Sulfur Isotope Fractionation Research Articles

Micro-scale S isotope studies of the Kharaelakh intrusion, Noril’sk region, Siberia: Constraints on the genesis of coexisting anhydrite and sulfide minerals

The coexistence of magmatic anhydrite and sulfide minerals in non-arc-related mafic magmas has only rarely been documented. Likewise the S isotope fractionation between sulfate and sulfide in mafic rocks has infrequently been measured. In the Kharaelakh intrusion associated with the world-famous Noril’sk ore district in Siberia coexisting magmatic anhydrite and sulfide minerals have been identified. Sulfur isotope compositions of the anhydrite–sulfide assemblages have been measured via both ion microprobe and conventional analyses to help elucidate the origin of the anhydrite–sulfide pairs. Magmatic anhydrite and chalcopyrite are characterized by δ 34S values between 18.8‰ and 22.8‰, and 9.3‰ and 13.2‰, respectfully. Coexisting anhydrite and chalcopyrite show Δ values that fall between 8.5‰ and 11.9‰. Anhydrite in the Kharaelakh intrusion is most readily explained by the assimilation of sulfate from country rocks; partial reduction to sulfide led to mixing between sulfate-derived sulfide and sulfide of mantle origin. The variable anhydrite and sulfide δ 34S values are a function of differing degrees of sulfate reduction, variable mixing of sulfate-derived and mantle sulfide, incomplete isotopic homogenization of the magma, and a lack of uniform attainment of isotopic equilibrium during subsolidus cooling. The δ 34S values of sulfide minerals have changed much less with cooling than have anhydrite values due in large part to the high sulfide/sulfate ratio. Variations in both sulfide and anhydrite δ 34S values indicate that isotopically distinct domains existed on a centimeter scale. Late stage hydrothermal anhydrite and pyrite also occur associated with Ca-rich hydrous alteration assemblages (e.g., thomsonite, prehnite, pectolite, epidote, xonotlite). δ 34S values of secondary hydrothermal anhydrite and pyrite determined by conventional analyses are in the same range as those of the magmatic minerals. Anhydrite–pyrite Δ values are in the 9.1–10.1‰ range, and are smaller than anticipated for the low temperatures indicated by the silicate alteration assemblages. The small Δ values are suggestive of either sulfate–sulfide isotopic disequilibrium or closure of the system to further exchange between ∼550 and 600 °C. Our results confirm the importance of the assimilation of externally derived sulfur in the generation of the elevated δ 34S values in the Kharaelakh intrusion, but highlight the sulfur isotopic variability that may occur in magmatic systems. In addition, our results confirm the need for more precise experimental determination of sulfate–sulfide sulfur isotope fractionation factors in high-T systems.

Biogeochemical and Isotopic Gradients in a BTEX/PAH Contaminant Plume: Model-Based Interpretation of a High-Resolution Field Data Set

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

Emarat carbonate-hosted Zn–Pb deposit, Markazi Province, Iran: A geological, mineralogical and isotopic (S, Pb) study

The Emarat deposit, with a total proved reserve of 10 Mt ore grading 6% Zn and 2.26% Pb, is one of the largest Zn–Pb deposits in the Malayer–Esfahan belt. The mineralization is stratabound and restricted to Early Cretaceous limestones and dolomites. The ore consists mainly of sphalerite and galena with small amounts of pyrite, chalcopyrite, calcite, quartz, and dolomite. Textural evidence shows that the ore has replaced the host rocks and thus is epigenetic. Sulfur isotopes indicate that the sulfur in sphalerite and galena has been derived from Cretaceous seawater through thermochemical sulfate reduction. Sulfur isotope compositions of four apparently coprecipitated sphalerite–galena pairs suggest their precipitation was under equilibrium conditions. The sulfur isotopic fractionation observed for the sphalerite–galena pairs corresponds to formation temperatures between 77 °C and 168 °C, which agree with homogenization temperatures of fluid inclusions. Lead-isotope studies indicate that the lead in galena has been derived from heterogeneous sources including orogenic and crustal reservoirs with high 238U/ 204Pb and 232Th/ 204Pb ratios. Ages derived from the Pb-isotope model give meaningless ages, ranging from Early Carboniferous to future. It is probable that the Pb-isotope model ages that point to an earlier origin than the Early Cretaceous host rocks are derived from older reservoirs in the underlying Carboniferous or Jurassic units, either from the host rocks or from earlier-formed ore deposits within these units. This research and other available data show that the Emarat Zn–Pb deposit has many important features of Mississippi Valley-type (MVT) lead–zinc deposits and thus we argue that it is an MVT-type ore deposit.

Iron isotope fractionation between pyrite (FeS 2), hematite (Fe 2O 3) and siderite (FeCO 3): A first-principles density functional theory study

In addition to equilibrium isotopic fractionation factors experimentally derived, theoretical predictions are needed for interpreting isotopic compositions measured on natural samples because they allow exploring more easily a broader range of temperature and composition. For iron isotopes, only aqueous species were studied by first-principles methods and the combination of these data with those obtained by different methods for minerals leads to discrepancies between theoretical and experimental isotopic fractionation factors. In this paper, equilibrium iron isotope fractionation factors for the common minerals pyrite, hematite, and siderite were determined as a function of temperature, using first-principles methods based on the density functional theory (DFT). In these minerals belonging to the sulfide, oxide and carbonate class, iron is present under two different oxidation states and is involved in contrasted types of interatomic bonds. Equilibrium fractionation factors calculated between hematite and siderite compare well with the one estimated from experimental data (ln α 57Fe/ 54Fe = 4.59 ± 0.30‰ and 5.46 ± 0.63‰ at 20 °C for theoretical and experimental data, respectively) while those for Fe(III) aq-hematite and Fe(II) aq-siderite are significantly higher that experimental values. This suggests that the absolute values of the reduced partition functions ( β-factors) of aqueous species are not accurate enough to be combined with those calculated for minerals. When compared to previous predictions derived from Mössbauer or INRXS data [Polyakov V. B., Clayton R. N., Horita J. and Mineev S. D. (2007) Equilibrium iron isotope fractionation factors of minerals: reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy. Geochim. Cosmochim. Acta 71, 3833–3846], our iron β-factors are in good agreement for siderite and hematite while a discrepancy is observed for pyrite. However, the detailed investigation of the structural, electronic and vibrational properties of pyrite as well as the study of sulfur isotope fractionation between pyrite and two other sulfides (sphalerite and galena) indicate that DFT-derived β-factors of pyrite are as accurate as for hematite and siderite. We thus suggest that experimental vibrational density of states of pyrite should be re-examined.

Processes affecting δ 34S and δ 18O values of dissolved sulfate in alluvium along the Canadian River, central Oklahoma, USA

The δ 34S and δ 18O values for dissolved sulfate in groundwater are commonly used in aquifer studies to identify sulfate reservoirs and describe biogeochemical processes. The utility of these data, however, often is compromised by mixing of sulfate sources within reservoirs and isotope fractionation during sulfur redox cycling. Our study shows that, after all potential sulfate sources are identified and isotopically characterized, the δ 34S SO4 and δ 18O SO4 values differentiate processes such as sulfate-source mixing, sulfide oxidation, barite dissolution, and organosulfur decomposition. During bacterial reduction of sulfate, the values reflect kinetic sulfur isotope fractionation and exchange of oxygen isotopes between sulfate and water. Detailed analysis of the chemistry (Cl and SO 4 concentrations) and isotopic composition (δ 2H H2O and δ 18O H2O) of groundwater in an alluvial aquifer in Central Oklahoma, USA allowed the identification of five distinct end members that supply water to the aquifer (regional groundwater flowing into the study area, river water, leachate from a closed landfill that operated within the site, rain, and surface runoff). The δ 34S SO4 and δ 18O SO4 values in each end member differentiated three sources of sulfate: sulfate dissolved from Early to Late Permian rocks within the drainage basin (δ 34S SO4 = 8–12‰ and δ 18O SO4 = 10‰), iron sulfides oxidized by molecular oxygen during low water-table levels (δ 34S SO4 = − 16‰ and δ 18O SO4 = 10‰), and organosulfur compounds (predominately ester sulfates) from decomposition of vegetation on the surface and from landfill trash buried in the alluvium (δ 34S SO4 = 8‰ and δ 18O SO4 = 6‰). During bacterial reduction of these sulfate sources, similar isotope fractionation processes are recorded in the parallel trends of increasing δ 34S SO4 and δ 18O SO4 values. When extensive reduction occurs, the kinetic sulfur isotope fractionation (estimated by ε H2S–SO4 = − 23‰) results in the steady increase of δ 34S SO4 values to greater than 70‰. Equilibrium isotope fractionation during exchange of sulfate oxygen and water oxygen, a process not commonly observed in field-based studies, is documented in δ 18O SO4 values asymptotically approaching 21‰, the value predicted for conditions at the study site ( ε SO4–H2O = 27‰). These results show that recognition of all potential sulfate sources is a critical first step to resolving complexities in δ 34S SO4 and δ 18O SO4 data. The approach taken in this study can be used in other aquifer systems where the identification of multiple sulfate sources and sulfur redox cycling is important to understanding natural processes and anthropogenic influences.

Theoretical investigation of the anomalous equilibrium fractionation of multiple sulfur isotopes during adsorption

Adsorption processes of gaseous molecules are known to be associated with isotopic fractionation, this being supported both experimentally and theoretically. From theoretical considerations [Lasaga, A.C., Otake, T., Watanabe, Y., Ohmoto, H. (2008) Anomalous fractionation of sulfur isotopes during heterogeneous reactions Earth and Planetary Science Letters 268 225–238], this process might also result in a “mass-independent” isotopic fractionation (MIF) of sulfur [i.e. δ 33 S ≠ 0.515 × δ 34 S] and could bear on our understanding of the sulfur isotope geological record. The anomalous fractionation could find its origin in the difference in the number of vibrational bound states of the adsorption complex (i.e. unbound states are neglected) among the four sulfur isotopes. In the present study, the equilibrium isotopic fractionation of sulfur during adsorption is investigated using a similar 1-dimensional (1-D) Morse potential. We demonstrate that no anomalous fractionation is expected when the contribution of all the accessible states (both bound and unbound) is properly taken into account. These results thus contradict the conclusion of Lasaga et al. [Lasaga, A.C., Otake, T., Watanabe, Y., Ohmoto, H., 2008. Anomalous fractionation of sulfur isotopes during heterogeneous reactions. Earth Planet. Sci. Lett. 268, 225–238.] stating that adsorption reactions would result in anomalous fractionations. Neglecting unbound states in our calculations would actually led to similar anomalous isotope fractionation, showing that the anomalous effect indeed arises from this simplification. Equilibrium adsorption processes are thus not expected to be associated with anomalous fractionation among the four sulfur isotopes.

Reconstructing Earth's surface oxidation across the Archean-Proterozoic transition

The Archean-Proterozoic transition is characterized by the widespread deposition of organic-rich shale, sedimentary iron formation, glacial diamictite, and marine carbonates recording profound carbon isotope anomalies, but notably lacks bedded evaporites. All deposits refl ect environmental changes in oceanic and atmospheric redox states, in part associated with Earth’s earliest ice ages. Time-series data for multiple sulfur isotopes from carbonateassociated sulfate as well as sulfi des in sediments of the Transvaal Supergroup, South Africa, capture the concomitant buildup of sulfate in the ocean and the loss of atmospheric massindependent sulfur isotope fractionation. In phase with sulfur is the earliest recorded positive carbon isotope anomaly, convincingly linking these environmental perturbations to the Great Oxidation Event (ca. 2.3 Ga).

Anomalous Fractionations of Sulfur Isotopes During Thermochemical Sulfate Reduction

Anomalously fractionated sulfur isotopes in many sedimentary rocks older than 2.4 billion years have been widely believed to be the products of ultraviolet photolysis of volcanic sulfur dioxide in an anoxic atmosphere. Our laboratory experiments have revealed that reduced-sulfur species produced by reactions between powders of amino acids and sulfate at 150 degrees to 200 degrees C possess anomalously fractionated sulfur isotopes: Delta33S = +0.1 to +2.1 per mil and Delta36S = -1.1 to +1.1 per mil. These results suggest that reactions between organic matter in sediments and sulfate-rich hydrothermal solutions may have produced anomalous sulfur isotope signatures in some sedimentary rocks. If so, the sulfur isotope record of sedimentary rocks may be linked to the biological and thermal evolution of Earth in ways different than previously thought.

Elucidating microbial processes in nitrate- and sulfate-reducing systems using sulfur and oxygen isotope ratios: The example of oil reservoir souring control

Sulfate-reducing bacteria (SRB) are ubiquitous in anoxic environments where they couple the oxidation of organic compounds to the production of hydrogen sulfide. This can be problematic for various industries including oil production where reservoir “souring” (the generation of H 2S) requires corrective actions. Nitrate or nitrite injection into sour oil fields can promote SRB control by stimulating organotrophic nitrate- or nitrite-reducing bacteria (O-NRB) that out-compete SRB for electron donors (biocompetitive exclusion), and/or by lithotrophic nitrate- or nitrite-reducing sulfide oxidizing bacteria (NR-SOB) that remove H 2S directly. Sulfur and oxygen isotope ratios of sulfide and sulfate were monitored in batch cultures and sulfidic bioreactors to evaluate mitigation of SRB activities by nitrate or nitrite injection. Sulfate reduction in batch cultures of Desulfovibrio sp. strain Lac15 indicated typical Rayleigh-type fractionation of sulfur isotopes during bacterial sulfate reduction (BSR) with lactate, whereas oxygen isotope ratios in unreacted sulfate remained constant. Sulfur isotope fractionation in batch cultures of the NR-SOB Thiomicrospira sp. strain CVO was minimal during the oxidation of sulfide to sulfate, which had δ 18O SO4 values similar to that of the water–oxygen. Treating an up-flow bioreactor with increasing doses of nitrate to eliminate sulfide resulted in changes in sulfur isotope ratios of sulfate and sulfide but very little variation in oxygen isotope ratios of sulfate. These observations were similar to results obtained from SRB-only, but different from those of NR-SOB-only pure culture control experiments. This suggests that biocompetitive exclusion of SRB took place in the nitrate-injected bioreactor. In two replicate bioreactors treated with nitrite, less pronounced sulfur isotope fractionation and a slight decrease in δ 18O SO4 were observed. This indicated that NR-SOB played a minor role during dosing with low nitrite and that biocompetitive exclusion was the major process. The results demonstrate that stable isotope data can contribute unique information for understanding complex microbial processes in nitrate- and sulfate-reducing systems, and offer important information for the management of H 2S problems in oil reservoirs and elsewhere.

Effect of NO2− on Stable Isotope Fractionation during Bacterial Sulfate Reduction

The effects of low NO2(-) concentrations on stable isotope fractionation during dissimilatory sulfate reduction by strain Desulfovibrio desulfuricans were investigated. Nitrite, formed as an intermediate during nitrification and denitrification processes in marine and freshwater habitats, inhibits the reduction of the sulfuroxy intermediate SO3(2-) to H2S even at low concentrations. To gain an understanding of the inhibition effect of the reduction of the sulfuroxy intermediate on stable isotope fractionation in sulfur and oxygen during bacterial sulfate reduction, nitrite was added in the form of short pulses. In the batch experiments that contained 0.02, 0.05, and 0.1 mM nitrite, sulfur enrichment factors epsilon of -12 +/- 1.6, -15 +/- 1.1, and -26 +/- 1.3 per thousand, respectively were observed. In the control experiment (no addition of nitrite) a sulfur enrichment factor epsilon of around -11 per thousand was calculated. In the experiments that contained no 18O enriched water (delta18O: -10 per thousand) and nitrite concentrations of 0.02, 0.05, and 0.1 mM, delta18O values in the remaining sulfate were fairly constant during the experiments (delta18O sulfate: approximately equal to 10 per thousand) and were similar to those obtained from the control experiment (no nitrite and no enriched water). However, in the batch experiments that contained 18O enriched water (+700 per thousand) and nitrite concentrations of 0.05 and 0.1 mM increasing delta18O values in the remaining sulfate from around 15 per thousand to approximately 65 and 85 per thousand, respectively, were found. Our experiments that contained isotopic enriched water and nitrite show clear evidence that the ratio of forward and backward fluxes regulated by adenosine-5'-phosphosulfate reductase (APSR) controls the extent of sulfur isotope fractionation during bacterial sulfate reduction in strain Desulfovibrio desulfuricans. Since the metabolic sulfuroxy intermediate SO3(2-) exchanges with water, evidence of 18O enriched water in the remaining sulfate in the experiments that contained nitrite also demonstrates that SO3(2-) recycling to sulfate affects sulfur and oxygen isotope fractionation during bacterial sulfate reduction to some extent. Even though reduction of adenosine-5'-phosphosulfate (APS) to sulfite of -25 per thousand was not fully expressed, SO3(2-) was recycled to SO4(2-). On the basis of the results of this study a sulfur isotope fractionation for APSR of upto approximately -30 per thousand can be assumed. However, reported NO2(-) concentrations of up to 20 microM in freshwater and marine habitats may not significantly impact the ability to use stable isotope analysis in assessing bacterial sulfate reduction.

The Crystal Structure of Desulfovibrio vulgaris Dissimilatory Sulfite Reductase Bound to DsrC Provides Novel Insights into the Mechanism of Sulfate Respiration

Sulfate reduction is one of the earliest types of energy metabolism used by ancestral organisms to sustain life. Despite extensive studies, many questions remain about the way respiratory sulfate reduction is associated with energy conservation. A crucial enzyme in this process is the dissimilatory sulfite reductase (dSiR), which contains a unique siroheme-[4Fe4S] coupled cofactor. Here, we report the structure of desulfoviridin from Desulfovibrio vulgaris, in which the dSiR DsrAB (sulfite reductase) subunits are bound to the DsrC protein. The alpha(2)beta(2)gamma(2) assembly contains two siroheme-[4Fe4S] cofactors bound by DsrB, two sirohydrochlorins and two [4Fe4S] centers bound by DsrA, and another four [4Fe4S] centers in the ferredoxin domains. A sulfite molecule, coordinating the siroheme, is found at the active site. The DsrC protein is bound in a cleft between DsrA and DsrB with its conserved C-terminal cysteine reaching the distal side of the siroheme. We propose a novel mechanism for the process of sulfite reduction involving DsrAB, DsrC, and the DsrMKJOP membrane complex (a membrane complex with putative disulfide/thiol reductase activity), in which two of the six electrons for reduction of sulfite derive from the membrane quinone pool. These results show that DsrC is involved in sulfite reduction, which changes the mechanism of sulfate respiration. This has important implications for models used to date ancient sulfur metabolism based on sulfur isotope fractionations.

Paleo-redox conditions during OAE 2 reflected in Demerara Rise sediment geochemistry (ODP Leg 207)

Cretaceous black shales deposited under severe oxygen-depletion are carriers of proxy signals for paleoenvironmental conditions. Using high-resolution patterns of iron and sulfur speciation, stable sulfur isotope discrimination, and trace element enrichment from black shale sequences of Sites 1258 and 1260 we identified alterations of the depositional environment during the Cenomanian/Turonian boundary Event (OAE 2) in the southern North Atlantic (ODP Leg 207, Demerara Rise). Changes in redox-conditions are suggested by high ratios of reactive to total iron which indicate that pyrite was formed both in the water column and within the sediment. This corresponds to euxinic paleoenvironmental conditions with at least temporarily free dissolved sulfide in the water column, a situation similar to the modern deep Black Sea. In addition, besides fixation of sulfide as iron sulfide, organic matter acted as an important sulfur trap during early diagenesis. Stable sulfur isotope fractionation went through a minimum within the OAE 2 interval indicating enhanced sulfur isotope discrimination during highest burial of organic matter (OM) potentially due to lower burial efficiency of reduced sulfur and/or a higher contributions from the oxidative part of the sulfur cycle (e.g., in the water column or the surface sediments). Elevated Fe/Al and Co/Al values within the Cenomanian/Turonian interval confirm euxinic conditions but, at the same time, require a zone where reducing but non-sulfidic conditions prevail, allowing reductive Fe and Co mobilization in oxygen-depleted nearshore sediments. The existence of an expanded oxygen-minimum-zone (OMZ) is demonstrated by extremely low Mn/Al ratios. A change in the trace metal (TM) inventory of seawater is postulated from a decline in seawater derived TM enrichment. Because hypoxic or even euxinic environments form an important sink for TM, the enlargement of euxinic depositional areas at the global onset of black shale deposition during OAE 2 have likely led to a drawdown of the seawater TM reservoir.

Fractionation of multiple sulfur isotopes during phototrophic oxidation of sulfide and elemental sulfur by a green sulfur bacterium

We present multiple sulfur isotope measurements of sulfur compounds associated with the oxidation of H 2S and S 0 by the anoxygenic phototrophic S-oxidizing bacterium Chlorobium tepidum. Discrimination between 34S and 32S was +1.8 ± 0.5‰ during the oxidation of H 2S to S 0, and −1.9 ± 0.8‰ during the oxidation of S 0 to SO 4 2 - , consistent with previous studies. The accompanying Δ 33S and Δ 36S values of sulfide, elemental sulfur, and sulfate formed during these experiments were very small, less than 0.1‰ for Δ 33S and 0.9‰ for Δ 36S, supporting mass conservation principles. Examination of these isotope effects within a framework of the metabolic pathways for S oxidation suggests that the observed effects are due to the flow of sulfur through the metabolisms, rather than abiotic equilibrium isotope exchange alone, as previously suggested. The metabolic network comparison also indicates that these metabolisms work to express some isotope effects (between sulfide, polysulfides, and elemental sulfur in the periplasm) and suppress others (kinetic isotope effects related to pathways for oxidation of sulfide to sulfate via the same enzymes involved in sulfate reduction acting in reverse). Additionally, utilizing fractionation factors for phototrophic S oxidation calculated from our experiments and for other oxidation processes calculated from the literature (chemotrophic and inorganic S oxidation), we constructed a set of ecosystem-scale sulfur isotope box models to examine the isotopic consequences of including sulfide oxidation pathways in a model system. These models demonstrate how the small δ 34S effects associated with S oxidation combined with large δ 34S effects associated with sulfate reduction (by SRP) and sulfur disproportionation (by SDP) can produce large (and measurable) effects in the Δ 33S of sulfur reservoirs. Specifically, redistribution of material along the pathways for sulfide oxidation diminishes the net isotope effect of SRP and SDP, and can mask the isotopic signal for sulfur disproportionation if significant recycling of S intermediates occurs. We show that the different sulfide oxidation processes produce different isotopic fields for identical proportions of oxidation, and discuss the ecological implications of these results to interpreting minor S isotope patterns in modern systems and in the geologic record.

Response to comment by I.C. Bourg on “Modeling sulfur isotope fractionation and differential diffusion during sulfate reduction in sediments of the Cariaco Basin” by M.A. Donahue, J.P. Werne, C. Meile, and T.W. Lyons

Response to comment by I.C. Bourg on “Modeling sulfur isotope fractionation and differential diffusion during sulfate reduction in sediments of the Cariaco Basin” by M.A. Donahue, J.P. Werne, C. Meile, and T.W. Lyons

Comment on “Modeling sulfur isotope fractionation and differential diffusion during sulfate reduction in sediments of the Cariaco Basin” by M.A. Donahue, J.P. Werne, C. Meile and T.W. Lyons

Comment on “Modeling sulfur isotope fractionation and differential diffusion during sulfate reduction in sediments of the Cariaco Basin” by M.A. Donahue, J.P. Werne, C. Meile and T.W. Lyons

Geology and geochemistry of the Mammoth breccia pipe, Copper Creek mining district, southeastern Arizona: evidence for a magmatic–hydrothermal origin

The Copper Creek mining district, southeastern Arizona, contains more than 500 mineralized breccia pipes, buried porphyry-style, copper-bearing stockworks, and distal lead–silver veins. The breccia pipes are hosted by the Copper Creek Granodiorite and the Glory Hole volcanic rocks. The unexposed Mammoth breccia pipe, solely recognized by drilling, has a vertical extent of 800 m and a maximum width of 180 m. The pipe consists of angular clasts of granodiorite cemented by quartz, chalcopyrite, bornite, anhydrite, and calcite. Biotite 40Ar/39Ar dates suggest a minimum age of 61.5 ± 0.7 Ma for the host Copper Creek Granodiorite and 40Ar/39Ar dates on hydrothermal sericite indicate an age of 61.0 ± 0.5 Ma for copper mineralization. Fluid inclusion studies suggest that a supercritical fluid with a salinity of approximately 10 wt.% NaCl equiv. condensed to a dilute aqueous vapor (1–2.8 wt.% NaCl equiv.) and a hypersaline brine (33.4–35.1 wt.% NaCl equiv.). Minimum trapping temperatures are 375°C and trapping depths are estimated at 2 km. Sulfur isotope fractionation of cogenetic anhydrite and chalcopyrite yields a temperature of mineralization of 469 ± 25°C. Calculated oxygen and hydrogen isotope values for fluids in equilibrium with quartz and sericite range from 10.2‰ to 13.4‰ and −60‰ to −39‰, respectively, suggesting that the mineralizing fluid was dominantly magmatic. Evidence from the stable isotope and fluid inclusion analyses suggests that the fluids responsible for Cu mineralization within the Mammoth breccia pipe exsolved from a gray porphyry phase found at the base of the breccia pipe.

Pyrite paragenesis and multiple sulfur isotope distribution in late Archean and early Paleoproterozoic Hamersley Basin sediments

The sulfur isotope record in late Archean and early Paleoproterozoic rocks is of considerable importance because it provides evidence for changes in early Earth atmospheric oxygen levels and potentially constrains the origin and relative impact of various microbial metabolisms during the transition from an anoxic to oxic atmosphere. Mass independently fractionated (MIF) sulfur isotopes reveal late Archean and early Paleoproterozoic sulfur sources in different pyrite morphologies in Western Australia's Hamersley Basin. Multiple sulfur isotope values in late Archean pyrite vary according to morphology. Fine grained pyrite has positive sulfur MIF, indicating a reduced elemental sulfur source, whereas pyrite nodules have negative sulfur MIF, potentially derived from soluble sulfate via microbial sulfate reduction. The Hamersley Basin δ 34S–Δ 33S record suggests that the extent of oxygenation of the surface ocean fluctuated through the Late Archean from at least 2.6 Ga, more than 150 million yr before the Great Oxidation Event. In the early Paleoproterozoic, there is less distinction between pyrite morphologies with respect to sulfur isotope fractionation, and pyrite from the Brockman Iron Formation trends toward modern sulfur isotope values. An important exception to this is the strong negative MIF recorded in layer parallel pyrite in Paleoproterozoic carbonate facies iron formation. This may suggest that deeper water hydrothermal environments remained anoxic while shallower water environments became more oxidised by the early Paleoproterozoic. The results of the current study indicate that sulfide paragenesis is highly significant when investigating Archean and early Paleoproterozoic multiple sulfur isotope compositions and sulfur sources.

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

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 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, δ17O labels, and Δ33S.

Stable sulfur isotope fractionation and discrimination between the sulfur atoms of thiosulfate during oxidation by Halothiobacillus neapolitanus

Growing cultures and nongrowing suspensions of Halothiobacillus neapolitanus selectively fractionated (32)S and (34)S during the oxidation of the sulfane- and sulfonate-sulfur atoms of thiosulfate. Sulfate was enriched in (32)S, with delta(34)S reaching -6.3 per thousand relative to the precursor sulfonate-sulfur of thiosulfate, which was progressively resynthesized from the thiosulfate-sulfane-sulfur during thiosulfate metabolism. Polythionates, principally trithionate, accumulated during thiosulfate oxidation and showed progressive increase in the relative (34)S content of their sulfonate groups, with delta(34)S values up to +20 per thousand, relative to the substrate sulfur. The origins of the sulfur in the sulfate and polythionate products of oxidation were tracked by the use thiosulfate labelled with (35)S in each of its sulfur atoms, enabling determination of the flow of the sulfur atoms into the oxidation products. The results confirm that highly significant fractionation of stable sulfur isotopes can be catalyzed by thiobacilli oxidizing thiosulfate, but that differences in the (34)S/(32)S ratios of the nonequivalent constituent sulfur atoms of the thiosulfate used as substrate mean that the oxidative fate of each atom needs separate determination. The data are very significant to the understanding of bacterial sulfur-compound oxidation and highly relevant to the origins of biogenic sulfate minerals.

Modeling sulfur isotope fractionation and differential diffusion during sulfate reduction in sediments of the Cariaco Basin

Sulfur isotope composition ( δ 34S) profiles in sediment pore waters often show an offset between sulfate and sulfide ( Δ δ 34 S SO 4 – H 2 S ) much greater in magnitude than S isotope fractionations observed in pure cultures. A number of workers have invoked an additional reaction, microbial disproportionation of sulfur intermediates, to explain the offset between experimental and natural systems. Here, we present an alternative explanation based on modeling of pore water sulfate and sulfide concentrations and stable isotope data from the Cariaco Basin (ODP Leg 165, Site 1002B). The use of unique diffusion coefficients for 32 SO 4 2 - and 34 SO 4 2 - , based on their unequal molecular masses, resulted in an increase in the computed fractionation by almost 10‰, when compared to the common assumption of equal diffusion coefficients for the two species. These small differences in diffusion coefficients yield calculated isotopic offsets between coeval sediment pore water sulfate and sulfide without disproportionation (up to 53.4‰) that exceed the largest fractionations observed in experimental cultures. Furthermore, the diffusion of sulfide within sediment pore waters leads to Δ δ 34 S SO 4 – H 2 S values that are even greater than those predicted by our model for sulfate reduction with unique diffusion coefficients. These diffusive effects on the sulfur isotope composition of pore water sulfate and sulfide can impact our interpretations of geologic records of sulfate and sulfide minerals, and should be considered in future studies.