzed by consortia of archaea and bacteria that both contribute to the reduction of sulfate to sulfide. We studied sulfur and oxygen isotope effects by AOM-SR at various aqueous methane concentrations from 1.4±0.6 mM up to 58.8±10.5 mM in continuous incubation at steady state. Changes in the concentration of methane induced strong changes in sulfur isotope enrichment (εS34) and oxygen isotope exchange between water and sulfate relative to sulfate reduction (θO), as well as sulfate reduction rates (SRR). Smallest εS34 (21.9±1.9‰) and θO (0.5±0.2) as well as highest SRR were observed for the highest methane concentration, whereas highest εS34 (67.3±26.1‰) and θO (2.5±1.5) and lowest SRR were reached at low methane concentration. Our results show that εS34, θO and SRR during AOM-SR are very sensitive to methane concentration and thus also correlate with energy yield. In sulfate-methane transition zones, AOM-SR is likely

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

    NASA Astrophysics Data System (ADS)

    Balci, Nurgul; Mayer, Bernhard; Shanks, Wayne C.; Mandernack, Kevin 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 & Zn0.88Fe0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant δ34S and δ18O 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 δ18O values to determine the relative contributions of H2O-derived and O2-derived oxygen in the newly formed sulfate. . Experiments were conducted under aerobic and anaerobic conditions using O2 and Fe(III)aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and So as the sole energy source were also conducted. The δ34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnSFe by Fe(III)aq produced sulfur isotope fractionations (ε34SSO4-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 (ε34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnSFe by Fe(III)aq all of the sulfate oxygen was derived from water, with measured ε18OSO4-H2O values of 8.2 ± 0.2‰ and 7.5 ± 0.1‰, respectively. Also, during the aerobic oxidation of ZnSFe and So by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ε18OSO4-H2O values of 8.1 ± 0.1‰ and 8.3 ± 0.3‰, respectively. During biological oxidation of ZnS by O

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

    USGS Publications Warehouse

    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

  6. Sulfur Isotope Fractionation Due to SO2 Photolysis in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Lyons, J. R.; Blackie, D.; Stark, G.; Pickering, J.

    2012-12-01

    The discovery of unusual (i.e. mass-independent) sulfur isotope fractionation (or MIF) in Archean and Paleoproterozoic sedimentary rocks has promised to yield insights into the rise of O2 and the nature of the sulfur cycle on ancient Earth [1], but interpretation has been hampered by the lack of a clear mechanism for the sulfur isotope signature. Proposed MIF mechanisms include SO2 photolysis [1-4], atmospheric S3 (thiozone) formation, and thermal sulfate reduction in sediments [5]. Studies focusing only on SO2 photolysis, including measurements of isotopic cross sections [6], have yielded results differing greatly from theory [4], and have resulted in improbable interpretations [7]. In addition to ancient rocks, there are sulfur isotope MIF signatures in polar ice core sulfates associated with massive Plinian eruptions over the past ~1000 years (e.g., [8]). The ice core MIF signatures differ significantly from the ancient Earth MIF signatures, suggesting a different source mechanism. SO2 photolysis can generate sulfur isotope MIF signatures in two ways: 1) self-shielding by an optically-thick column of SO2, and 2) isotope-dependent differences in absorption line intensities and widths, which are espcially important for optically-thin conditions. The MIF signatures in ice core sulfates appear to be consistent with self-shielding in an optically-thick plume, but the Archean MIF clearly is not. To address the optically-thin case, we've made high-resolution ultraviolet cross section measurements of the sulfur isotopologues of SO2 made with the UV FTS at Imperial College. We measured cross sections at 1 cm-1 spectral resolution for 32SO2, 33SO2, 34SO2 and for a 36SO2/34SO2 mixture. Incorporating these cross sections into a simple atmospheric photochemical model with a solar UV flux, we find sulfur MIF signatures for SO and S that.are consistent with the Archean pyrites. We also find that additional mass-dependent fractionation during self-shielding by 32SO2 places an

  7. Sulfur isotope geochemistry of ore and gangue minerals from the Silesian-Cracow Mississippi Valley-type ore district, Poland

    USGS Publications Warehouse

    Leach, D.L.; Vets, J.G.; Gent, C.A.

    1996-01-01

    Studies of the sulfur isotopic composition of ore and gangue minerals from the Silesian-Cracow Zn-Pb district were conducted to gain insights into processes that controlled the location and distribution of the ore deposits. Results of this study show that minerals from the Silesian-Cracow ore district have the largest range of sulfur isotope compositions in sulfides observed from any Mississippi Valley-type ore district in the world. The ??34S values for sulfide minerals range from +38 to -32 per mil for the entire paragenetic sequence but individual stages exhibit smaller ranges. There is a well developed correlation between the sulfur isotope composition and paragenetic stage of ore deposition. The first important ore stage contains mostly positive ??34S values, around 5 per mil. The second stage of ore formation are lower, with a median value of around -5 to -15 per mil, and with some values as low as -32 per mil. Late stage barite contains isotopically heavy sulfur around +32 per mil. The range in sulfur isotope compositions can be explained by contributions of sulfur from a variety of source rocks together with sulfur isotope fractionations produced by the reaction paths for sulfate reduction. Much of the variation in sulfur isotope compositions can be explained by bacterial reduction of sedimentary sulfate and disequilibrium reactions by intermediate-valency sulfur species, especially in the late-stage pyrite and sphalerite. Organic reduction of sulfate and thermal release of sulfur from coals in the Upper Silesian Coal Basin may have been important contributors to sulfur in the ore minerals. The sulfur isotopic data, ore mineral textures, and fluid inclusion data, are consistent with the hypothesis that fluid mixing was the dominant ore forming mechanism. The rather distinct lowering of ?? 34S values in sulfides from stage 2 to stage 3 is believed to reflect some fundamental change in the source of reduced sulfur and/or hydrology of the ore

  8. Experimentally determined sulfur isotope fractionation between metal and silicate and implications for planetary differentiation

    NASA Astrophysics Data System (ADS)

    Labidi, J.; Shahar, A.; Le Losq, C.; Hillgren, V. J.; Mysen, B. O.; Farquhar, J.

    2016-02-01

    The Earth's mantle displays a subchondritic 34S/32S ratio. Sulfur is a moderately siderophile element (i.e. iron-loving), and its partitioning into the Earth's core may have left such a distinctive isotope composition on the terrestrial mantle. In order to constrain the sulfur isotope fractionation occurring during core-mantle differentiation, high-pressure and temperature experiments were conducted with synthetic mixtures of metal and silicate melts. With the purpose to identify the mechanism(s) responsible for the S isotope fractionations, we performed our experiments in different capsules - namely, graphite and boron nitride capsules - and thus at different fO2, with varying major element chemistry of the silicate and metal fractions. The S isotope fractionations Δ34Smetal-silicate of equilibrated metal alloys versus silicate melts is +0.2 ± 0.1‰ in a boron-free and aluminum-poor system quenched at 1-1.5 GPa and 1650 °C. The isotope fractionation increases linearly with increasing boron and aluminum content, up to +1.4 ± 0.2‰, and is observed to be independent of the silicon abundance as well as of the fO2 over ∼3.5 log units of variations explored here. The isotope fractionations are also independent of the graphite or nitride saturation of the metal. Only the melt structural changes associated with aluminum and boron concentration in silicate melts have been observed to affect the strength of sulfur bonding. These results establish that the structure of silicate melts has a direct influence on the S2- average bonding strengths. These results can be interpreted in the context of planetary differentiation. Indeed, the structural environments of silicate evolve strongly with pressure. For example, the aluminum, iron or silicon coordination numbers increase under the effect of pressure. Consequently, based on our observations, the sulfur-bonding environment is likely to be affected. In this scheme, we tentatively hypothesize that S isotope fractionations

  9. Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt

    USGS Publications Warehouse

    Johnson, Craig A.; Bookstrom, Arthur A.; Slack, John F.

    2012-01-01

    Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ34S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ (n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H2S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit

  10. Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

    NASA Astrophysics Data System (ADS)

    Meshoulam, Alexander; Ellis, Geoffrey S.; Said Ahmad, Ward; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

    2016-09-01

    The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n-hexadecane (n-C16) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H2S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H2S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4‰ for H2S and as much as 22.2‰ for BT. The fractionations decrease as the H2S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H2S and sulfate (∼17‰). Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4 dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and

  11. Sulfur isotopic variations during subduction of hydrated lithosphere: the Erro Tobbio case

    NASA Astrophysics Data System (ADS)

    Santiago Ramos, D.; Shimizu, N.; Scambelluri, M.

    2012-12-01

    High-pressure serpentinites provide unique opportunities for advancing our understanding of geochemical changes in hydrated lithosphere during subduction, and deep recycling of elements. The Erro Tobbio serpentinized peridotites range from hydrated Jurassic oceanic lithosphere to those recrystallized at ~550°C 2 - 2.5 GPa during Alpine subduction (Scambelluri et al., 2001), and are shown to possess boron signatures indicating addition and retention of seawater-derived boron up to the highest pressure-temperature conditions recorded (Scambelluri and Tonarini, 2012). We conducted in-situ sulfur isotope analysis of individual sulfide grains (pentlandite and heazlewoodite) in samples representing early low-temperature serpentinization and those in serpentinized peridotites and serpentinites recrystallized at high pressures and temperatures, using the Cameca IMS 1280 at Woods Hole Oceanographic Institution. Instrumental mass fractionation was shown to be identical for pyrrhotite and pentlandite, indicating that Fe/Ni ratios do not bias observed sulfur isotopic compositions. A pyrrhotite standard with known δ34S was mounted in an indium substrate together with polished pieces of rock specimens with sulfide grains, and analyses of unknowns were bracketed by repeated analyses of the standard. A primary ion beam of 133Cs+ with a current of ~10 pA was focused to a spot of <5μm in diameter for analysis of micron-size grains. Internal and external precisions generally range from 0.4‰ to 0.7‰ (2σ standard error). Salient features of the results include: (1) pentlandites in low-temperature "early serpentinites" are light in δ34S, ranging from -3.2 - -0.4‰ in one sample to +0.7 - +5.9‰ in another; (2) two mylonitic high-pressure serpentinites are heavy in δ34S, with +9.8 - +11.1‰ in one sample and +8.8 - +11.6‰ in another; (3) an undeformed high pressure serpentinized peridotite shows a bimodal isotopic compositions with -1.1 - +0.5‰ in one group of grains and

  12. Sulfur-based absolute quantification of proteins using isotope dilution inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lee, Hyun-Seok; Heun Kim, Sook; Jeong, Ji-Seon; Lee, Yong-Moon; Yim, Yong-Hyeon

    2015-10-01

    An element-based reductive approach provides an effective means of realizing International System of Units (SI) traceability for high-purity biological standards. Here, we develop an absolute protein quantification method using double isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) combined with microwave-assisted acid digestion for the first time. We validated the method and applied it to certify the candidate protein certified reference material (CRM) of human growth hormone (hGH). The concentration of hGH was determined by analysing the total amount of sulfur in hGH. Next, the size-exclusion chromatography method was used with ICP-MS to characterize and quantify sulfur-containing impurities. By subtracting the contribution of sulfur-containing impurities from the total sulfur content in the hGH CRM, we obtained a SI-traceable certification value. The quantification result obtained with the present method based on sulfur analysis was in excellent agreement with the result determined via a well-established protein quantification method based on amino acid analysis using conventional acid hydrolysis combined with an ID liquid chromatography-tandem mass spectrometry. The element-based protein quantification method developed here can be generally used for SI-traceable absolute quantification of proteins, especially pure-protein standards.

  13. Sulfur Biogeochemistry and Isotope Fractionation in Shallow Groundwater of Owens Dry Lake, California

    NASA Astrophysics Data System (ADS)

    Ryu, J.; Zierenberg, R. A.; Dahlgren, R. A.; Gao, S.

    2003-12-01

    The redox status of hypersaline, strongly alkaline groundwaters at Owens Dry Lake was investigated to help guide mitigation efforts for attenuating dust generated from the dry lakebed. Shallow (<1 m), anoxic groundwaters have been identified as a major limitation to vegetation establishment on the lakebed due to the inability of roots to growth in anoxic conditions. Previous work indicates that sulfate reduction is the dominant reaction regulating the redox status of shallow groundwaters. The purpose of this study was to evaluate sulfur biogeochemistry and formation of solid-phase sulfides in the shallow groundwater/sediments using selective sulfur speciation techniques coupled with isotopic measurements. In addition to groundwater and subsurface sediment samples (1-2 m depth) at sites representative of different groundwater pathways, selected sediment samples at 5 different depths (from oxic to anoxic layers) were collected. Sediment samples were examined for monosulfide, pyrite, sulfate, organic sulfur, and total sulfur. Organic sulfur was less than 0.01% of the total, and pyrite was the predominant sulfur-bearing phase below the groundwater capillary zone ( ˜20cm depth) where anoxic conditions were developed. The concentration of monosulfide and pyrite were less than detection limits above the capillary zone as these unsaturated layers were exposed to oxygen. High concentrations of dissolved sulfide (4.81 to 134.7 mg /L) and low concentrations of dissolved Fe (generally <0.5 mg/L) indicate that the availability of Fe limits pyrite formation. The high values ( ˜50‰ ) of isotopic fractionations between δ 34Spyrite and δ 34Ssulfate(Δ sulfate-pyrite) in anoxic zones suggest that bioavailability of organic carbon is a limiting factor for the reduction of sulfate. The values of Δ sulfate-pyrite along the hydrologic flowpath indicate that the isotopic fractionations were significantly correlated with dissolved sulfate concentration, which was strongly

  14. Chemical weathering and the role of sulfuric and nitric acids in carbonate weathering: Isotopes (13C, 15N, 34S, and 18O) and chemical constraints

    NASA Astrophysics Data System (ADS)

    Li, Cai; Ji, Hongbing

    2016-05-01

    Multiple isotopes (13C-DIC, 34S and 18O-SO42-, 15N and 18O-NO3-) and water chemistry were used to evaluate weathering rates and associated CO2 consumption by carbonic acid and strong acids (H2SO4 and HNO3) in a typical karst watershed (Wujiang River, Southwest China). The dual sulfate isotopes indicate that sulfate is mainly derived from sulfide oxidation in coal stratum and sulfide-containing minerals, and dual nitrate isotopes indicate that nitrate is mainly derived from soil N and nitrification. The correlation between isotopic compositions and water chemistry suggests that sulfuric and nitric acids, in addition to carbonic acid, are involved in carbonate weathering. The silicate and carbonate weathering rates are 7.2 t km-2 yr-1 and 76 t km-2 yr-1, respectively. In comparison with carbonate weathering rates (43 t km-2 yr-1) by carbonic acid alone, the subsequent increase in rates indicates significant enhancement of weathering when combined with sulfuric and nitric acids. Therefore, the role of sulfuric and nitric acids in the rock weathering should be considered in the global carbon cycle.

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

    PubMed Central

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

    2014-01-01

    Achondrite meteorites have anomalous enrichments in 33S, relative to chondrites, which have been attributed to photochemistry in the solar nebula. However, the putative photochemical reactions remain elusive, and predicted accompanying 33S depletions have not previously been found, which could indicate an erroneous assumption regarding the origins of the 33S anomalies, or of the bulk solar system S-isotope composition. Here, we report well-resolved anomalous 33S depletions in IIIF iron meteorites (<−0.02 per mil), and 33S enrichments in other magmatic iron meteorite groups. The 33S depletions support the idea that differentiated planetesimals inherited sulfur that was photochemically derived from gases in the early inner solar system (<∼2 AU), and that bulk inner 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. PMID:25453079

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

    PubMed

    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 (<-0.02 per mil), and (33)S enrichments in other magmatic iron meteorite groups. The (33)S depletions support the idea that differentiated planetesimals inherited sulfur that was photochemically derived from gases in the early inner solar system (<∼2 AU), and that bulk inner 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. PMID:25453079

  17. Isotope Biogeochemistry of Sulfur in a Cold-Water Carbonate Mound (IODP Site 1317)

    NASA Astrophysics Data System (ADS)

    Ferdelman, T. G.; Boettcher, M. E.

    2007-12-01

    To establish a depositional model for cold-water carbonate mounds, Challenger Mound and adjacent continental slope sites were drilled during IODP Expedition 307 in May 2005. Although a role for methane seepage and subsequent anaerobic oxidation was discounted both as a hard-round substrate for mound initiation and as a principal source of carbonate within the mound succession, interstitial water profiles of sulfate, alkalinity, Mg, and Sr indicated a tight coupling between carbonate diagenesis and mircrobial sulfate reduction. The reaction of sulfide with siliciclastic iron-bearing minerals to form pyrite was proposed to account for enhanced diagenetic carbonate precipitation (Ferdelman et al., 2006; Proc. IODP, vol. 307; doi:10.2204/iodp.proc.307.2006). To characterize these geomicrobial sulfur transformations in the carbonate mound sediments, the inorganic and stable isotope geochemical compositions of pore water sulfate and solid phase reduced sulfur compounds were performed. Acid-volatile sulfur (AVS) and pyrite del 34S compositions were usually similar and exhibited an increasing trend of from -40 per mil near surface to -20 per mil at the mound base at 132 mbsf. However, several excursions to more 34S sulfur enriched pyrite to values >0 per mil were observed in the deeper sections of the mound sequence. These excursions may be linked transitory changes in the depth of the methane-sulfate transition zone during mound build-up. The oxygen isotopic composition of residual dissolved sulfate indicates intracellular isotope exchange processes within the cells of SRBs, leading to increasing equilibration between extracellular pore water and sulfate.

  18. Rare Isotopic Species of Sulfur Monoxide: The Rotational Spectrum in the THz Region

    NASA Astrophysics Data System (ADS)

    Lattanzi, Valerio; Cazzoli, Gabriele; Puzzarini, Cristina

    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 34SO and S18O. 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, 34SO, S17O, and S18O, 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.

  19. Stable Isotope Phenotyping via Cluster Analysis of NanoSIMS Data As a Method for Characterizing Distinct Microbial Ecophysiologies and Sulfur-Cycling in the Environment.

    PubMed

    Dawson, Katherine S; Scheller, Silvan; Dillon, Jesse G; Orphan, Victoria J

    2016-01-01

    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 (13)C-acetate, (15)N-ammonium, and (33)S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope ((13)C/(12)C, (15)N/(14)N, and (33)S/(32)S) and elemental ratio (C/CN and S/CN) profiles, our analysis partitioned ~2200 cellular regions of interest (ROIs) into five 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. PMID:27303371

  20. Stable Isotope Phenotyping via Cluster Analysis of NanoSIMS Data As a Method for Characterizing Distinct Microbial Ecophysiologies and Sulfur-Cycling in the Environment

    PubMed Central

    Dawson, Katherine S.; Scheller, Silvan; Dillon, Jesse G.; Orphan, Victoria J.

    2016-01-01

    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 five 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. PMID:27303371

  1. Trace sulfate in mid-Proterozoic carbonates and the sulfur isotope record of biospheric evolution

    NASA Astrophysics Data System (ADS)

    Gellatly, Anne M.; Lyons, Timothy W.

    2005-08-01

    Concentrations of oceanic and atmospheric oxygen have varied over geologic time as a function of sulfur and carbon cycling at or near the Earth's surface. This balance is expressed in the sulfur isotope composition of seawater sulfate. Given the near absence of gypsum in pre-Phanerozoic sediments, trace amounts of carbonate-associated sulfate (CAS) within limestones or dolostones provide the best available constraints on the isotopic composition of sulfate in Precambrian seawater. Although absolute CAS concentrations, which range from those below detection to ˜120 ppm sulfate in this study, may be compromised by diagenesis, the sulfur isotope compositions can be buffered sufficiently to retain primary values. Stratigraphically controlled δ 34S measurements for CAS from three mid-Proterozoic carbonate successions (˜1.2 Ga Mescal Limestone, Apache Group, Arizona, USA; ˜1.45-1.47 Ga Helena and Newland formations, Belt Supergroup, Montana, USA; and ˜1.65 Ga Paradise Creek Formation, McNamara Group, NW Queensland, Australia) show large isotopic variability (+9.1‰ to +18.9‰, -1.1‰ to +27.3‰, and +14.1‰ to +37.3‰, respectively) over stratigraphic intervals of ˜50 to 450 m. This rapid variability, ranging from scattered to highly systematic, and overall low CAS abundances can be linked to sulfate concentrations in the mid-Proterozoic ocean that were substantially lower than those of the Phanerozoic but higher than values inferred for the Archean. Results from the Belt Supergroup specifically corroborate previous arguments for seawater contributions to the basin. Limited sulfate availability that tracks the oxygenation history of the early atmosphere is also consistent with the possibility of extensive deep-ocean sulfate reduction, the scarcity of bedded gypsum, and the stratigraphic δ 34S trends and 34S enrichments commonly observed for iron sulfides of mid-Proterozoic age.

  2. Oxygen and sulfur isotope fractionation during sulfide oxidation by anoxygenic phototrophic bacteria

    NASA Astrophysics Data System (ADS)

    Brabec, Michelle Y.; Lyons, Timothy W.; Mandernack, Kevin W.

    2012-04-01

    Sulfide-mediated anoxygenic photosynthesis (SMAP) carried out by anaerobic phototrophic bacteria may have played an important role in sulfur cycling, formation of sulfate, and, perhaps, primary production in the Earth’s early oceans. Determination of ε34SSO4-Sulfide- and ε18OSO4-H2O values for bacterial sulfide oxidation will permit more refined interpretation of the δ34S and δ18OSO4 values measured in modern anoxic environments, such as meromictic lakes where sulfide commonly extends into the photic zone, and in the ancient rock record, particularly during periods of the Precambrian when anoxic and sulfidic (euxinic) conditions were believed to be more pervasive than today. Laboratory experiments with anaerobic purple and green sulfur phototrophs, Allochromatium vinosum and Chlorobaculum tepidum, respectively, were conducted to determine the sulfur and oxygen isotope fractionation during the oxidation of sulfide to sulfate. Replicate experiments were conducted at 25 °C for A. vinosum and 45 °C for C. tepidum, and in duplicate at three different starting oxygen isotope values for water to determine sulfate-water oxygen isotope fractionations accurately (ε18OSO4-H2O). ε18OSO4-H2O values of 5.6 ± 0.2‰ and 5.4 ± 0.1‰ were obtained for A. vinosum and C. tepidum, respectively. Temperature had no apparent effect on the ε18OSO4-H2O values. By combining all data from both cultures, an average ε18OSO4-H2O value of 5.6 ± 0.3‰ was obtained for SMAP. This value falls between those previously reported for bacterial oxidation of sphalerite and elemental sulfur (7-9‰) and abiotic and biotic oxidation of pyrite and chalcopyrite (2-4‰). Sulfur isotope fractionation between sulfide and sulfate formed by A.vinosum was negligible (0.1 ± 0.2‰) during all experiments. For C. tepidum an apparent fractionation of -2.3 ± 0.5‰ was observed during the earlier stages of oxidation based on bulk δ34S measurements of sulfate and sulfide and became smaller (-0.7

  3. Sulfur isotope evidence for low and fluctuating sulfate levels in the Late Devonian ocean and the potential link with the mass extinction event

    NASA Astrophysics Data System (ADS)

    Sim, Min Sub; Ono, Shuhei; Hurtgen, Matthew T.

    2015-06-01

    High amplitude positive carbon isotope excursions in the Late Devonian, the punctata and Kellwasser events, reflect major perturbations in the global carbon cycle that have been attributed to increased continental weathering and subsequent ocean eutrophication. Despite the comparable carbon isotope anomalies, however, a major extinction has been reported only for the Kellwasser Events, while the punctata Event is marked by low extinction intensity. This study presents multiple sulfur isotope records of carbonate-associated sulfate (CAS) and pyrite from Late Devonian sections in the Great Basin, USA, in order to document changes in the coupled (or decoupled) geochemical cycles of carbon and sulfur during the punctata and Upper Kellwasser events. A positive sulfur isotope shift in both CAS and pyrite accompanies the onset of the punctata Event, but to a larger extent in the latter. As a result, the sulfur isotope offset between CAS and pyrite (Δ34SCAS-py) dropped to less than 10‰. In the middle of the punctata Event, a sharp negative δ34SCAS excursion and negative Δ34SCAS-py values coincide with the Alamo impact. Unlike the rapid δ34Spy and δ34SCAS oscillations associated with the punctata Event, the Upper Kellwasser was a period of relative stability, except for a brief δ34SCAS drop before the event. Paired sulfur isotope data, aided by a simple box model, suggest that the geochemical cycle of sulfur may have been partly responsible for the contrasting biological responses that define these events. High stratigraphic δ34Spy and δ34SCAS variability, coupled with strong reservoir effect, demonstrates a relatively small oceanic sulfate pool existed during the punctata Event. Further, the Alamo impact likely triggered the rapid oxidation of microbially-produced sulfide within this event. The expansion of sulfidic bottom water thus may have been impeded during the punctata Event. In contrast, the lack of a positive shift in δ34SCAS and sizable Δ34SCAS

  4. Rare sulfur and triple oxygen isotope geochemistry of volcanogenic sulfate aerosols

    NASA Astrophysics Data System (ADS)

    Bindeman, I. N.; Eiler, J. M.; Wing, B. A.; Farquhar, J.

    2007-05-01

    We present analyses of stable isotopic ratios 17O/ 16O, 18O/ 16O, 34S/ 32S, and 33S/ 32S, 36S/ 32S in sulfate leached from volcanic ash of a series of well known, large and small volcanic eruptions. We consider eruptions of Mt. St. Helens (Washington, 1980, ˜1 km 3), Mt. Spurr (Alaska, 1953, <1 km 3), Gjalp (Iceland, 1996, 1998, <1 km 3), Pinatubo (Phillipines, 1991, 10 km 3), Bishop tuff (Long Valley, California, 0.76 Ma, 750 km 3), Lower Bandelier tuff (Toledo Caldera, New Mexico, 1.61 Ma, 600 km 3), and Lava Creek and Huckleberry Ridge tuffs (Yellowstone, Wyoming, 0.64 Ma, 1000 km 3 and 2.04 Ma 2500 km 3, respectively). This list covers much of the diversity of sizes and the character of silicic volcanic eruptions. Particular emphasis is paid to the Lava Creek tuff for which we present wide geographic sample coverage. This global dataset spans a significant range in δ34S, δ18O, and Δ17O of sulfate (29‰, 30‰, and 3.3‰, respectively) with oxygen isotopes recording mass-independent ( Δ17O > 0.2‰) and sulfur isotopes exhibiting mass-dependent behavior. Products of large eruptions account for most of' these isotopic ranges. Sulfate with Δ17O > 0.2‰ is present as 1-10 μm gypsum crystals on distal ash particles and records the isotopic signature of stratospheric photochemical reactions. Sediments that embed ash layers do not contain sulfate or contain little sulfate with Δ17O near 0‰, suggesting that the observed sulfate in ash is of volcanic origin. Mass-dependent fractionation of sulfur isotopic ratios suggests that sulfate-forming reactions did not involve photolysis of SO 2, like that inferred for pre-2.3 Ga sulfates from Archean sediments or Antarctic ice-core sulfate associated with few dated eruptions. Even though the sulfate sulfur isotopic compositions reflect mass-dependent processes, the products of caldera-forming eruptions display a large δ34S range and exhibit fractionation relationships that do not follow the expected equilibrium

  5. The Phosphorus, Sulfur, Argon, and Calcium Isotopic Composition of the Galactic Cosmic Ray Source

    NASA Astrophysics Data System (ADS)

    Ogliore, R. C.; Stone, E. C.; Leske, R. A.; Mewaldt, R. A.; Wiedenbeck, M. E.; Binns, W. R.; Israel, M. H.; von Rosenvinge, T. T.; de Nolfo, G. A.; Moskalenko, I. V.

    2009-04-01

    Galactic cosmic ray (GCR) measurements of the phosphorus, sulfur, argon, and calcium isotopes made by the Cosmic Ray Isotope Spectrometer aboard the Advanced Composition Explorer are reported over the energy range from ~100 to ~400 MeV nucleon-1. The propagation of cosmic rays through the Galaxy and heliosphere is modeled with constraints imposed by measurements. Isotopic source abundance ratios 31P/32S, 34S/32S, 38Ar/36Ar, and 44Ca/40Ca are deduced. The derived 31P/32S ratio is 2.34 ± 0.34 times larger than the solar system value, lending further credence to the suggestion that refractory elements are enriched in the GCRs due to the sputtering of ions off grains in the cores of superbubbles. By determining the GCR source abundances of argon (a noble gas) and calcium (a refractory), it is determined that material in grains is accelerated to GCR energies a factor of 6.4 ± 0.3 more efficiently than gas-phase material in this charge range. With this information, the dust fraction of phosphorus and sulfur in the interstellar material that is mixed with stellar ejecta to form the GCR seed material is found to be consistent with astronomical observations.

  6. A nitrogen and sulfur isotope investigation of redox conditions occurring in a shallow outwash aquifer.

    NASA Astrophysics Data System (ADS)

    Spalding, R.; Hartke, E.

    2001-12-01

    The sources and distribution of elevated nitrate and sulfate concentrations were determined using nitrogen and sulfur isotopes in groundwater from an unconfined outwash aquifer located in Jackson County, southern Indiana. Land use is mostly agricultural. Local farmers apply nitrogeneous inorganic fertilizers to their fields. In addition, two commercial confined feedlots house over two million chickens, and wastes are stored in seven interconnected lagoons at the larger feedlot. These wastes are later applied to an adjacent field via spray irrigation. Over 50 shallow wells (5 m deep), domestic wells (7 m deep) and deep wells (15to 20 m deep) were sampled over a two- year period to monitor nitrogen and sulfur inputs from these sources. Most shallow groundwater in the study area is above the EPA drinking water standards for nitrate-N (>10 mgL). Nitrate concentrations are highest down gradient from the spray irrigation field (53.5 mgL), yet are also elevated in up gradient groundwaters. Nitrogen isotopes are enriched in the heavier isotope (d15N-NO3 > +13.7 ooo) down gradient from the large feedlot and lightest signatures (d15N-NO3 < +2.0 ooo) are found in up gradient groundwater underlying fields that use inorganic fertilizers. Analytes associated with feedlot wastes (sodium, potassium, chloride and sulfate) are also elevated down gradient from the larger feedlot. Deep groundwater has no nitrate and higher sulfate concentrations than shallow waters. In two sets of multi-level wells, enrichment in both oxygen and nitrogen isotopes indicates that denitrification may occur at two depths: 1) locally in shallow waters adjacent to the waste lagoons; and 2) in deeper waters (approximately 10 m) throughout the study area. Sulfate isotopic signatures in deep groundwater approach the signature of pyrite found within the outwash (d34S-SO4 = -11.6 ooo). Autotrophic denitrification may be occurring where nitrate is reduced and the oxidation of pyrite is adding sulfate with depth.

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

    NASA Astrophysics Data System (ADS)

    Jimenez, A.

    2012-04-01

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

  8. Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: interaction of seawater with fayalite and magnetite at 200–350°C

    USGS Publications Warehouse

    Shanks, Wayne C., III; Bischoff, James L.; Rosenbauer, Robert J.

    1981-01-01

    Systematics of sulfur isotopes in the 250 and 350°C experiments indicate that isotopic equilibrium is reached, and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H2S 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.

  9. Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2 and the implications to the early earth's atmosphere.

    PubMed

    Whitehill, Andrew R; Xie, Changjian; Hu, Xixi; Xie, Daiqian; Guo, Hua; Ono, Shuhei

    2013-10-29

    Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen ((16)O,(17)O,(18)O) and sulfur ((32)S, (33)S, (34)S, (36)S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ(33)S up to 78‰ and Δ(36)S up to 110‰, from the broadband excitation of SO2 in the 250-350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO2 ( (3)B1), which results from intersystem crossing from the excited singlet ( (1)A2/ (1)B1) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO2 and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO2 to the singlet states but from an isotope selective spin-orbit interaction between the singlet ( (1)A2/ (1)B1) and triplet ( (3)B1) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for (33)SO2 and (36)SO2 for the low vibrational levels of the (1)A2 state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems. PMID:23836655

  10. Biosynthesis and Isotopic Composition of Bacteriochlorophyll a and Okenone in Purple Sulfur Bacteria

    NASA Astrophysics Data System (ADS)

    Smith, D.; Scott, J. H.; Steele, A.; Cody, G. D.; Ohara, S.; Bowden, R.; Fogel, M. L.

    2011-12-01

    Phototrophic sulfur bacteria play an integral part in the anaerobic cycling of sulfur. Bacteriochloroyphll a (Bchl a) is a well-studied photosynthetic compound required for photosynthesis in the organisms that possess it. The only known fossil of purple sulfur bacteria (PSB) in the geologic record is okenane, believed to be of biologic origin originating from the carotenoid pigment okenone, which has only been documented in eleven species of Chromatiaceae. Organic geochemical studies have identified okenane in preserved organic matter in rocks and ancient sediments and further, okenone production has been observed in modern water columns and sediment surfaces. We have undertaken a comprehensive study on the biosynthesis of bacterial pigments including okenone and C, N, and S isotopic fractionation during various growth modes in controlled laboratory experiments of purple sulfur bacteria. Cultures of Marichromatium purpuratum 1591, M. purpuratum 1711, Thiocapsa marina 5653, and FGL21 (isolated from the chemocline of Fayetteville Green Lake, NY) were grown under autotrophic and photoheterotrophic (e.g. acetate or pyruvate) conditions in batch cultures. Concentrations of okenone and Bchl a were quantified as a function of time and growth by Ultra Performance-Liquid Chromatography-Mass Spectrometry (UP-LC-MS) and spectrophotometry. Overall okenone and Bchl a concentrations reached μM levels in the cultures. At stationary phase, all four strains achieved concentrations of okenone and Bchl a that were approximately 2.5 fM and 0.2 fM per cell, respectively, with okenone to Bchl a ratios of approximately 12 to 1. Isotope Ratio Mass Spectrometry (IRMS) was performed on bulk cells and compound specific analysis of Bchl a and okenone to better understand the fractionation associated with the production of the compounds.

  11. Sulfur and oxygen isotope study of sulfate reduction in experiments with natural populations from Fællestrand, Denmark

    NASA Astrophysics Data System (ADS)

    Farquhar, James; Canfield, Don E.; Masterson, Andrew; Bao, Huiming; Johnston, David

    2008-06-01

    This study investigates the sulfur and oxygen isotope fractionations of dissimilatory sulfate reduction and works to reconcile the relationships between the oxygen and sulfur isotopic and elemental systems. We report results of experiments with natural populations of sulfate-reducing bacteria using sediment and seawater from a marine lagoon at Fællestrand on the northern shore of the island of Fyn, Denmark. The experiments yielded relatively large magnitude sulfur isotope fractionations for dissimilatory sulfate reduction (up to approximately 45‰ for 34S/32S) with higher δ18O accompanying higher δ34S, similar to that observed in previous studies. The seawater used in the experiments was spiked by addition of 17O-labeled water and the 17O content of residual sulfate was found to depend on the fraction of sulfate reduced in the experiments. The 17O data provides evidence for recycling of sulfur from metabolic intermediates and for an 18O/16O fractionation of ∼25-30‰ for dissimilatory sulfate reduction. The close correlation between the 17O data and the sulfur isotope data suggests that isotopic exchange between cell water and external water (reactor water) was rapid under experimental conditions. The molar ratio of oxygen exchange to sulfate reduction was found to be about 2.5. This value is slightly lower than observed in studies of natural ecosystems [e.g., Wortmann U. G., Chernyavsky B., Bernasconi S. M., Brunner B., Böttcher M. E. and Swart P. K. (2007) Oxygen isotope biogeochemistry of pore water sulfate in the deep biosphere: dominance of isotope exchange reactions with ambient water during microbial sulfate reduction (ODP Site 1130). Geochim. Cosmochim. Acta71, 4221-4232]. Using recent models of sulfur isotope fractionations we find that our combined sulfur and oxygen isotopic data places constraints on the proportion of sulfate recycled to the medium (78-96%), the proportion of sulfur intermediate sulfite that was recycled by way of APS to sulfate

  12. Indicating atmospheric sulfur by means of S-isotope in leaves of the plane, osmanthus and camphor trees.

    PubMed

    Xiao, Hua-Yun; Wang, Yan-Li; Tang, Cong-Guo; Liu, Cong-Qiang

    2012-03-01

    Foliar δ(34)S values of three soil-growing plant species (Platanus Orientalis L., Osmanthus fragrans L. and Cinnamomum camphora) have been analyzed to indicate atmospheric sulfur. The foliar δ(34)S values of the three plant species averaged -3.11±1.94‰, similar to those of both soil sulfur (-3.73±1.04‰) and rainwater sulfate (-3.07±2.74‰). This may indicate that little isotopic fractionation had taken place in the process of sulfur uptake by root or leaves. The δ(34)S values changed little in the transition from mature leaves to old/senescing leaves for both the plane tree and the osmanthus tree, suggestive of little isotope effect during sulfur redistribution in plant tissues. Significantly linear correlation between δ(34)S values of leaves and rainwater sulfate for the plane and osmanthus trees allowed the tracing of temporal variations of atmospheric sulfur by means of foliar sulfur isotope, while foliage δ(34)S values of the camphor is not an effective indicator of atmospheric sulfur. PMID:22243850

  13. Oxygen isotope constraints on the sulfur cycle over the past 10 million years.

    PubMed

    Turchyn, Alexandra V; Schrag, Daniel P

    2004-03-26

    Oxygen isotopes in marine sulfate (delta18O(SO4)) measured in marine barite show variability over the past 10 million years, including a 5 per mil decrease during the Plio-Pleistocene, with near-constant values during the Miocene that are slightly enriched over the modern ocean. A numerical model suggests that sea level fluctuations during Plio-Pleistocene glacial cycles affected the sulfur cycle by reducing the area of continental shelves and increasing the oxidative weathering of pyrite. The data also require that sulfate concentrations were 10 to 20% lower in the late Miocene than today. PMID:15044800

  14. 3.4-Billion-year-old biogenic pyrites from Barberton, South Africa: sulfur isotope evidence

    NASA Technical Reports Server (NTRS)

    Ohmoto, H.; Kakegawa, T.; Lowe, D. R.

    1993-01-01

    Laser ablation mass spectroscopy analyses of sulfur isotopic compositions of microscopic-sized grains of pyrite that formed about 3.4 billion years ago in the Barberton Greenstone Belt, South Africa, show that the pyrite formed by bacterial reduction of seawater sulfate. These data imply that by about 3.4 billion years ago sulfate-reducing bacteria had become active, the oceans were rich in sulfate, and the atmosphere contained appreciable amounts (>>10(-13) of the present atmospheric level) of free oxygen.

  15. 3.4-Billion-year-old biogenic pyrites from Barberton, South Africa: sulfur isotope evidence.

    PubMed

    Ohmoto, H; Kakegawa, T; Lowe, D R

    1993-10-22

    Laser ablation mass spectroscopy analyses of sulfur isotopic compositions of microscopic-sized grains of pyrite that formed about 3.4 billion years ago in the Barberton Greenstone Belt, South Africa, show that the pyrite formed by bacterial reduction of seawater sulfate. These data imply that by about 3.4 billion years ago sulfate-reducing bacteria had become active, the oceans were rich in sulfate, and the atmosphere contained appreciable amounts (>10(-13) of the present atmospheric level) of free oxygen. PMID:11539502

  16. Massive sulfide deposits and hydrothermal solutions: incremental reaction modeling of mineral precipitation and sulfur isotopic evolution

    SciTech Connect

    Janecky, D.R.

    1986-01-01

    Incremental reaction path modeling of chemical and sulfur isotopic reactions occurring in active hydrothermal vents on the seafloor, in combination with chemical and petrographic data from sulfide samples from the seafloor and massive sulfide ore deposits, allows a detailed examination of the processes involved. This paper presents theoretical models of reactions of two types: (1) adiabatic mixing between hydrothermal solution and seawater, and (2) reaction of hydrothermal solution with sulfide deposit materials. In addition, reaction of hydrothermal solution with sulfide deposit minerals and basalt in feeder zones is discussed.

  17. 3. 4-billion-year-old biogenic pyrites from Barberton, South Africa: Sulfur isotope evidence

    SciTech Connect

    Ohmoto, H.; Kakegawa, T. ); Lowe, D.R. )

    1993-10-22

    Laser ablation mass spectroscopy analysis of sulfur isotopic compositions of microscopic-sized grains of pyrite that formed about 3.4 billion years ago in the Barberton Greenstone Belt, South Africa, show that the pyrite formed by bacterial reduction of seawater sulfate. These data imply that by about 3.4 billion years ago sulfate-reducing bacteria had become active, the oceans were rich in sulfate, and the atmosphere contained appreciable amounts (> > 10[sup [minus]13] of the present atmospheric level) of free oxygen.

  18. Constraints from sulfur isotopes on the origin of gypsum at concrete/claystone interfaces

    NASA Astrophysics Data System (ADS)

    Lerouge, Catherine; Claret, Francis; Tournassat, Christophe; Grangeon, Sylvain; Gaboreau, Stéphane; Boyer, Bernard; Borschnek, Daniel; Linard, Yannick

    Two in situ concrete/claystone interfaces were sampled at the laboratory level in the Andra Meuse/Haute Marne (France) Underground Research Laboratory (URL) in order to study five years of interactions between Callovian-Oxfordian (COx) claystone and two cementitious materials (concrete bottom slab and shotcrete on the walls of the main gallery), with a specific focus on sulfur. Combined mineralogical, chemical and sulfur isotopic investigations were carried out to define the degree of the perturbation of the sulfur system in the claystone and in both the cementitious materials. At both interfaces, results show that the main perturbation on the claystone side is the formation of scarce μm-sized gypsum, the sulfur content of which is essentially derived from pyrite oxidation. The distribution of gypsum is highly correlated with the fissure network of the damaged zone due to excavation of the gallery. Its presence is also often associated with a loss of cohesion of the concrete/claystone interface. Due to the small amounts of gypsum and its μm-size, measurements were performed by ion microprobe. Adaptations were needed on account of the reactivity of gypsum and sulfates in general under the beam. The use of ion microprobe analysis provided evidence of high local isotopic heterogeneity that could be attributed to kinetic fractionation effects. Some analyses suggest a minor contribution of dissolved sulfates in pore water of claystone and possibly of concrete. The perturbation on the concrete side is marked by a significant increase in the bulk sulfur content within three millimeters of the interface with the claystone, showing a sulfur gradient from claystone to concrete. The main objective of this work was to define the extent of the chemical and mineralogical perturbations, taking into account in situ URL conditions, i.e. hydrodynamic conditions (shotcrete sprayed on the gallery walls and subjected to ventilation of the galleries), damaged zone of claystone induced

  19. Fermentation, Hydrogen, and Sulfur Metabolism in Multiple Uncultivated Bacterial Phyla

    SciTech Connect

    Wrighton, Kelly C.; Thomas, Brian C.; Sharon, I.; Miller, Christopher S.; Castelle, Cindy; VerBerkmoes, Nathan C.; Wilkins, Michael J.; Hettich, Robert L.; Lipton, Mary S.; Williams, Kenneth H.; Long, Philip E.; Banfield, Jillian F.

    2012-09-27

    BD1-5, OP11, and OD1 bacteria have been widely detected in anaerobic environments, but their metabolisms remain unclear owing to lack of cultivated representatives and minimal genomic sampling. We uncovered metabolic characteristics for members of these phyla, and a new lineage, PER, via cultivation-independent recovery of 49 partial to near-complete genomes from an acetate-amended aquifer. All organisms were nonrespiring anaerobes predicted to ferment. Three augment fermentation with archaeal-like type II and III ribulose-1,5-bisphosphate carboxylase-oxygenase (RuBisCO) that couples adenosine monophosphate salvage with CO2 fixation, a pathway previously not described in Bacteria. Members of OD1 reduce sulfur and may pump protons using archaeal-type hydrogenases. For six organisms, the UGA stop codon is translated as tryptophan. All bacteria studied here may play previously unrecognized roles in hydrogen production, sulfur cycling, and fermentation of refractory sedimentary carbon.

  20. Fermentation, Hydrogen, and Sulfur Metabolism in Multiple Uncultivated Bacterial Phyla

    SciTech Connect

    Wrighton, Kelly C.; Thomas, BC; Sharon, I; Miller, CS; Castelle, Cindy J; Verberkmoes, Nathan C; Wilkins, Michael J.; Hettich, Robert {Bob} L; Lipton, Mary S; Williams, Ken; Long, Philip E; Banfield, Jillian F.

    2012-01-01

    BD1-5, OP11, and OD1 bacteria have been widely detected in anaerobic environments, but their metabolisms remain unclear owing to lack of cultivated representatives and minimal genomic sampling. We uncovered metabolic characteristics for members of these phyla, and a new lineage, PER, via cultivation-independent recovery of 49 partial to near-complete genomes from an acetate-amended aquifer. All organisms were nonrespiring anaerobes predicted to ferment. Three augment fermentation with archaeal-like hybrid type II/III ribulose-1,5-bisphosphate carboxylase-oxygenase (RuBisCO) that couples adenosine monophosphate salvage with CO2 fixation, a pathway not previously described in Bacteria. Members of OD1 reduce sulfur and may pump protons using archaeal-type hydrogenases. For six organisms, the UGA stop codon is translated as tryptophan. All bacteria studied here may play previously unrecognized roles in hydrogen production, sulfur cycling, and fermentation of refractory sedimentary carbon.

  1. An Ion Microprobe Study of Fractionated Sulfur Isotopes in Hydrothermal Sulfides of the Kaidun Meteorite Breccia

    NASA Astrophysics Data System (ADS)

    McSween, H. Y., Jr.; Riciputi, L. R.; Paterson, B. A.

    1996-03-01

    The Kaidun breccia contains diverse clasts of enstatite and carbonaceous chondrite, identified by their petrography and oxygen isotopic compositions. One distinctive lithology, classified as CM1 to reflect its CM parentage and highly altered state, contains texturally unusual pyrrhotite needles wrapped in sheaths of phyllosilicate, as well as aggregates and crosscutting veins of pentlandite. The unique textures and associated alteration minerals (serpentine, saponite, melanite garnet, framboidal magnetite) indicate that these sulfides formed in a precursor parent body by reactions with hydrothermal fluids at temperatures as high as 450 degrees C . The alteration conditions recorded by these clasts are extreme in comparison to other carbonaceous chondrites, and coated, jackstraw pyrrhotites are unknown from other meteorites. Thus, it is important to document the reaction products as completely as possible. Here we report the results of in situ analyses of sulfur isotopes in Kaidun pyrrhotite and pentlandite, obtained using a Cameca ims-4f ion microprobe.

  2. Sulfur isotope dynamics in two central european watersheds affected by high atmospheric deposition of SO x

    NASA Astrophysics Data System (ADS)

    Novák, Martin; Kirchner, James W.; Groscheová, Hana; Havel, Miroslav; Černý, Jiří; Krejčí, Radovan; Buzek, František

    2000-02-01

    Sulfur fluxes and δ34S values were determined in two acidified small watersheds located near the Czech-German border, Central Europe. Sulfur of sulfate aerosol in the broader region (mean δ 34S of 7.5‰ CDT) was isotopically heavier than sulfur of airborne SO 2 (mean δ 34S of 4.7‰). The annual atmospheric S deposition to the Jezeřı´ watershed decreased markedly in 1993, 1994, and 1995 (40, 33, and 29 kg/ ha · yr), reflecting reductions in industrial S emissions. Sulfur export from Jezeří via surface discharge was twice atmospheric inputs, and increased from 52 to 58 to 85 kg/ha · yr over the same three-year period. The δ 34S value of Jezeřı´ streamflow was 4.5 ± 0.3‰, intermediate between the average atmospheric deposition (5.4 ± 0.2‰) and soil S (4.0 ± 0.5‰), suggesting that the excess sulfate in runoff comes from release of S from the soil. Bedrock is not a plausible source of the excess S, because its S concentration is very low (<0.003 wt.%) and because its δ 34S value is too high (5.8‰) to be consistent with the δ 34S of runoff. A sulfur isotope mixing model indicated that release of soil S accounted for 64 ± 33% of sulfate S in Jezeřı´ discharge. Approximately 30% of total sulfate S in the discharge were organically cycled. At Načetı´n, the same sequence of δ34S IN > δ34S OUT > δ34S SOIL was observed. The seasonality found in atmospheric input (higher δ 34S in summer, lower δ 34S in winter) was preserved in shallow (<10 cm) soil water, but not in deeper soil water. δ 34S values of deeper (>10 cm) soil water (4.8 ± 0.2‰) were intermediate between those of atmospheric input (5.9 ± 0.3‰) and Nac̆etín soils (2.4 ± 0.1‰), again suggesting that remobilization of soil S accounts for a significant fraction (roughly 40 ± 10%) of the S in soil water at Načetı´n. The inventories of soil S at both of these sites are legacies of more intense atmospheric pollution during previous decades, and are large enough (740

  3. Gas-phase Mechanisms of Sulfur Isotope Mass-independent Fractionation

    NASA Astrophysics Data System (ADS)

    Lyons, J. R.

    2006-12-01

    Mass-independent fractionation (MIF) in sulfur isotopes in ancient sulfur-bearing rocks (Farquhar et al. 2000a) is interpreted as evidence for gas-phase MIF processes in the early Earth atmosphere. This interpretation is made by analogy with oxygen isotope MIF in the modern atmosphere (produced during ozone formation), and by laboratory photolysis experiments on SO2 (Farquhar et al. 2001; Wing et al. 2004) that yield both elemental sulfur and sulfate with S MIF signatures at wavelengths above and below the SO2 dissociation limit. What is lacking is a quantitative understanding of the mechanisms of gas-phase S MIF. Quantification is essential in order to extract the full implications of sulfur MIF throughout Earth history, including for bacterial sulfate reduction processes which largely conserve D33S and D36S. Several sulfur MIF mechanisms are possible. The most obvious is the gas-phase thiozone reaction, which is isovalent to the ozone formation reaction. Ozone formation produces a well-known MIF signature in oxygen isotopes (Thiemens and Heidenreich 1983), and a symmetry-dependent non-RRKM mechanism has been proposed as the origin of O MIF (Gao and Marcus 2001). It is possible and perhaps likely that S3 formation also proceeds by a non-RRKM process. Data are lacking on isotopic (an even non-isotopic) rates of S3 formation, so it is not possible to make definitive statements about MIF in S3 at this time. However modeling results suggest that the vapor pressure of S2 is too low for gas-phase S3 formation to be significant. Two additional species that may exhibit a non-RRKM MIF signature are S2O2 and S4. Again, there is a lack of isotopomer-specific kinetic data for these reactions, and gas-phase formation of S4 is likely inconsequential. Perhaps the most obvious mechanism is simply the primary act of SO2 photolysis. The SO2 absorption spectrum is highly structured, with strong vibronic bands above and below the dissociation limit. In contrast H2S, with its mostly

  4. The ecophysiology of sulfur isotope fractionation by sulfate reducing bacteria in response to variable environmental conditions

    NASA Astrophysics Data System (ADS)

    Leavitt, W.; Bradley, A. S.; Johnston, D. T.; Pereira, I. A. C.; Venceslau, S.; Wallace, C.

    2014-12-01

    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 sulfide produced is depleted in the heavier isotopes of sulfur relative to sulfate. The magnitude of discrimination (fractionation) depends on: i) the cell-specific sulfate reduction rate (csSRR, Kaplan & Rittenberg (1964) Can. J. Microbio.; Chambers et al. (1975) Can. J. Microbio; Sim et al. (2011) GCA; Leavitt et al. (2013) PNAS), ii) the ambient sulfate concentration (Harrison & Thode (1958) Research; Habicht et al. (2002) Science; Bradley et al. in review), iii) both sulfate and electron donor availability, or iv) an intrinsic physiological limitation (e.g. cellular division rate). When neither sulfate nor electron donor limits csSRR a more complex function relates the magnitude of isotope fractionation to cell physiology and environmental conditions. In recent and on-going work we have examined the importance of enzyme-specific fractionation factors, as well as the influence of electron donor or electron acceptor availability under carefully controlled culture conditions (e.g. Leavitt et al. (2013) PNAS). In light of recent advances in MSR genetics and biochemistry we utilize well-characterized mutant strains, along with a continuous-culture methodology (Leavitt et al. (2013) PNAS) to further probe the fractionation capacity of this metabolism under controlled physiological conditions. We present our latest findings on the magnitude of S and D/H isotope fractionation in both wild type and mutant strains. We will discuss these in light of recent theoretical advances (Wing & Halevy (2014) PNAS), examining the mode and relevance of MSR isotope fractionation in the laboratory to modern and ancient environmental settings, particularly anoxic marine sediments.

  5. Rethinking the Ancient Sulfur Cycle

    NASA Astrophysics Data System (ADS)

    Fike, David A.; Bradley, Alexander S.; Rose, Catherine V.

    2015-05-01

    The sulfur biogeochemical cycle integrates the metabolic activity of multiple microbial pathways (e.g., sulfate reduction, disproportionation, and sulfide oxidation) along with abiotic reactions and geological processes that cycle sulfur through various reservoirs. The sulfur cycle impacts the global carbon cycle and climate primarily through the remineralization of organic carbon. Over geological timescales, cycling of sulfur is closely tied to the redox state of Earth's exosphere through the burial of oxidized (sulfate) and reduced (sulfide) sulfur species in marine sediments. Biological sulfur cycling is associated with isotopic fractionations that can be used to trace the fluxes through various metabolic pathways. The resulting isotopic data provide insights into sulfur cycling in both modern and ancient environments via isotopic signatures in sedimentary sulfate and sulfide phases. Here, we review the deep-time δ34S record of marine sulfates and sulfides in light of recent advances in understanding how isotopic signatures are generated by microbial activity, how these signatures are encoded in marine sediments, and how they may be altered following deposition. The resulting picture shows a sulfur cycle intimately coupled to ambient carbon cycling, where sulfur isotopic records preserved in sedimentary rocks are critically dependent on sedimentological and geochemical conditions (e.g., iron availability) during deposition.

  6. Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

    USGS Publications Warehouse

    Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C., III

    2010-01-01

    Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

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

    NASA Technical Reports Server (NTRS)

    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.

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

    PubMed Central

    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. PMID:11536609

  9. Linking Food Webs and Biogeochemical Processes in Wetlands: Insights From Sulfur Isotopes

    NASA Astrophysics Data System (ADS)

    Stricker, C. A.; Guntenspergen, G. R.; Rye, R. O.

    2005-05-01

    To better understand the transfer of nutrients into prairie wetland food webs we have investigated the cycling of S (via S isotope systematics and geochemistry) in a prairie wetland landscape by characterizing sources (ground water, interstitial water, surface water) and processes in a small catchment comprised of four wetlands in eastern South Dakota. We focused on S to derive process information that is not generally available from carbon isotopes alone. The wetlands chosen for study spanned a considerable range in SO4 concentration (0.1-13.6 mM), which corresponded with landscape position. Ground water δ34SSO4 values remained relatively constant (mean = -13.2 per mil) through time. However, δ34SSO4 values of wetland surface waters ranged from -2.9 to -30.0 per mil (CDT) and were negatively correlated with SO4 concentrations (p<0.05). The isotopic variability of surface water SO4 resulted from mixing with re-oxidized sulfides associated with recently flushed wetland soils. The δ34S signatures of wetland primary (Gastropoda: Stagnicola elodes) and secondary (Odonata: Anax sp.) consumers were significantly related to surface water δ34SSO4 values (p<0.05) suggesting that food web components were responding to changes in the isotopic composition of the S source. Both primary and secondary consumer δ34S signatures differed between wetlands (ANOVA, p<0.05). These data illustrate the complexity of S cycling in prairie wetlands and the influence of wetland hydrologic and biogeochemical processes on prairie wetland food webs. Additionally, this work has demonstrated that sulfur isotopes can provide unique source and process information that cannot be derived from traditional carbon and nitrogen isotope studies.

  10. Nitrogen, carbon, and sulfur isotopic change during heterotrophic (Pseudomonas aureofaciens) and autotrophic (Thiobacillus denitrificans) denitrification reactions

    NASA Astrophysics Data System (ADS)

    Hosono, Takahiro; Alvarez, Kelly; Lin, In-Tian; Shimada, Jun

    2015-12-01

    In batch culture experiments, we examined the isotopic change of nitrogen in nitrate (δ15NNO3), carbon in dissolved inorganic carbon (δ13CDIC), and sulfur in sulfate (δ34SSO4) during heterotrophic and autotrophic denitrification of two bacterial strains (Pseudomonas aureofaciens and Thiobacillus denitrificans). Heterotrophic denitrification (HD) experiments were conducted with trisodium citrate as electron donor, and autotrophic denitrification (AD) experiments were carried out with iron disulfide (FeS2) as electron donor. For heterotrophic denitrification experiments, a complete nitrate reduction was accomplished, however bacterial denitrification with T. denitrificans is a slow process in which, after seventy days nitrate was reduced to 40% of the initial concentration by denitrification. In the HD experiment, systematic change of δ13CDIC (from - 7.7‰ to - 12.2‰) with increase of DIC was observed during denitrification (enrichment factor εN was - 4.7‰), suggesting the contribution of C of trisodium citrate (δ13C = - 12.4‰). No SO42 - and δ34SSO4 changes were observed. In the AD experiment, clear fractionation of δ13CDIC during DIC consumption (εC = - 7.8‰) and δ34SSO4 during sulfur use of FeS2-S (around 2‰), were confirmed through denitrification (εN = - 12.5‰). Different pattern in isotopic change between HD and AD obtained on laboratory-scale are useful to recognize the type of denitrification occurring in the field.

  11. Nitrogen, carbon, and sulfur isotopic change during heterotrophic (Pseudomonas aureofaciens) and autotrophic (Thiobacillus denitrificans) denitrification reactions.

    PubMed

    Hosono, Takahiro; Alvarez, Kelly; Lin, In-Tian; Shimada, Jun

    2015-12-01

    In batch culture experiments, we examined the isotopic change of nitrogen in nitrate (δ(15)NNO3), carbon in dissolved inorganic carbon (δ(13)CDIC), and sulfur in sulfate (δ(34)SSO4) during heterotrophic and autotrophic denitrification of two bacterial strains (Pseudomonas aureofaciens and Thiobacillus denitrificans). Heterotrophic denitrification (HD) experiments were conducted with trisodium citrate as electron donor, and autotrophic denitrification (AD) experiments were carried out with iron disulfide (FeS2) as electron donor. For heterotrophic denitrification experiments, a complete nitrate reduction was accomplished, however bacterial denitrification with T. denitrificans is a slow process in which, after seventy days nitrate was reduced to 40% of the initial concentration by denitrification. In the HD experiment, systematic change of δ(13)CDIC (from -7.7‰ to -12.2‰) with increase of DIC was observed during denitrification (enrichment factor εN was -4.7‰), suggesting the contribution of C of trisodium citrate (δ(13)C=-12.4‰). No SO4(2-) and δ(34)SSO4 changes were observed. In the AD experiment, clear fractionation of δ(13)CDIC during DIC consumption (εC=-7.8‰) and δ(34)SSO4 during sulfur use of FeS2-S (around 2‰), were confirmed through denitrification (εN=-12.5‰). Different pattern in isotopic change between HD and AD obtained on laboratory-scale are useful to recognize the type of denitrification occurring in the field. PMID:26529303

  12. Concentrations and isotope ratios of carbon, nitrogen and sulfur in ocean-floor basalts

    USGS Publications Warehouse

    Sakai, H.; Marais, D.J.D.; Ueda, A.; Moore, J.G.

    1984-01-01

    Fresh submarine basalt glasses from Galapagos Ridge, FAMOUS area, Cayman Trough and Kilauea east rift contain 22 to 160 ppm carbon and 0.3 to 2.8 ppm nitrogen, respectively, as the sums of dissolved species and vesicle-filling gases (CO2 and N2). The large range of variation in carbon content is due to combined effect of depth-dependency of the solubility of carbon in basalt melt and varying extents of vapour loss during magma emplacement as well as in sample crushing. The isotopic ratios of indigenous carbon and nitrogen are in very narrow ranges,-6.2 ?? 0.2% relative to PDB and +0.2 ?? 0.6 %. relative to atmospheric nitrogen, respectively. In basalt samples from Juan de Fuca Ridge, however, isotopically light carbon (??13C = around -24%.) predominates over the indigenous carbon; no indigenous heavy carbon was found. Except for Galapagos Ridge samples, these ocean-floor basalts contain 670 to 1100 ppm sulfur, averaging 810 ppm, in the form of both sulfide and sulfate, whereas basalts from Galapagos Ridge are higher in both sulfur (1490 and 1570 ppm) and iron (11.08% total iron as FeO). The ??34S values average +0.3 ?? 0.5%. with average fractionation factor between sulfate and sulfide of +7.4 ?? 1.6%.. The sulfate/sulfide ratios tend to increase with increasing water content of basalt, probably because the oxygen fugacity increases with increasing water content in basalt melt. ?? 1984.

  13. Measurements of radioactive and stable sulfur isotopes at Mt. Everest and its geochemical implications

    NASA Astrophysics Data System (ADS)

    Lin, M.; Thiemens, M. H.; Zhang, Q.; Li, C.; Kang, S.; Hsu, S. C.; Zhang, Z.; Su, L.

    2015-12-01

    The Himalayas were recently identified as a global hotspot for deep stratosphere-to-troposphere transport (STT) during spring [1]. Although STT transport in this region may play a vital role in tropospheric chemistry, the hydrological cycle and aquatic ecosystems in Asia, there is no direct measurement of a specific chemical stratospheric tracer to verify and evaluate its possible impact. Here, cosmogenic 35S tracer (half-life: ~87 days) produced in the stratosphere was measured for the first time in surface snow and river runoff samples collected at Mt. Everest in April 2013 using a low-noise liquid scintillation spectroscopy [2]. Strikingly, we find extraordinarily high concentrations of 35S in these samples (>10 times higher than the southern Tibetan Plateau), verifying the Himalayas as a gateway of springtime STT. In light of this, two studies were conducted: a) Measurements of 35SO2 and 35SO42- at the southern Tibetan Plateau reveals that the oxidative life time of SO2 is reduced to 2.1 days under the influence of aged stratospheric air masses from the Himalayas. A concept box model for estimating the influence of STT on surface O3 using 35S tracer is proposed. b) Quadruple stable sulfur isotopes in a sediment core (~250 years) from the Gokyo Lake (the world's highest freshwater lake) [3] near Mt. Everest are being measured to investigate the possible impact of STT on sulfur budget at the Himalayas. The absence of sulfide suggests that bacterial sulfate reduction may be negligible in this lake. Enrichment of uranium (EF ≈ 10) in 20th century samples highlights the impact of atmospheric deposition. S-isotope sulfate anomalies are not found (∆33S and ∆36S ≈ 0‰), implying that sulfate in this lake may be mainly contributed by eolian dust or derived from rock. This is also supported by the low enrichments of most trace elements (EF ≈ 1). Rare earth elements will be used to assist in identifying the potential sources and interpreting the variation of

  14. Sulfur isotopes of organic matter preserved in 3.45-billion-year-old stromatolites reveal microbial metabolism.

    PubMed

    Bontognali, Tomaso R R; Sessions, Alex L; Allwood, Abigail C; Fischer, Woodward W; Grotzinger, John P; Summons, Roger E; Eiler, John M

    2012-09-18

    The 3.45-billion-year-old Strelley Pool Formation of Western Australia preserves stromatolites that are considered among the oldest evidence for life on Earth. In places of exceptional preservation, these stromatolites contain laminae rich in organic carbon, interpreted as the fossil remains of ancient microbial mats. To better understand the biogeochemistry of these rocks, we performed microscale in situ sulfur isotope measurements of the preserved organic sulfur, including both Δ(33)S and . This approach allows us to tie physiological inference from isotope ratios directly to fossil biomass, providing a means to understand sulfur metabolism that is complimentary to, and independent from, inorganic proxies (e.g., pyrite). Δ(33)S values of the kerogen reveal mass-anomalous fractionations expected of the Archean sulfur cycle, whereas values show large fractionations at very small spatial scales, including values below -15‰. We interpret these isotopic patterns as recording the process of sulfurization of organic matter by H(2)S in heterogeneous mat pore-waters influenced by respiratory S metabolism. Positive Δ(33)S anomalies suggest that disproportionation of elemental sulfur would have been a prominent microbial process in these communities. PMID:22949693

  15. Sulfur isotopes of organic matter preserved in 3.45-billion-year-old stromatolites reveal microbial metabolism

    PubMed Central

    Bontognali, Tomaso R. R.; Sessions, Alex L.; Allwood, Abigail C.; Fischer, Woodward W.; Grotzinger, John P.; Summons, Roger E.; Eiler, John M.

    2012-01-01

    The 3.45-billion-year-old Strelley Pool Formation of Western Australia preserves stromatolites that are considered among the oldest evidence for life on Earth. In places of exceptional preservation, these stromatolites contain laminae rich in organic carbon, interpreted as the fossil remains of ancient microbial mats. To better understand the biogeochemistry of these rocks, we performed microscale in situ sulfur isotope measurements of the preserved organic sulfur, including both Δ33S and . This approach allows us to tie physiological inference from isotope ratios directly to fossil biomass, providing a means to understand sulfur metabolism that is complimentary to, and independent from, inorganic proxies (e.g., pyrite). Δ33S values of the kerogen reveal mass-anomalous fractionations expected of the Archean sulfur cycle, whereas values show large fractionations at very small spatial scales, including values below -15‰. We interpret these isotopic patterns as recording the process of sulfurization of organic matter by H2S in heterogeneous mat pore-waters influenced by respiratory S metabolism. Positive Δ33S anomalies suggest that disproportionation of elemental sulfur would have been a prominent microbial process in these communities. PMID:22949693

  16. Sulfur stable isotopic compositions measured on whole rock samples from the Navan Pb-Zn Mine

    NASA Astrophysics Data System (ADS)

    Davidheiser-Kroll, B.; Boyce, A. J.

    2012-12-01

    Sulfide bearing ore bodies are major geochemical anomalies that reflect changing geologic conditions. The world-class sulfide deposit at Navan, Ireland contains > 100 Mt of ore that holds > 1.5 Mt of sulfide. The economic implications of understanding these deposits allow for scientific benefit from the data sets produced. The Navan ore body is located in central Ireland along a failed rift system active during the Carboniferous and has been studied since the 1970s. The role of sulfur in the creation of the deposit gives us insights into the scale of biological pathways and is critical to understanding the exploration potential within Ireland as well as the creation of such geochemical anomalies. The two main sources of sulfur identified at Navan have been a hydrothermal component (δ34S = +10 to +15‰) from the deep crust as well as a shallow sulfur component (δ34S = -25 to -50‰) from bacteriogenic sulfate reducing bacteria (Anderson 1989). The major methods used to understand the sulfur isotopes of the Irish ore fields have been conventional techniques, using mineral separates or micro-drilled minerals, as well as in situ laser analyses. These methods have all been applied to well-categorized (petrographically and texturally) samples and have data sets that range in the low hundreds. It is thought these studies bias analyses towards hydrothermal sources due to grain size differences, and it has been shown that over 90% of sulfide originated as shallow seawater sulfate that was reduced by bacteriogenic metabolisms (Fallick et al 2002). Here, we are able to see how the two distinct δ34S fluids interacted on a larger (km) scale. This is made feasible by using the milled sections of diamond drill core created by normal mining operations. We have measured δ34S on 75 whole rock core samples that have also been analyzed geochemically by ICP-MS. The range in δ34S is from -32.6 to -4.0‰, providing confidence that we are seeing the full range of mixing of the two

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

    NASA Astrophysics Data System (ADS)

    Pašava, Jan; Tornos, Fernando; Chrastný, Vladislav

    2014-10-01

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

  18. Complex Sedimentary and Tectonic Events Captured in Stable Sulfur Isotope Profiles from the IODP Expedition 344

    NASA Astrophysics Data System (ADS)

    Gott, C.; Riedinger, N.; Torres, M. E.; Solomon, E. A.; Bates, S. M.; Lyons, T. W.

    2014-12-01

    The impact of dynamic sedimentary and tectonic systems on biogeochemical processes, particularly the sulfur cycle, is poorly understood. To better elucidate these relationships, analyses were conducted on sediments collected during Integrated Ocean Drilling Project (IODP) Expedition 344. A primary goal of the CRISP (Costa Rica Seismogenesis Project) expedition is to explore diagenetic processes, e.g. fluid flow; relating to the complex sedimentary and tectonic environments along the Costa Rica margin. Samples collected from sites U1381C, U1413B, and U1414A record non-steady state conditions in both the solid phase and the pore water profiles, although it is most pronounced in the latter. The penetration depth of pore water sulfate at these sites varies strongly with depth between 100, 15 and several hundreds of meters, respectively. The corresponding hydrogen sulfide concentrations are >400 μM at Holes U1381C, and U1413B while they are <4 μM at Hole U1414A. The measured concentrations of iron sulfides in the sediments indicate that pyrite is the main sulfur-bearing mineral, with concentrations of 2-3 wt. % at sites U1413B and U1414A. Recorded in the sulfur isotope signal is the likely origin of the heterogeneity between sites. At Site U1414, the 34S isotopically enriched sulfate (δ34S>+60 ‰) is reflected in the δ34S profile of the in situ iron sulfides. We interpret these data as being indicative of fluid flow, potentially along fracture zones, seeps and/or pockmark features seen elsewhere in this region.

  19. Fractionation of Sulfur Isotopes by Desulfovibrio vulgaris Mutants Lacking Periplasmic Hydrogenases or the Type I Tetraheme Cytochrome c3

    NASA Astrophysics Data System (ADS)

    Sim, M.; Ono, S.; Bosak, T.

    2012-12-01

    A large fraction of anaerobic mineralization of organic compounds relies on microbial sulfate reduction. Sulfur isotope fractionation by these microbes has been widely used to trace the biogeochemical cycling of sulfur and carbon, but intracellular mechanisms behind the wide range of fractionations observed in nature and cultures are not fully understood. In this study, we investigated the influence of electron transport chain components on the fractionation of sulfur isotopes by culturing Desulfovibrio vulgaris Hildenborough mutants lacking hydrogenases or type I tetraheme cytochrome c3 (Tp1-c3). The mutants were grown both in batch and continuous cultures. All tested mutants grew on lactate or pyruvate as the sole carbon and energy sources, generating sulfide. Mutants lacking cytoplasmic and periplasmic hydrogenases exhibited similar growth physiologies and sulfur isotope fractionations to their parent strains. On the other hand, a mutant lacking Tp1-c3 (ΔcycA) fractionated the 34S/32S ratio more than the wild type, evolving H2 in the headspace and exhibiting a lower specific respiration rate. In the presence of high concentrations of pyruvate, the growth of ΔcycA relied largely on fermentation rather than sulfate reduction, even when sulfate was abundant, producing the largest sulfur isotope effect observed in this study. Differences between sulfur isotope fractionation by ΔcycA and the wild type highlight the effect of electron transfer chains on the magnitude of sulfur isotope fractionation. Because Tp1-c3 is known to exclusively shuttle electrons from periplasmic hydrogenases to transmembrane complexes, electron transfers in the absence of Tp1-c3 should bypass the periplasmic hydrogen cycling, and the loss of reducing equivalents in the form of H2 can impair the flow of electrons from organic acids to sulfur, increasing isotope fractionation. Larger fractionation by ΔcycA can inform interpretations of sulfur isotope data at an environmental scale as well

  20. [Investigations on Sulfur and Carbon Isotopic Compositions of Potential Polluted Sources in Atmospheric PM₂.₅ in Nanjing Region].

    PubMed

    Shi, Lei; Guo, Zhao-bing; Jiang, Wen-juan; Rui, Mao-ling; Zeng, Gang

    2016-01-15

    Potential pollution sources of atmospheric PM₂.₅ in Nanjing region were collected, and sulfur and carbon isotopic compositions were determined by EA-IRMS synchronously. The results showed that δ³⁴S and δ¹³C values ranged from 1.8‰-3.7‰ and -25.50‰- -23.57‰ in coal soot particles; 4.6‰-9.7‰ and -26.32‰- -23.57‰ in vehicle exhaust; 5.2‰-9.9‰ and -19.30‰- -30.42‰ in straw soot particles, respectively. Besides, the δ¹³C value of dust was -13.45‰. It can be observed that sulfur isotopic compositions in coal soot were lower, while the carbon isotopic composition in dust was higher. Comparing with δ³⁴S and δ¹³C values in domestic and foreign polluted sources, we found that sulfur and carbon isotopes in atmospheric PM₂.₅ in Nanjing region presented an obvious regional characteristics. Therefore, the source spectrum of sulfur and carbon isotopic compositions in Nanjing region might provide an insight into source apportionment of atmospheric PM₂.₅. PMID:27078936

  1. Patterns of mortality among South Florida Manatees: Evidence from oxygen, sulfur and deuterium stable isotopes

    NASA Astrophysics Data System (ADS)

    MacAvoy, S. E.; Bacalan, V.; Kazantseva, M.; Rhodes, J.; Kim, K.

    2012-12-01

    The Florida manatee (Trichechus manatus latirostris) is an endangered marine mammal whose coastal habitat has been heavily altered by human development. Sources of mortality include anthropogenic and environmental causes. Necropsies were completed on 75 deceased individuals, and tissues, including bone samples, were collected for later analysis. This study investigates the utility of manatee bone stable oxygen (δ18O), sulfur (δ34S) and deuterium (δD) for determining where the animals lived (which may not be where they where their bodies were recovered), and the relative importance of marine versus freshwater for the individual animals. The isotopes can provide a "geochemical map" showing the distribution of mortality, aiding in the evaluation of geographical patterns in mortality. The δ18O signatures of the bones ranged from 14 to 18.5‰, with no significant difference between male and female mean values. δ18O significantly decreased with increasing latitude (p=.0016), a trend positively correlated with coastal Florida seawater δ18O literature values obtained from the NASA Global Seawater Oxygen-18 Database (http://data.giss.nasa.gov/o18data/) and the EAIA stable isotope database (http://www.univie.ac.at/cartography/project/wiser/). Bone δ34S indicated the influence of marine versus coastal freshwater dietary sources on the animals. Most individuals showed 34S-depleted signatures, which indicated a non-marine sulfur source; however some individuals clearly had taken up marine sulfate (mean 4.9 ± 3.7‰, range 0.8 to 13.8‰). Deuterium values were not available at the time this abstract was written, however we hypothesize that those values will co-vary with δ18O. We conclude that manatee diets are based on both marine and freshwater sources, but freshwater sources exert more influence. Marine water and manatee δ18O co-vary with latitude, suggesting that stable oxygen isotopes may be useful indicators of the latitude where manatees lived.

  2. Use of stable sulfur isotopes to identify sources of sulfate in Rocky Mountain snowpacks

    USGS Publications Warehouse

    Mast, M.A.; Turk, J.T.; Ingersoll, G.P.; Clow, D.W.; Kester, C.L.

    2001-01-01

    Stable sulfur isotope ratios and major ions in bulk snowpack samples were monitored at a network of 52 high-elevation sites along and near the Continental Divide from 1993 to 1999. This information was collected to better define atmospheric deposition to remote areas of the Rocky Mountains and to help identify the major source regions of sulfate in winter deposition. Average annual ??34S values at individual sites ranged from + 4.0 to + 8.2??? and standard deviations ranged from 0.4 to 1.6???. The chemical composition of all samples was extremely dilute and slightly acidic; average sulfate concentrations ranged from 2.4 to 12.2 ??eql-1 and pH ranged from 4.82 to 5.70. The range of ??34S values measured in this study indicated that snowpack sulfur in the Rocky Mountains is primarily derived from anthropogenic sources. A nearly linear relation between ??34S and latitude was observed for sites in New Mexico, Colorado, and southern Wyoming, which indicates that snowpack sulfate in the southern part of the network was derived from two isotopically distinct source regions. Because the major point sources of SO2 in the region are coal-fired powerplants, this pattern may reflect variations in the isotopic composition of coals burned by the plants. The geographic pattern in ??34S for sites farther to the north in Wyoming and Montana was much less distinct, perhaps rflecting the paucity of major point sources of SO2 in the northern part of the network.

  3. Combined Sulfur K-edge XANES Spectroscopy and Stable Isotope Analysis of Fulvic Acids and Groundwater Sulfate Identify Sulfur Cycling in a Karstic Catchment Area

    SciTech Connect

    Einsiedl,F.; Schafer, T.; Northrup, P.

    2007-01-01

    Chemical and isotope analyses on groundwater sulfate, atmospheric deposition sulfate and fulvic acids (FAs) associated sulfur were used to determine the S cycling in a karstic catchment area of the Franconian Alb, Southern Germany. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy provided information on the oxidation state and the mechanism of the incorporation of sulfur in FAs. During base flow {delta}{sup 34}S values of groundwater sulfate were slightly depleted to those of recent atmospheric sulfate deposition with mean amount-weighted {delta}{sup 34}S values of around + 3{per_thousand}. The {delta}{sup 18}O values of groundwater sulfate shifted to lower values compared to those of atmospheric deposition and indicated steadiness from base flow to peak flow. The reduced sulfur species (S{sub -1}/thiol; S{sub 0}/thiophene, disulfide, S{sub +2}2/sulfoxide) of soil FAs averaged around 49% of the total sulfur and {delta}{sup 34}S value in FAs was found to be 0.5{per_thousand}. The formation of polysulfides and thiols in FAs in concert with a decreasing isotope value of {delta}{sup 34}S in FAs with respect to those of atmospheric deposition sulfate suggests oxidation of H{sub 2}S, enriched in the {sup 32}S isotope, with organic material. The depletion of {delta}{sup 18}O-SO{sub 4}{sup 2-} by several per mil in groundwater sulfate with respect to those of atmospheric deposition is, therefore, consistent with the hypothesis that SO{sub 4}{sup 2-} has been cycled through the organic S pool as well as that groundwater sulfate is formed by oxidation of H{sub 2}S with organic matter in the mineral soil of the catchment area.

  4. Multi-isotope biogeochemistry of sulfur in the water column and surface sediments of the Baltic Sea

    NASA Astrophysics Data System (ADS)

    Böttcher, M. E.; Kamyshny, A.; Dellwig, O.; Farquhar, J.

    2012-04-01

    The anoxic deeps of the modern Baltic Sea with the temporal development of a pelagic redoxcline offer the opportunity to study the fundamental processes in the sulfur cycle of natural dynamic euxinic systems. In the low-temperature sulfur cycle multi-sulfur isotope discrimination has been found to be of particular value for the evaluation of fundamental biogeochemical processes and has, therefore, reached a lot of attention within the past decade. We analyzed the concentrations and stable sulfur isotope (S-32, S-33, S-34, S-36) compositions of dissolved sulfide and sulfate, as well as elemental sulfur in the water column, and of sulfate, acid-volatile sulfide (FeS + HS-) and CrII-reducible sulfur (essentially pyrite) in surface sediments of several stations in the Landsort Deep (LD) and the Gotland Basin (GB). Samples were recovered during several research cruises to the Baltic Sea. Water column samples were obtained via the IOW pump-CTD system or a conventional CTD-rosette system; short sediment cores were retrieved with a multi coring device. Special focus was set on the zone at and below the pelagic redoxcline. Stable isotope results are compared to previous measurements of the traditional sulfur isotopes (S-32, S-34), and findings from other euxinic systems. The direct correlation between salinity and dissolved sulfate and the low concentrations of dissolved sulfide (below 40 µM in the LD and 130 µM in the GB) indicate that now significant net pelagic sulfate reduction took place. Most of the sulfide originates from microbial processes in the surface sediments and further diffusion into the water column. The magnitude of overall 34S/32S discrimination between dissolved sulfate and sulfide in the anoxic water column was 49±1 (LD) and 46±2 (GB) per mil, with only small vertical variations and significantly smaller than in the modern Black Sea. This partitioning is within the range of published results found in experiments with pure cultures of sulfate

  5. Sulfur Isotopic Inferences of the Controls on Porewater Sulfate Profiles in the Northern Cascadia Margin Gas Hydrate System

    NASA Astrophysics Data System (ADS)

    Bui, T.; Pohlman, J.; Lapham, L.; Riedel, M.; Wing, B. A.

    2010-12-01

    The flux of methane from gas hydrate bearing seeps in the marine environment is partially mitigated by the anaerobic oxidation of methane coupled with sulfate reduction. Sedimentary porewater sulfate profiles above gas hydrate deposits are frequently used to estimate the efficacy of this important microbial biofilter. However, to differentiate how other processes (e.g., sulfate reduction coupled to organic matter oxidation, sulfide re-oxidation and sulfur disproportionation) affect sulfate profiles, a complete accounting of the sulfur cycle is necessary. To this end, we have obtained the first ever measurements of minor sulfur isotopic ratios (33S/32S, 36S/32S), in conjunction with the more commonly measured 34S -32S ratio, from porewater sulfate above a gas hydrate-bearing seep. Characteristic minor isotopic fractionations, even when major isotopic fractionations are similar in magnitude, help to quantify the contributions of different microbial processes to the overall sulfur cycling in the system. Down to sediment depths of 1.5 to 4 meters, the δ34S values of porewater sulfate generally increased in association with a decrease in sulfate concentrations as would be expected for active sulfate reduction. Of greater interest, covariance between the δ34S values and measured minor isotopic fractionation suggests sulfide reoxidation and sulfur disproportionation are important components of the local sulfur cycle. We hypothesize that sulfide reoxidation is coupled to redox processes involving Fe(III) and Mn(IV) reduction and that the reoxidized forms of sulfur are available for additional methane oxidation. Recognizing that sulfate reduction is only one of several microbial processes controlling sulfate profiles challenges current paradigms for interpreting sulfate profiles and may alter our understanding of methane oxidation at gas hydrate-bearing seeps.

  6. Pigment production and isotopic fractionations in continuous culture: okenone producing purple sulfur bacteria Part II.

    PubMed

    Smith, D A; Steele, A; Fogel, M L

    2015-05-01

    Okenone is a carotenoid pigment unique to certain members of Chromatiaceae, the dominant family of purple sulfur bacteria (PSB) found in euxinic photic zones. Diagenetic alteration of okenone produces okenane, the only recognized molecular fossil unique to PSB. The in vivo concentrations of okenone and bacteriochlorophyll a (Bchl a) on a per cell basis were monitored and quantified as a function of light intensity in continuous cultures of the purple sulfur bacterium Marichromatium purpuratum (Mpurp1591). We show that okenone-producing PSB have constant bacteriochlorophyll to carotenoid ratios in light-harvesting antenna complexes. The in vivo concentrations of Bchl a, 0.151 ± 0.012 fmol cell(-1), and okenone, 0.103 ± 0.012 fmol cell(-1), were not dependent on average light intensity (10-225 Lux) at both steady and non-steady states. This observation revealed that in autotrophic continuous cultures of Mpurp1591, there was a constant ratio for okenone to Bchl a of 1:1.5. Okenone was therefore constitutively produced in planktonic cultures of PSB, regardless of light intensity. This confirms the legitimacy of okenone as a signature for autotrophic planktonic PSB and by extrapolation water column euxinia. We measured the δ(13)C, δ(15)N, and δ(34)S bulk biomass values from cells collected daily and determined the isotopic fractionations of Mpurp1591. There was no statistical relationship in the bulk isotope measurements or stable isotope fractionations to light intensity or cell density under steady and non-steady-state conditions. The carbon isotope fractionation between okenone and Bchl a with respect to overall bulk biomass ((13)ε pigment - biomass) was 2.2 ± 0.4‰ and -4.1 ± 0.9‰, respectively. The carbon isotopic fractionation (13ε pigment-CO2) for the production of pigments in PSB is more variable than previously thought with our reported values for okenone at -15.5 ± 1.2‰ and -21.8 ± 1.7‰ for Bchl a. PMID:25857754

  7. Production, preservation, and biological processing of mass-independent sulfur isotope fractionation in the Archean surface environment

    PubMed Central

    Halevy, Itay

    2013-01-01

    Mass-independent fractionation of sulfur isotopes (S MIF) in Archean and Paleoproterozoic rocks provides strong evidence for an anoxic atmosphere before ∼2,400 Ma. However, the origin of this isotopic anomaly remains unclear, as does the identity of the molecules that carried it from the atmosphere to Earth’s surface. Irrespective of the origin of S MIF, processes in the biogeochemical sulfur cycle modify the primary signal and strongly influence the S MIF preserved and observed in the geological record. Here, a detailed model of the marine sulfur cycle is used to propagate and distribute atmospherically derived S MIF from its delivery to the ocean to its preservation in the sediment. Bulk pyrite in most sediments carries weak S MIF because of microbial reduction of most sulfur compounds to form isotopically homogeneous sulfide. Locally, differential incorporation of sulfur compounds into pyrite leads to preservation of S MIF, which is predicted to be most highly variable in nonmarine and shallow-water settings. The Archean ocean is efficient in diluting primary atmospheric S MIF in the marine pools of sulfate and elemental sulfur with inputs from SO2 and H2S, respectively. Preservation of S MIF with the observed range of magnitudes requires the S MIF production mechanism to be moderately fractionating (20–40‰). Constraints from the marine sulfur cycle allow that either elemental sulfur or organosulfur compounds (or both) carried S MIF to the surface, with opposite sign to S MIF in SO2 and H2SO4. Optimal progress requires observations from nonmarine and shallow-water environments and experimental constraints on the reaction of photoexcited SO2 with atmospheric hydrocarbons. PMID:23572589

  8. Production, preservation, and biological processing of mass-independent sulfur isotope fractionation in the Archean surface environment.

    PubMed

    Halevy, Itay

    2013-10-29

    Mass-independent fractionation of sulfur isotopes (S MIF) in Archean and Paleoproterozoic rocks provides strong evidence for an anoxic atmosphere before ~2,400 Ma. However, the origin of this isotopic anomaly remains unclear, as does the identity of the molecules that carried it from the atmosphere to Earth's surface. Irrespective of the origin of S MIF, processes in the biogeochemical sulfur cycle modify the primary signal and strongly influence the S MIF preserved and observed in the geological record. Here, a detailed model of the marine sulfur cycle is used to propagate and distribute atmospherically derived S MIF from its delivery to the ocean to its preservation in the sediment. Bulk pyrite in most sediments carries weak S MIF because of microbial reduction of most sulfur compounds to form isotopically homogeneous sulfide. Locally, differential incorporation of sulfur compounds into pyrite leads to preservation of S MIF, which is predicted to be most highly variable in nonmarine and shallow-water settings. The Archean ocean is efficient in diluting primary atmospheric S MIF in the marine pools of sulfate and elemental sulfur with inputs from SO2 and H2S, respectively. Preservation of S MIF with the observed range of magnitudes requires the S MIF production mechanism to be moderately fractionating ( 20-40‰). Constraints from the marine sulfur cycle allow that either elemental sulfur or organosulfur compounds (or both) carried S MIF to the surface, with opposite sign to S MIF in SO2 and H2SO4. Optimal progress requires observations from nonmarine and shallow-water environments and experimental constraints on the reaction of photoexcited SO2 with atmospheric hydrocarbons. PMID:23572589

  9. Determination of the sulfur isotope ratio in carbonyl sulfide using gas chromatography/isotope ratio mass spectrometry on fragment ions 32S+, 33S+, and 34S+.

    PubMed

    Hattori, Shohei; Toyoda, Akari; Toyoda, Sakae; Ishino, Sakiko; Ueno, Yuichiro; Yoshida, Naohiro

    2015-01-01

    Little is known about the sulfur isotopic composition of carbonyl sulfide (OCS), the most abundant atmospheric sulfur species. We present a promising new analytical method for measuring the stable sulfur isotopic compositions (δ(33)S, δ(34)S, and Δ(33)S) of OCS using nanomole level samples. The direct isotopic analytical technique consists of two parts: a concentration line and online gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions (32)S(+), (33)S(+), and (34)S(+). The current levels of measurement precision for OCS samples greater than 8 nmol are 0.42‰, 0.62‰, and 0.23‰ for δ(33)S, δ(34)S, and Δ(33)S, respectively. These δ and Δ values show a slight dependence on the amount of injected OCS for volumes smaller than 8 nmol. The isotope values obtained from the GC-IRMS method were calibrated against those measured by a conventional SF6 method. We report the first measurement of the sulfur isotopic composition of OCS in air collected at Kawasaki, Kanagawa, Japan. The δ(34)S value obtained for OCS (4.9 ± 0.3‰) was lower than the previous estimate of 11‰. When the δ(34)S value for OCS from the atmospheric sample is postulated as the global signal, this finding, coupled with isotopic fractionation for OCS sink reactions in the stratosphere, explains the reported δ(34)S for background stratospheric sulfate. This suggests that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. PMID:25439590

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

    NASA Astrophysics Data System (ADS)

    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

  11. Investigations of the oxidation capacities of polar atmospheres with multiple oxygen isotopes

    NASA Astrophysics Data System (ADS)

    McCabe, Justin R.

    This study provides new perspectives on the atmospheric chemistry in Polar Regions using multiple oxygen isotopes of nitrate and sulfate. Despite their remote locations, these unique environments play an important role in the present state of global climate and contain invaluable clues to observing past relationships between earth's atmosphere and surface temperature. With current temperatures and greenhouse gas concentrations rising rapidly as a result of human activities, continued investigation of the effects on polar environments will elucidate their relationship to the global climate system. Three studies are presented here to constrain the oxidation pathways of nitrogen and sulfur compounds in polar atmospheres. These findings provide a new means to observe current and past oxidation conditions of tropospheric and stratospheric polar atmospheres. Currently, two uncertain aspects of climate are the projected changes in tropospheric and stratospheric oxidation chemistry and the role of aerosols in cloud formation and the global radiation budget. Because the levels of oxidants in the atmosphere directly influence greenhouse gas concentrations and aerosol distribution, the following work presents results implicit to improving knowledge of the climate system. The results presented in this dissertation include measurements of oxygen isotopes (delta17O, delta18O, and Delta 17O) in nitrate and sulfate from South Pole, Antarctica and Alert, Canada, respectively. In addition, a photochemistry experiment was conducted to measure the effects of ultraviolet (UV) irradiation on oxygen isotopes of nitrate in water and ice. Chapter 2 compares oxygen isotopes in sulfate aerosol collected at Alert, Canada over the course of one year (July 1999--June 2000) to a chemical transport model describing sulfate formation. Chapter 3 presents the results from the nitrate photochemistry experiments conducted at California Institute of Technology in Pasadena, California. Chapter 4

  12. Carbon and sulfur isotopes as tracers of fluid-fluid and fluid-rock interaction in geothermal systems

    NASA Astrophysics Data System (ADS)

    Stefansson, A.; Keller, N. S.; Gunnarsson Robin, J.; Kjartansdottir, R.; Ono, S.; Sveinbjörnsdottir, A. E.

    2014-12-01

    Carbon and sulfur are among major components in geothermal systems. They are found in various oxidation state and present in solid phases and fluids (water and vapor). In order to study the reactions and mass movement within multiphase geothermal systems, we have combined geochemical fluid-fluid and fluid-rock modelling with sulfur and carbon isotope fractionation modelling and compared the results with measured carbon and sulfur isotopes in geothermal fluids (water and vapor) for selected low- and high-enthalpy geothermal systems in Iceland. In this study we have focused on δ34S for H2S in vapor and water and SO4 in water as well as δ13C for CO2 in vapor and water phases. Isotope fractionations for CO2 and H2S between vapor and liquid water, upon aqueous speciation and upon carbonate and sulfide mineral formation were revised. These were combined with reaction modelling involving closed system boiling and progressive water-rock interaction to constrain the mass movement and isotope abundance between various phases. The results indicate that for a closed system, carbon and sulfur isotope abundance is largely dependent on progressive fluid-fluid and fluid-rock interaction and the initial total δ34S and δ13C value of the system. Initially, upon progressive fluid rock interaction the δ34S and δ13C values for the bulk aqueous phase approach that of the host rocks. Secondary mineral formation may alter these values, the exact isotope value of the mineral and resulting aqueous phase depending on aqueous speciation and isotope fractionation factor. In turn, aqueous speciation and mineral saturation depends on progressive fluid-rock interaction, fluid-fluid interaction, temperature and acid supply to the system. Depressurization boiling also results in isotope fractionation, the exact isotope value of the vapor and aqueous phase depending on aqueous speciation and isotope fractionation fractor. In this way, carbon and sulfur isotopes may be used combined with

  13. Delineating the effect of El-Nino Southern Oscillations using oxygen and sulfur isotope anomalies of sulfate aerosols

    NASA Astrophysics Data System (ADS)

    Shaheen, R.; Abaunza Quintero, M. M.; Jackson, T.; McCabe, J.; Savarino, J. P.; Thiemens, M. H.

    2013-12-01

    Sulfate aerosols, unlike greenhouse gases, contribute to global cooling by acting as cloud condensation nuclei in the troposphere and by directly reflecting solar radiation in the stratosphere. To understand the long-term effect of natural and anthropogenic sulfate aerosol on the climate cycle, it is critical to obtain a clear picture of the factors controlling the transport and transformation of sulfate aerosols. We have employed both oxygen triple isotopes and sulfur quadruple isotopes on sulfates from Antarctic ice samples to define the oxidation history, long range transport dynamics, and sources of sulfate aerosols over time. The measurements are used to deconvolve the impact of natural and anthropogenic aerosols on the stratospheric sulfate aerosol composition. Sulfate aerosols were extracted from a snow pit at the South Pole (1979-2002) with a high resolution temporal (6 month) record of the winter and summer seasons covering two largest volcanic events, Pinatubo and El-chichon and three largest ENSO events of the century. All three oxygen and four sulfur isotopes were measured on the extracted sulfate (Shaheen et al., 2013). The high temperature pyrolysis (1000oC) of silver sulfate yielded O2 and SO2. The oxygen triple isotopic composition of the O2 gas was used to determine the oxidation history of sulfate aerosol and SO2 gas obtained during this reaction was utilized to measure sulfur quadruple isotopes following appropriate reaction chemistry (Farquhar et al., 2001). The data revealed that oxygen isotope anomalies in Antarctic aerosols (Δ17O = 0.8-3.7‰) from 1990 to 2001 are strongly linked to the variation in ozone levels in the upper stratosphere/lower stratosphere. The variations in ozone levels are reflective of the intensity of the ENSO events and changes in relative humidity in the atmosphere during this time period. Sulfate concentrations and sulfur quadruple isotopic composition and associated anomalies were used to elucidate the sources of

  14. Sulfur isotope and trace element data from ore sulfides in the Noranda district (Abitibi, Canada): implications for volcanogenic massive sulfide deposit genesis

    NASA Astrophysics Data System (ADS)

    Sharman, Elizabeth R.; Taylor, Bruce E.; Minarik, William G.; Dubé, Benoît; Wing, Boswell A.

    2015-06-01

    We examine models for volcanogenic massive sulfide (VMS) mineralization in the ~2.7-Ga Noranda camp, Abitibi subprovince, Superior Province, Canada, using a combination of multiple sulfur isotope and trace element data from ore sulfide minerals. The Noranda camp is a well-preserved, VMS deposit-rich area that is thought to represent a collapsed volcanic caldera. Due to its economic value, the camp has been studied extensively, providing a robust geological framework within which to assess the new data presented in this study. We explore previously proposed controls on mineralization within the Noranda camp and, in particular, the exceptional Au-rich Horne and Quemont deposits. We present multiple sulfur isotope and trace element compositional data for sulfide separates representing 25 different VMS deposits and "showings" within the Noranda camp. Multiple sulfur isotope data for this study have δ34SV-CDT values of between -1.9 and +2.5 ‰, and Δ33SV-CDT values of between -0.59 and -0.03 ‰. We interpret the negative Δ33S values to be due to a contribution of sulfur that originated as seawater sulfate to form the ore sulfides of the Noranda camp VMS deposits. The contribution of seawater sulfate increased with the collapse and subsequent evolution of the Noranda caldera, an inference supported by select trace and major element analyses. In particular, higher concentrations of Se occur in samples with Δ33S values closer to 0 ‰, as well as lower Fe/Zn ratios in sphalerite, suggesting lower pressures and temperatures of formation. We also report a relationship between average Au grade and Δ33S values within Au-rich VMS deposits of the Noranda camp, whereby higher gold grades are associated with near-zero Δ33S values. From this, we infer a dominance of igneous sulfur in the gold-rich deposits, either leached from the volcanic pile and/or directly degassed from an associated intrusion.

  15. Simultaneous Analysis of Nitrogen, Carbon and Sulfur Stable Isotopes and Concentrations in Organics and Soils

    NASA Astrophysics Data System (ADS)

    Mambelli, S.; Brooks, P. D.; Sutka, R.; Hughes, S.; Finstad, K. M.; Pakes, M. J.; Dawson, T. E.

    2014-12-01

    To date, analysis of diet, food web complexities, biogeochemical cycles, and ecosystem functioning have largely focused on using variation in carbon (C) and nitrogen (N) stable isotope ratios. This is because a great deal is understood about what leads to this variation and because the dual stable isotope analysis of these two elements using continuous flow isotope ratio mass spectrometry (IRMS) is now commonplace. However, the aforementioned studies may all greatly benefit from the additional information one can get from also having sulfur (S) stable isotopes ratio data. Until very recently the analysis of δ34S has traditionally required an additional and often more difficult analytical procedure. Here, we report on the development of a new method that simultaneously analyzes the elemental and isotopic composition of N, C and S in a single sample. The new commercially available instrument includes a modified NCS elemental analyzer in line with an IRMS outfitted with 100 volt AD converters for wide dynamic range. We tested, and modified, this instrument to achieve maximum accuracy and precision for the isotopic measurements of all three elements. We found that the original design needed improvements to achieve our goals by: a) including a component (originally designed for trapping water) as buffer to reduce S memory and obtain reliable δ34S analysis; b) adding an external furnace for complete reduction of nitrogen oxides to N2 gas for accurate δ15N; c) adding a magnesium perchlorate water trap immediately after the reduction tube to minimize any water condensation that could also influence S memory. We analyzed a selection of organic materials and soils with approximately a 1:2 standards versus unknowns ratio per run. Using this NCS set-up, the precision of the N and C isotopic measurements was comparable to the one usually attained in NC mode alone (standard deviation of ± 0.13 δ15N in the range 30 to 400 µg N, and of ± 0.12 δ13C in the range 0.20 to 4 mg

  16. Sulfur isotopic fractionation in vacuum UV photodissociation of hydrogen sulfide and its potential relevance to meteorite analysis

    PubMed Central

    Chakraborty, Subrata; Jackson, Teresa L.; Ahmed, Musahid; Thiemens, Mark H.

    2013-01-01

    Select meteoritic classes possess mass-independent sulfur isotopic compositions in sulfide and organic phases. Photochemistry in the solar nebula has been attributed as a source of these anomalies. Hydrogen sulfide (H2S) is the most abundant gas-phase species in the solar nebula, and hence, photodissociation of H2S by solar vacuum UV (VUV) photons (especially by Lyman-α radiation) is a relevant process. Because of experimental difficulties associated with accessing VUV radiation, there is a paucity of data and a lack of theoretical basis to test the hypothesis of a photochemical origin of mass-independent sulfur. Here, we present multiisotopic measurements of elemental sulfur produced during the VUV photolysis of H2S. Mass-independent sulfur isotopic compositions are observed. The observed isotopic fractionation patterns are wavelength-dependent. VUV photodissociation of H2S takes place through several predissociative channels, and the measured mass-independent fractionation is most likely a manifestation of these processes. Meteorite sulfur data are discussed in light of the present experiments, and suggestions are made to guide future experiments and models. PMID:23431159

  17. Sulfur isotopic fractionation in vacuum UV photodissociation of hydrogen sulfide and its potential relevance to meteorite analysis.

    PubMed

    Chakraborty, Subrata; Jackson, Teresa L; Ahmed, Musahid; Thiemens, Mark H

    2013-10-29

    Select meteoritic classes possess mass-independent sulfur isotopic compositions in sulfide and organic phases. Photochemistry in the solar nebula has been attributed as a source of these anomalies. Hydrogen sulfide (H2S) is the most abundant gas-phase species in the solar nebula, and hence, photodissociation of H2S by solar vacuum UV (VUV) photons (especially by Lyman-α radiation) is a relevant process. Because of experimental difficulties associated with accessing VUV radiation, there is a paucity of data and a lack of theoretical basis to test the hypothesis of a photochemical origin of mass-independent sulfur. Here, we present multiisotopic measurements of elemental sulfur produced during the VUV photolysis of H2S. Mass-independent sulfur isotopic compositions are observed. The observed isotopic fractionation patterns are wavelength-dependent. VUV photodissociation of H2S takes place through several predissociative channels, and the measured mass-independent fractionation is most likely a manifestation of these processes. Meteorite sulfur data are discussed in light of the present experiments, and suggestions are made to guide future experiments and models. PMID:23431159

  18. Risk management for sulfur dioxide abatement under multiple uncertainties

    NASA Astrophysics Data System (ADS)

    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.

  19. Triple isotope composition of sulfur from sulfate on the MC-ICPMS Neptune

    NASA Astrophysics Data System (ADS)

    Paris, G.; Adkins, J. F.; Sessions, A. L.; Subhas, A.; Waldbauer, J.; Fischer, W. W.

    2011-12-01

    We present a new method to measure precise and accurate 34S/32S and 33S/32S ratios from small amounts of sulfate in solution. The sulfur cycle plays an important role in many earth system processes at a variety of timescales. Exploring the isotopic composition of sulfur from Carbonate Associated Sulfates (CAS) during geological times or from dissolved sulfate in modern seawater and porewater can provide important constraints on these processes. For carbonates, existing methods focus on samples rather rich in CAS (>100 ppm) or samples available in large amounts (>1g). Samples with either very low sulfate concentration (e.g., Archean-aged carbonates) and/or limited sample sizes (such as foraminifera) require a more sensitive analytical method. An attractive technique involves MC-ICPMS (multiCollector inductively-coupled plasma mass spectrometry), which has been used successfully for bulk and in-situ δ34S evaluation of sulfate and sulfide minerals (Craddock et al., 2008) and organic compounds (Amrani et al., 2009). Two main advantages of working with a MC-ICPMS (here a ThermoScientific Neptune) compared to conventional SO2 gas source mass spectrometry are an increased sensitivity and the ability to introduce sulfur as either sulfate or sulfide. However, this approach requires removal of the complex sample matrix so samples can be analyzed as sodium sulfate diluted in 5% HNO3. IAEA BaSO4 standards, on the other hand, can be run as dissolved BaSO4 through chelation of Ba with EDTA. Sample purification is achieved through Ca++ removal using either a cation-exchanging membrane or a micro-column of Dionex AG50X8 resin. These two methods allow exchange of Ca++ (or other cations) for H++. Sulfate can then be concentrated by evaporation for subsequent isotope analysis. The membrane is preferred for samples with sulfate concentrations lower than 100 ppm to decrease sulfur contamination from the AG50X8 sulfonyl groups and the resin is favored for samples with sulfate

  20. Assessment of sulfate sources in high-elevation Asian precipitation using stable sulfur isotopes.

    PubMed

    Pruett, Lee E; Kreutz, Karl J; Wadleigh, Moire; Aizen, Vladimir

    2004-09-15

    Stable sulfur isotope measurements (delta34S) made on samples collected from a 2 m snowpit on the Inilchek Glacier, Tien Shan Mountains (42.16 degrees N, 80.25 degrees E, 5100 m) are used to estimate sources of sulfate (SO4(2-)) in high-elevation Central Asian precipitation. Comparison of snowpit oxygen isotope (delta18O) data with previous work constrains the age of the snowpit samples to the summer season during which they were retrieved (1999). Delta34S measurements were made at 10 cm resolution (20 samples total), with delta34S values ranging from 0.4/1000 during background ([SO4(2-)] < 1 microequiv L(-1)) periods to 19.4/1000 during a single high [SO4(2-)] event. On the basis of the significant correlation (r = 0.87) between [SO4(2-)] and delta34S values, coupled with major ion concentration time series and concentration ratios, we suggest a two-component mixing system consisting of evaporite dust and anthropogenic SO4(2-) to explain the observed delta34S values. Using a regression model, we estimate that during the 1999 summer season 60% of the deposited SO4(2-) was from an evaporite dust source, while 40% of the SO4(2-) was from anthropogenic sources. Due to the potentially large and unconstrained range of delta34S values for both evaporite and anthropogenic SO4(2-) sources in Asia, the error in our estimates is difficult to assess. However, the delta34S data from the 1999 Tien Shan snowpit provide the first unambiguous identification of evaporite and anthropogenic SO4(2-) in high-elevation Asian precipitation, and future ice core studies using improved analysis techniques and source delta34S values can provide detailed information on sulfur biogeochemistry and anthropogenic impacts in Asian alpine regions. PMID:15487779

  1. SO2 in the Fall in the Arctic: Source Identification Using Sulfur Isotopes

    NASA Astrophysics Data System (ADS)

    Norman, A. L.; Seguin, A.; Rempillo, O. T.

    2011-12-01

    The Arctic atmosphere, although far from industrial sources, has a large anthropogenic SO2 load. Sulfur dioxide can have other sources including from dimethylsulphide (DMS) oxidation. One way to distinguish between these two types of SO2 is through sulfur isotope apportionment. During the Fall seasons of 2007 and 2008 aerosol sulfate and SO2 were measured at two sites in the Arctic. One site was on board the Canadian Coast Guard Ship, The Amundsen, as it traveled throughout the Arctic and the other site was at Alert, Nunavut, Canada. Sulfur dioxide concentrations at Alert varied between 0.02 and 18 nmol/m3 throughout the study with a median of 0.4 nmol/m3. δ34S values ranged between 0 and +11%. Concentrations and δ34S values aboard the Amundsen were much more diverse with concentrations ranging between 0.09 and 134 nmol/m3 (2007 median = 9.4 nmol/m3; 2008 median = 2.0 nmol/m3) and δ34S values ranging between -15 and +18%. High concentrations of SO2 on board the Amundsen were not directly from the Amundsen itself as there was no correlation with peaks in coincident CO2 measurements. Low concentrations of SO2 may, in a few instances, be associated with DMS oxidation. Negative δ34S values were present for samples collected near the Amundsen Gulf and are consistent with a third source of SO2 in the Arctic. This is likely the local source of SO2 from the Smoking Hills in the North West Territories. Distinguishing between these sources of SO2 in the Arctic and the importance of local verses regional sources will be discussed.

  2. On-line sulfur isotope analysis of organic material by direct combustion: Preliminary results and potential applications

    USGS Publications Warehouse

    Kester, C.L.; Rye, R.O.; Johnson, C.A.; Schwartz, C.H.; Holmes, C.H.

    2001-01-01

    Sulfur isotopes have received little attention in ecology studies because plant and animal materials typically have low sulfur concentrations (< 1 wt.%) necessitating labor-intensive chemical extraction prior to analysis. To address the potential of direct combustion of organic material in an elemental analyzer coupled with a mass spectrometer, we compared results obtained by direct combustion to results obtained by sulfur extraction with Eschka's mixture. Direct combustion of peat and animal tissue gave reproducibility of better than 0.5??? and on average, values are 0.8??? higher than values obtained by Eschka extraction. Successful direct combustion of organic material appears to be a function of sample matrix and sulfur concentration. Initial results indicate that direct combustion provides fast, reliable results with minimal preparation. Pilot studies underway include defining bear diets and examining fluctuations between freshwater and brackish water in coastal environments.

  3. Counting individual sulfur atoms in a protein by ultrahighresolution Fourier transform ion cyclotron resonance mass spectrometry: Experimental resolution of isotopic fine structure in proteins

    PubMed Central

    Shi, Stone D.-H.; Hendrickson, Christopher L.; Marshall, Alan G.

    1998-01-01

    A typical molecular ion mass spectrum consists of a sum of signals from species of various possible isotopic compositions. Only the monoisotopic peak (e.g., all carbons are 12C; all nitrogens are 14N, etc.) has a unique elemental composition. Every other isotope peak at approximately integer multiples of ∼1 Da higher in nominal mass represents a sum of contributions from isotope combinations differing by a few mDa (e.g., two 13C vs. two 15N vs. one 13C and one 15N vs. 34S, vs. 18O, etc., at ∼2 Da higher in mass than the monoisotopic mass). At sufficiently high mass resolving power, each of these nominal-mass peaks resolves into its isotopic fine structure. Here, we report resolution of the isotopic fine structure of proteins up to 15.8 kDa (isotopic 13C,15N doubly depleted tumor suppressor protein, p16), made possible by electrospray ionization followed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass analysis at 9.4 tesla. Further, a resolving power of m/Δm50% ≈8,000,000 has been achieved on bovine ubiquitin (8.6 kDa). These results represent a 10-fold increase in the highest mass at which isotopic fine structure previously had been observed. Finally, because isotopic fine structure reveals elemental composition directly, it can be used to confirm or determine molecular formula. For p16, for example, we were able to determine (5.1 ± 0.3) the correct number (five) of sulfur atoms solely from the abundance ratio of the resolved 34S peak to the monoisotopic peak. PMID:9751700

  4. Sulfur Isotopes as Indicators of Bacterial Sulfate Reduction Processes Influencing Field Scale Uranium Bioremediation

    NASA Astrophysics Data System (ADS)

    Druhan, J. L.; Conrad, M. E.; Williams, K. H.; N'guessan, L.; Long, P. E.; Hubbard, S. S.

    2007-12-01

    An in-situ acetate amendment at a DOE Uranium Mill Tailings Remedial Action (UMTRA) site near Rifle, CO demonstrated successful reduction of aqueous U(VI), to less soluble U(IV) through stimulated microbial activity. U(VI) reduction rates were highest during iron reduction and decreased with the onset of sulfate reduction. However, sustained U(IV) attenuation was observed following subsequent termination of the acetate amendment. These findings illustrate the importance of the transition between iron and sulfate reducing conditions in stimulating bioreduction of uranium. The sulfur isotope compositions of sulfate and sulfide were measured through this transition in order to explore the utility of these data in tracking the extent of microbial sulfate reduction and to assess the stability of sulfide precipitates. Samples for isotopic analyses and aqueous measurements of sulfate, ferrous iron, U(VI) and acetate were collected in one background well and three monitoring wells down-gradient of the acetate injection. Results show an increase of up to 7‰ in the δ34S of sulfate at the onset of sulfate reduction, followed by a return to background δ34S values of -8‰ following cessation of the acetate amendment. The δ34S values of sulfide increased from roughly -20‰ at the onset of sulfate reduction to a maximum of -0.8‰ during peak sulfate removal, followed by a gradual return to values of roughly -28‰ upon cessation of the acetate amendment. These data present a unique perspective on the processes governing the bioreduction experiment in that the sulfate isotopes are a function of both transport and mixing processes, whereas the sulfide isotopes represent biogenic sulfide that is rapidly removed from the aqueous phase. Thus a comparable enrichment in sulfate isotopic data noted in the closest and furthest wells from the injection gallery suggest bioreduction in both of these locations, while a larger increase in sulfide isotopic values in the closest well

  5. Sulfur and oxygen isotope tracing in zero valent iron based In situ remediation system for metal contaminants.

    PubMed

    Kumar, Naresh; Millot, Romain; Battaglia-Brunet, Fabienne; Négrel, Philippe; Diels, Ludo; Rose, Jérôme; Bastiaens, Leen

    2013-01-01

    In the present study, controlled laboratory column experiments were conducted to understand the biogeochemical changes during the microbial sulfate reduction. Sulfur and oxygen isotopes of sulfate were followed during sulfate reduction in zero valent iron incubated flow through columns at a constant temperature of 20±1°C for 90 d. Sulfur isotope signatures show considerable variation during biological sulfate reduction in our columns in comparison to abiotic columns where no changes were observed. The magnitude of the enrichment in δ(34)S values ranged from 9.4‰ to 10.3‰ compared to initial value of 2.3‰, having total fractionation δS between biotic and abiotic columns as much as 6.1‰. Sulfur isotope fractionation was directly proportional to the sulfate reduction rates in the columns. Oxygen isotopes in this experiment seem less sensitive to microbial activities and more likely to be influenced by isotopic exchange with ambient water. A linear relationship is observed between δ(34)S and δ(18)O in biotic conditions and we also highlight a good relationship between δ(34)S and sulfate reduction rate in biotic columns. PMID:23000047

  6. Sulfur Isotopic Composition and Behavior in Granitoid Intrusions, southwestern New Brunswick, Canada

    NASA Astrophysics Data System (ADS)

    Yang, X.; Lentz, D. R.

    2004-05-01

    Bulk sulfur isotopic composition and sulfur content were determined for 12 granitoid intrusions (48 samples) associated with various types of mineralization (e.g., Au, Sb-W-Mo-Au, W-Sn-In-Zn-Pb-Cu) and the pertinent wallrocks (7 samples), in southwestern New Brunswick, Canada. This data together with data from field relations, magnetic susceptibility, sulfide mineralogy, petrology, and geochemistry, were used to characterize these intrusions. Two distinct groups can be established, although both show some features of I-type grantiods: (1) a Late Devonian granitic series (GS) including the Mount Pleasant, True Hill, Beech Hill, Pleasant Ridge, Kedron, Sorrel Ridge granites, and (2) a Late Silurian to Early Devonian granodioritic to monzogranitic series (GMS) including the Magaguadavic, Bocabec, Utopia, Tower Hill, Evandale, and Lake George intrusions. The former occur along the northwestern flank of the Saint George Batholith as satellite plutons, and the later form parts of this batholith and the Pokiok Batholith to the north. The GS rocks show the attributes of evolved I-type with some A-type features, whereas the GMS rocks are either reduced I-type (ilmenite-series), or normal I-type (magnetite-series). Strong assimilation and contamination by local metasedimentary rocks lead to the Tower Hill granite resembling S-type, e.g., the presence of muscovite and garnet. The GS type rocks have δ 34S values between -7.1 and +13 per mil with bulk-S content ranging from 33 to 3434 ppm. The GMS type rocks have relatively narrower variation in δ 34S values (-4.4 to +7.3 per mil), but with larger ranges of bulk-S content (45 to 11100 ppm). The granite samples with S contents much higher than its solubility in felsic melts are interpreted to be affected either by local metasedimentary rocks or by late stage hydrothermal alteration. The metasedimentary rocks contain variable S contents (707 to 14000 ppm) with δ 34S values of -10.6 to 0.1 per mil. In terms of mass balance, a

  7. Determination of sulfur in biodiesel microemulsions using the summation of the intensities of multiple emission lines.

    PubMed

    Young, Carl G; Amais, Renata S; Schiavo, Daniela; Garcia, Edivaldo E; Nóbrega, Joaquim A; Jones, Bradley T

    2011-05-15

    A method for the determination of sulfur in biodiesel samples by inductively coupled plasma optical emission spectrometry which uses microemulsion for sample preparation and the summation of the intensities of multiple emission lines has been developed. Microemulsions were prepared using 0.5 mL of 20% v/v HNO(3), 0.5 mL of Triton X-100, 2-3 mL of biodiesel sample, and diluted with n-propanol to a final volume of 10 mL. Summation of the emission intensities of multiple sulfur lines allowed for increased accuracy and sensitivity. The amounts of sulfur determined experimentally were between 2 and 7 mg L(-1), well below legislative standards for many countries. Recoveries obtained ranged from 72 to 119%, and recoveries obtained for the 182.562 nm line were slightly lower. This is most likely due to its lower sensitivity. Using microemulsion for sample preparation and the summation of the intensities of multiple emission lines for the successful determination of sulfur in biodiesel has been demonstrated. PMID:21482315

  8. Compound-specific sulfur isotope analysis of thiadiamondoids of oils from the Smackover Formation, USA

    USGS Publications Warehouse

    Zvi Gvirtzman; Ward Said-Ahmad; Ellis, Geoffrey S.; Ronald J. Hill; J. Michael Moldowan; Zhibin Wei; Alon Amrani

    2015-01-01

    Thiadiamondoids (TDs) are diamond-like compounds with a sulfide bond located within the cage structure. These compounds were suggested as a molecular proxy for the occurrence and extent of thermochemical sulfate reduction (TSR). Compound-specific sulfur-isotope analysis of TDs may create a multi-parameter system, based on molecular and δ34S values that may be sensitive over a wider range of TSR and thermal maturation stages. In this study, we analyzed a suite of 12 Upper Jurassic oil and condensate samples generated from source rocks in the Smackover Formation to perform a systematic study of the sulfur isotope distribution in thiadiamondoids (one and two cages). For comparison we measured the δ34S composition of benzothiophenes (BTs) and dibenzothiophenes (DBTs). We also conducted pyrolysis experiments with petroleum and model compounds to have an insight into the formation mechanisms of TDs. The δ34S of the TDs varied significantly (ca 30‰) between the different oils depending on the degree of TSR alteration. The results showed that within the same oil, the one-cage TDs were relatively uniform, with 34S enriched values similar to those of the coexisting BTs. The two-cage TDs had more variable δ34S values that range from the δ34S values of BTs to those of the DBTs, but with general 34S depletion relative to one cage TDs. Hydrous pyrolysis experiments (360 °C, 40 h) with either CaSO4 or elemental S (equivalent S molar concentrations) and adamantane as a model compound demonstrate the formation of one cage TDs in relatively low yields (<0.2%). Higher concentrations of TDs were observed in the elemental sulfur experiments, most likely because of the higher rates of reaction with adamantane under these experimental conditions. These results show that the formation of TDs is not exclusive to TSR reactions, and that they can also form by reaction with reduced S species apart from sulfate reduction, though at low yields. Oxygenated compounds, most notably 2

  9. Compound-specific sulfur isotope analysis of thiadiamondoids of oils from the Smackover Formation, USA

    NASA Astrophysics Data System (ADS)

    Gvirtzman, Zvi; Said-Ahmad, Ward; Ellis, Geoffrey S.; Hill, Ronald J.; Moldowan, J. Michael; Wei, Zhibin; Amrani, Alon

    2015-10-01

    Thiadiamondoids (TDs) are diamond-like compounds with a sulfide bond located within the cage structure. These compounds were suggested as a molecular proxy for the occurrence and extent of thermochemical sulfate reduction (TSR). Compound-specific sulfur-isotope analysis of TDs may create a multi-parameter system, based on molecular and δ34S values that may be sensitive over a wider range of TSR and thermal maturation stages. In this study, we analyzed a suite of 12 Upper Jurassic oil and condensate samples generated from source rocks in the Smackover Formation to perform a systematic study of the sulfur isotope distribution in thiadiamondoids (one and two cages). For comparison we measured the δ34S composition of benzothiophenes (BTs) and dibenzothiophenes (DBTs). We also conducted pyrolysis experiments with petroleum and model compounds to have an insight into the formation mechanisms of TDs. The δ34S of the TDs varied significantly (ca 30‰) between the different oils depending on the degree of TSR alteration. The results showed that within the same oil, the one-cage TDs were relatively uniform, with 34S enriched values similar to those of the coexisting BTs. The two-cage TDs had more variable δ34S values that range from the δ34S values of BTs to those of the DBTs, but with general 34S depletion relative to one cage TDs. Hydrous pyrolysis experiments (360 °C, 40 h) with either CaSO4 or elemental S (equivalent S molar concentrations) and adamantane as a model compound demonstrate the formation of one cage TDs in relatively low yields (<0.2%). Higher concentrations of TDs were observed in the elemental sulfur experiments, most likely because of the higher rates of reaction with adamantane under these experimental conditions. These results show that the formation of TDs is not exclusive to TSR reactions, and that they can also form by reaction with reduced S species apart from sulfate reduction, though at low yields. Oxygenated compounds, most notably 2

  10. Sulfur and oxygen isotopic evidence of country rock contamination in the Voisey's Bay Ni Cu Co deposit, Labrador, Canada

    NASA Astrophysics Data System (ADS)

    Ripley, Edward M.; Park, Young-Rok; Li, Chusi; Naldrett, Anthony J.

    1999-06-01

    The emplacement of basaltic magma into sulfide-bearing country rocks provides a favorable geologic environment for magmatic sulfide ore formation related either directly to assimilation of country rock sulfur or indirectly to a depression of sulfide solubility caused by assimilation-induced changes in magma composition. Pelitic country rocks of the Proterozoic Tasiuyak Gneiss in the area of the Voisey's Bay Ni-Cu-Co deposit contain sulfidic layers that may have provided sulfur to basaltic magmas during emplacement of the Voisey's Bay intrusion. Sulfur isotopic compositions of the Tasiuyak Gneiss range from -0.9 to -17.0‰, values typical for sulfides produced via bacterial sulfate reduction in an open marine environment. Archean gneisses in the area contain low amounts of sulfide and are less likely to have served as a source of externally-derived sulfur. Sulfur isotopic compositions of the sulfide minerals from the Voisey's Bay deposit show consistent variations, both spatially and with rock types. Disseminated and massive sulfides show a decrease in δ 34S to the west, with values typically between 0 and -2‰ in the Eastern Deeps, Ovoid, and Discovery Hill zone, and between -2 and -4‰ in the Reid Brook zone. δ 34S values of the Mushua intrusion to the north and the Normal Troctolite in the Eastern Deeps are more positive, ranging between -0.5 and 1.8‰. This range is taken to represent the isotopic composition of primary mantle-derived sulfur in the area because the Mushua intrusion and Normal Troctolite show the least geochemical evidence for contamination by country rocks. Sulfur isotopic data from the Reid Brook zone are consistent with up to a 50% sulfur contribution from the Tasiuyak Gneiss. Correspondingly lower proportions are indicated for the eastern portion of the deposit where country rocks are predominantly low-sulfide enderbitic and quartzofeldspathic gneisses. Oxygen isotopic values of gneiss fragments in the Basal Breccia Sequence and Feeder