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 H₂S and S⁰ by the anoxygenic phototrophic S-oxidizing bacterium Chlorobium tepidum. Discrimination between ³⁴S and ³²S was +1.8 ± 0.5‰ during the oxidation of H₂S to S⁰, and −1.9 ± 0.8‰ during the oxidation of S⁰ to , consistent with previous studies. The accompanying Δ³³S and Δ³⁶S values of sulfide, elemental sulfur, and sulfate formed during these experiments were very small, less than 0.1‰ for Δ³³S and 0.9‰ for Δ³⁶S, 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 δ³⁴S effects associated with S oxidation combined with large δ³⁴S effects associated with sulfate reduction (by SRP) and sulfur disproportionation (by SDP) can produce large (and measurable) effects in the Δ³³S 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.     

Sulfide Oxidation across Diffuse Flow Zones of Hydrothermal Vents

The sulfide (H₂S/HS^?) that is emitted from hydrothermal vents begins to oxidize abiotically with oxygen upon contact with ambient bottom water, but the reaction kinetics are slow. Here, using in situ voltammetry, we report detection of the intermediate sulfur oxidation products polysulfides [ $ {\text{S}}_{\text{x}}^{2 - } $ ] and thiosulfate [ $ {\text{S}}_{ 2} {\text{O}}_{ 3}^{ 2- } $ ], along with contextual data on sulfide, oxygen, and temperature. At Lau Basin in 2006, thiosulfate was identified in less than one percent of approximately 10,500 scans and no polysulfides were detected. Only five percent of 11,000 voltammetric scans taken at four vent sites at Lau Basin in May 2009 show either thiosulfate or polysulfides. These in situ data indicate that abiotic sulfide oxidation does not readily occur as H₂S contacts oxic bottom waters. Calculated abiotic potential sulfide oxidation rates are <10^?3 ??M/min and are consistent with slow oxidation and the observed lack of sulfur oxidation intermediates. It is known that the thermodynamics for the first electron transfer step for sulfide and oxygen during sulfide oxidation in these systems are unfavorable, and that the kinetics for two electron transfers are not rapid. Here, we suggest that different metal catalyzed and/or biotic reaction pathways can readily produce sulfur oxidation intermediates. Via shipboard high-pressure incubation experiments, we show that snails with chemosynthetic endosymbionts do release polysulfides and may be responsible for our field observations of polysulfides.     

Stable sulfur isotopes in the water column of the Cariaco Basin

Previous geochemical and microbiological studies in the Cariaco Basin indicate intense elemental cycling and a dynamic microbial loop near the oxic-anoxic interface. We obtained detailed distributions of sulfur isotopes of total dissolved sulfide and sulfate as part of the on-going CARIACO time series project to explore the critical pathways at the level of individual sulfur species. Isotopic patterns of sulfate (δ³⁴S_SO4) and sulfide (δ³⁴S_H2S) were similar to trends observed in the Black Sea water column: δ³⁴S_H2S and δ³⁴S_SO4 were constant in the deep anoxic water (varying within 0.6‰ for sulfide and 0.3‰ for sulfate), with sulfide roughly 54‰ depleted in ³⁴S relative to sulfate. Near the oxic-anoxic interface, however, the δ³⁴S_H2S value was ∼3‰ heavier than that in the deep water, which may reflect sulfide oxidation and/or a change in fractionation during in situ sulfide production through sulfate reduction (SR). δ³⁴S_H2S and Δ³³S_H2S data near the oxic-anoxic interface did not provide unequivocal evidence to support the important role of sulfur-intermediate disproportionation suggested by previous studies. Repeated observation of minimum δ³⁴S_SO4 values near the interface suggests ‘readdition’ of ³⁴S-depleted sulfate during sulfide oxidation. A slight increase in δ³⁴S_SO4 values with depth extended over the water column may indicate a reservoir effect associated with removal of ³⁴S-depleted sulfur during sulfide production through SR. Our δ³⁴S_H2S and Δ³³S_H2S data also do not show a clear role for sulfur-intermediate disproportionation in the deep anoxic water column. We interpret the large difference in δ³⁴S between sulfate and sulfide as reflecting fractionations during SR in the Cariaco deep waters that are larger than those generally observed in culturing studies.     

An integrated sulfur isotope model for Namibian shelf sediments

In this study the sulfur cycle in the organic-rich mud belt underlying the highly productive upwelling waters of the Namibian shelf is quantified using a 1D reaction-transport model. The model calculates vertical concentration and reaction rate profiles in the top 500 cm of sediment which are compared to a comprehensive dataset which includes carbon, sulfur, nitrogen and iron compounds as well as sulfate reduction (SR) rates and stable sulfur isotopes (³²S, ³⁴S). The sulfur dynamics in the well-mixed surface sediments are strongly influenced by the activity of the large sulfur bacteria Thiomargaritanamibiensis which oxidize sulfide (H₂S) to sulfate () using sea water nitrate () as the terminal electron acceptor. Microbial sulfide oxidation (SOx) is highly efficient, and the model predicts intense cycling between and H₂S driven by coupled SR and SOx at rates exceeding 6.0 mol S m⁻² y⁻¹. More than 96% of the SR is supported by SOx, and only 2-3% of the pool diffuses directly into the sediment from the sea water. A fraction of the produced by Thiomargarita is drawn down deeper into the sediment where it is used to oxidize methane anaerobically, thus preventing high methane concentrations close to the sediment surface. Only a small fraction of total H₂S production is trapped as sedimentary sulfide, mainly pyrite (FeS₂) and organic sulfur (S_org) (∼0.3 wt.%), with a sulfur burial efficiency which is amongst the lowest values reported for marine sediments (<1%). Yet, despite intense SR, FeS₂ and S_org show an isotope composition of ∼5 ‰ at 500 cm depth. These heavy values were simulated by assuming that a fraction of the solid phase sulfur exchanges isotopes with the dissolved sulfide pool. An enrichment in H₂S of ³⁴S towards the sediment-water interface suggests that Thiomargarita preferentially remove H₂³²S from the pore water. A fractionation of 20-30‰ was estimated for SOx (ε_SOx) with the model, along with a maximum fractionation for SR (ε_SR-max) of 100‰. These values are far higher than previous laboratory-based estimates for these processes. Mass balance calculations indicate negligible disproportionation of autochthonous elemental sulfur; an explanation routinely cited in the literature to account for the large fractionations in SR. Instead, the model indicates that repeated multi-stepped sulfide oxidation and intracellular disproportionation by Thiomargarita could, in principle, allow the measured isotope data to be simulated using much lower fractionations for ε_SOx (5‰) and ε_SR (78‰).     

Time dependence of organic matter decay and mixing processes in Framvaren, a permanently anoxic fjord in South Norway

Three different layers have been identified in Framvaren, which has a maximum water depth of 184 m. One oxic layer above the redoxcline at 18–20 m. One anoxic layer from 20 to 100 m which is occasionally ventilated by a flow over the sill (which has a depth of 2.5 m), and finally a stagnant layer below 100 m. Using the release rate of silica from the bottom and measurements of the concentration of HTO it is possible to make some calculations on the annual volume of interleaving in the layers 25–50 m, 50–75 m, and 75–100 m together with the advective flows. Reliable values of the sulfide concentration were obtained by precipitating and weighing HgS together with careful protection of all anoxic water samples with argon. The light yellow color of the precipitate in the depth range 25 to 80 m indicates that the occasional ventilation will cause such reactions as 0.50₂ + H₂S S(colloidal) + H₂O. The elemental sulfur, being stabilized with HS^–, is set free upon the precipitation of HgS. The new data for the concentration of sulfide give an acceptable stoichiometry for the decay reaction of organic matter. This is not the case with the data of Yao and Millero. The mean values for the concentrations of ammonium and phosphate agree with the new data of Yao and Millero. The mol/mol C/N ratio of 10.1 found in trapped material by Naess and coworkers (1988) agrees with the stoichiometry of the dissolved constituents, i.e. C/N = 9.92 ± 0.45. A denitrification reaction is suggested to explain the high values of C/N. The vertical diffusion coefficient at 100 m calculated from the depth profile of silica was 0.92 × 10^–6 m² s^–1 which lies in the range of values given by Fröyland. Finally, the ¹⁴C age of the total dissolved inorganic carbon (Ct) in the water below 90 m was about 1600 years indicating a bioproduction in the period 8000 years B.P. to A.D. 1853 when a channel was opened between the fjord outside (Helvikfjord) and Framvaren.     

Pyrite (FeS2) oxidation: A sub-micron synchrotron investigation of the initial steps

Pyrite is an environmentally significant mineral being the major contributor to acid rock drainage. Synchrotron based SPEM (scanning photoelectron microscopy) and micro-XPS (X-ray photoelectron spectroscopy) have been used to characterise fresh and oxidised pyrite (FeS₂) with a view to understanding the initial oxidation steps that take place during natural weathering processes. Localised regions of the pyrite surface containing Fe species of reduced coordination have been found to play a critical role. Such sites not only initiate the oxidation process but also facilitate the formation of highly reactive hydroxyl radical species, which then lead the S oxidation process.Four different S species are found to be present on fresh fractured pyrite surfaces: S₂²⁻_(bulk) (4-fold coordination), S₂²⁻_(surface) (3-fold coordination), S²⁻ and S⁰/S_n²⁻ (metal deficient sulfide and polysulfide respectively). These species were found to be heterogeneously distributed on the fractured pyrite surface. Both O₂ and H₂O gases are needed for effective oxidation of the pyrite surface. The process is initiated when O₂ dissociatively and H₂O molecularly adsorb onto the surface Fe sites where high dangling bond densities exist. H₂O may then dissociate to produce OH radicals. The adsorption of these species leads to the formation of Fe-oxy species prior to the formation of sulfoxy species. Evidence suggests that Fe-O bonds form prior to Fe-OH bonds. S oxidation occurs through interactions of OH radicals formed at the Fe sites, with formation of SO₄²⁻ occurring via S₂O₃²⁻/SO₃²⁻ intermediates. The pyrite oxidation process is electrochemical in nature and was found to occur in patches, where site specific adsorption of O₂ and H₂O has occurred. Fe and S oxidation was found to occur within the same area of oxidation probably in atomic scale proximity. Furthermore, the O in SO₄²⁻ arises largely from H₂O; however, depending on the surface history, SO₄²⁻ formed early in the oxidation process may also contain O from O₂.     

Modeling CO2 chemistry, δC, and oxidation of organic carbon and methane in sediment porewater: Implications for paleo-proxies in benthic foraminifera

I present a numerical diffusion-advection-reaction model to simulate CO₂ chemistry, δ¹³C, and oxidation of organic carbon and methane in sediment porewater. The model takes into account detailed reaction kinetics of dissolved CO₂ compounds, H₂O, H⁺, OH⁻, boron and sulfide compounds. These reactions are usually assumed to be in local equilibrium, which is shown to be a good approximation in most cases. The model also includes a diffusive boundary layer across which chemical species are transported between bottom water and the sediment-water interface. While chemical concentrations and δ¹³C_TCO2 at these locations are frequently assumed equal, I demonstrate that they can be quite different. In this case, shells of benthic foraminifera do not reflect the desired properties of bottom water, even for species living at the sediment-water interface (z = 0 cm). Environmental conditions recorded in their shells are strongly influenced by processes occurring within the sediment. The model is then applied to settings in the Santa Barbara Basin and at Hydrate Ridge (Cascadia Margin), locations of strong organic carbon and methane oxidation. In contrast to earlier studies, I show that a limited contribution of methane-derived carbon to porewater TCO₂ in the Santa Barbara Basin cannot be ruled out. Simulation of methane venting shows that at oxidation rates greater than , the δ¹³C of porewater TCO₂ at z > 1 cm is depleted by more than 15‰ relative to bottom water. Depletions of this magnitude have not been observed in living benthic foraminifera, even at methane vents with much higher oxidation rates. This suggests that foraminifera at these sites either calcify at very shallow sediment depth or during times when oxidation rates are much lower than ∼50 μmol cm⁻² y⁻¹.     

Reduction of Manganese Oxides: Thermodynamic,Kinetic and Mechanistic Considerations for One- Versus Two-Electron Transfer Steps

Manganese oxides, typically similar to δ-MnO₂, form in the aquatic environment at near neutral pH via bacterially promoted oxidation of Mn(II) species by O₂, as the reaction of [Mn(H₂O)₆]²⁺ with O₂ alone is not thermodynamically favorable below pH of ~?9. As manganese oxide species are reduced by the triphenylmethane compound leucoberbelein blue (LBB) to form the colored oxidized form of LBB (λ_max?=?623 nm), their concentration in the aquatic environment can be determined in aqueous environmental samples (e.g., across the oxic–anoxic interface of the Chesapeake Bay, the hemipelagic St. Lawrence Estuary and the Broadkill River estuary surrounded by salt marsh wetlands), and their reaction progress can be followed in kinetic studies. The LBB reaction with oxidized Mn solids can occur via a hydrogen atom transfer (HAT) reaction, which is a one-electron transfer process, but is unfavorable with oxidized Fe solids. HAT thermodynamics are also favorable for nitrite with LBB and MnO₂ with ammonia (NH₃). Reactions are unfavorable for NH₄⁺ and sulfide with oxidized Fe and Mn solids, and NH₃ with oxidized Fe solids. In laboratory studies and aquatic environments, the reduction of manganese oxides leads to the formation of Mn(III)-ligand complexes [Mn(III)L] at significant concentrations even when two-electron reductants react with MnO₂. Key reductants are hydrogen sulfide, Fe(II) and organic ligands, including the siderophore desferioxamine-B. We present laboratory data on the reaction of colloidal MnO₂ solutions (λ_max?~?370 nm) with these reductants. In marine waters, colloidal forms of Mn oxides (<?0.2 µm) have not been detected as Mn oxides are quantitatively trapped on 0.2-µm filters. Thus, the reactivity of Mn oxides with reductants depends on surface reactions and possible surface defects. In the case of MnO₂, Mn(IV) is an inert cation in octahedral coordination; thus, an inner-sphere process is likely for electrons to go into the empty e _g ^* conduction band of its orbitals. Using frontier molecular orbital theory and band theory, we discuss aspects of these surface reactions and possible surface defects that may promote MnO₂ reduction using laboratory and field data for the reaction of MnO₂ with hydrogen sulfide and other reductants.     

Prediction of the speciation of alkaline earths adsorbed on mineral surfaces in salt solutions

Despite the fact that the bulk compositions of most low temperature natural surface waters, groundwaters, and porewaters are heavily influenced by alkaline earths, an understanding of the development of proton surface charge in the presence of alkaline earth adsorption on the surfaces of minerals is lacking. In particular, models of speciation at the mineral-water interface in systems involving alkaline earths need to be established for a range of different minerals. In the present study, X-ray standing wave results for Sr²⁺ adsorption on rutile as a tetranuclear complex [Fenter, P., Cheng, L., Rihs, S., Machesky, M., Bedyzk, M.D., Sturchio, N.C., 2000. Electrical double-layer structure at the rutile-water interface as observed in situ with small-period X-ray standing waves. J. Colloid Interface Sci.225, 154-165] are used as constraints for all the alkaline earths in surface complexation simulations of proton surface charge, metal adsorption, and electrokinetic experiments referring to wide ranges of pH, ionic strength, surface coverage, and type of oxide. The tetranuclear reaction

4>SOH+M²⁺+H₂O=(>SOH)₂(>SO^-)₂_M(OH)⁺+3H⁺     

Conditions of sulfide formation in the metasomatized mantle beneath East Antarctica

Garnet–spinel lherzolites from Antarctica and peridotites from Mongolia were fluid saturated, which is indicated by the presence of fluid inclusions in their minerals. Flows of reactive fluids caused extensive metasomatic alteration of mantle materials. The cryometric and Raman spectroscopic investigation of the Antarctic xenoliths showed that their fluid was a complex mixture of CO₂, N₂, H₂S, and H₂O with a density of up to 1.23 g/cm³. The entrapment of fluids was accompanied by the formation of clusters of numerous sulfide inclusions. The compositions of these inclusions correspond to a Ni-rich sulfide melt and a monosulfide solid solution. The partition coefficient of Ni between them (D_Ni mss/melt) ranges from 0.99 to 3.23, which suggests that the two-phase sulfide assemblages in the partly decrepitated inclusions equilibrated at 920–1060°C. In order to refine the initial P-T conditions of the development of the Antarctic peridotites, the results of our investigation were evaluated in the light of experimental data on (1) the stability field of the two-phase assemblage mss + sulfide melt, (2) the solidus of peridotite + 0.9CO₂ + 0.1 H₂O, and (3) isochores of 0.8CO₂ + 0.2N₂ fluid. The obtained parameters are close to 1270–1280°C and 2.2 GPa and lie near the Sp–Gar boundary. The temperature of the existence of sulfide melt at a pressure of 2.2 GPa must be near 1300°C and corresponds to the boundary between the occurrence of carbon as CO₂ fluid and carbonate (carbonate melt).     

Hydrogen sulfide and organic carbon at the sediment–water interface in coastal brackish Lake Nakaumi, SW Japan

The relationship among H₂S, total organic carbon (TOC), total sulfur (TS) and total nitrogen contents of surface sediments (0–1 cm) was examined to quantify the relationship between H₂S concentrations and TOC content at the sediment water interface in a coastal brackish lake, Nakaumi, southwest Japan. In this lake, bottom water becomes anoxic during summer due to a strong halocline. Lake water has ample dissolved SO₄ ^2? and the surface sediments are rich in planktic organic matter (C/N 7–9), which is highly reactive in terms of sulfate reduction. In this setting the amount of TOC should be a critical factor regulating the activity of sulfate reduction and H₂S production. In portions of the lake where sediment TOC content is less than 3.5 %, H₂S was very low or absent in both bottom and pore waters. However, in areas with TOC >3.5 %, H₂S was correlated with TOC content (pore water H₂S (ppm) = 13.9 × TOC (%) ? 52.1, correlation coefficient: 0.72). H₂S was also present in areas with sediment TS above 1.2 % (present as iron sulfide), which suggests that iron sulfide formation is tied to the amount of TOC. Based on this relationship, H₂S production has progressively increased after the initiation of land reclamation projects in Lake Nakaumi, as the area of sapropel sediments has significantly increased. This TOC–H₂S relationship at sediment–water interface might be used to infer H₂S production in brackish–lagoonal systems similar to Lake Nakaumi, with readily available SO₄ ^2? and reactive organic matter.     

Natural realgar and amorphous AsS oxidation kinetics

The oxidation rates of natural realgar and amorphous synthetic AsS by dissolved oxygen were evaluated using mixed flow reactors at pH 7.2 to 8.8 and dissolved oxygen contents of 5.9 to 16.5 ppm over a temperature range of 25 to 40°C. The ratios of As/S are stoichiometric for all amorphous AsS oxidation experiments except for two experiments conducted at pH ∼8.8. In these experiments, stoichiometric ratios of As/S were only observed in the early stages of AsS (am) oxidation whereas lower As/S ratios were observed during steady state. For realgar oxidation experiments, the As/S ratio is less than the stoichiometric ratio of realgar, ranging between 0.61 and 0.71. This nonstoichiometric release of As and S to solution indicates that realgar oxidation is more selective for S after the rates of oxidation become constant. All measured oxidation rates at 25°C can be described within experimental uncertainties as follows: Table 1

Rate Expression	Activation Energy (kJ/mol)
R(Realgar/As) = 10−9.63(±0.41)[DO]0.51(±0.08)[H+]−0.28(±0.05)	64.2 ± 9.8
R(Realgar/S) = 10−9.74(±0.35)[DO]0.54(±0.05)[H+]−0.31(±0.04)	62.2 ± 9.0
R(AsS(am)) = 10−13.65(±0.82)[DO]0.92(±0.08)[H+]−1.09(±0.10)	124 ± 18.8

Full-size table

     

Atmospheric weathering of Scandinavian alum shales and the fractionation of C,N and S isotopes

Subaerial exposure and oxidation of organic carbon (C_org)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial C_org oxidation are expected to shift new biomass δ¹³C_org composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ¹³C_org at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, C_org-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, C_org-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of C_org without producing a δ¹³C shift between acid rock drainage precipitates and shale. Moreover, ¹³C enrichment in inorganic carbon of precipitates does not support microbial C_org oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ³⁴S = δ³⁴S_shale − δ³⁴S_precipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ¹⁵N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of C_org, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment.     

Manganese cycling in a eutrophic lake — Rates and pathways

The redox processes regulating transport of Mn in the water column of a eutrophic, dimictic lake (Lake Norrviken, Sweden) are interpreted based on a one-dimensional diffusion-reaction model for Mn(II). It is found that rates and rate constants for oxidation and reduction vary greatly with depth and also with time during the season of stratification. Calculated rates show that Mn(II) oxidation and reduction generally occur in narrow depth intervals (25–50 cm). This is in good agreement with measured profiles of particulate Mn (MnO _x ). Maximum oxidation rate constants (assuming first order kinetics) at each date are in the first half of the season <1 d^–1, but then increases to a rather constant value of about 25 d^–1. These high rate constants are indicative of microbiological involvement in the Mn(II) oxidation. This is further evidenced by SEM-EDS analysis showing Mn enriched particles morphologically similar toMetallogenium. Reductive dissolution of Mn oxides occurs mainly in the zone just below the zone of maximum oxidation rate. The release of Mn(II) is accompanied by production of alkalinity and CO₂. The relation between production rates of Mn(II) and alkalinity indicates that Mn oxides act as terminal electron acceptors in the bacterially mediated oxidation of organic matter. However, the Mn²⁺/CO₂ ratio is significantly lower than what is expected from this process. It is suggested that the Mn reduction is coupled to fermentation. Close coexistence of Mn reduction and oxidation at high rates, such as found in the water column of this lake, facilitates rapid and continuous regeneration of reducible Mn oxides. This gives rise to a quantitatively important mechanism of organic matter oxidation in the water column.     

Framvaren and the Black Sea – Similarities and Differences

The following determinations in the Norwegian fjord Framvaren and the Black Sea have been compared: carbon-14, carbon-13, alkalinity, total dissolved inorganic carbon, sulfide, tritium (HTO), trace metals, silica, ammonium and phosphate. The historical development of the two anoxic basins is quite different. The carbon-14 age of the total inorganic dissolved carbonate in the deep water is 2000 years in the Black Sea, but only 1600 in Framvaren. The fresh water supply and composition are different. The rivers entering the Black Sea have a high alkalinity, but the river input and runoff to Framvaren has a very low alkalinity. The alkalinity, carbonate and sulfide concentrations in the anoxic waters below the chemoclines are much higher in Framvaren. This is mainly an effect of the different surface to volume ratios. The difference in carbon-13 (-8 for the Black Sea deep water, -19 in the Framvaren bottom water) is mainly due to the smaller imprint of the decomposition of organic matter on the Black Sea deep water.The concentration of trace metals in the particulate form are about the same in the deep water. About 76% of the molybdate in seawater is lost in the sulfidic water of Framvaren, and about 82–96% of the molybdate carried into the Black Sea by the Bosporus undercurrent is lost in the deep water. The relation between silica, ammonium and phosphate can be understood if part of the ammonium is being removed by denitrification, a process that most likely has been going on for thousands of years.     

Sulfur redox reactions: Hydrocarbons,native sulfur,Mississippi Valley-type deposits,and sulfuric acid karst in the Delaware Basin,New Mexico and Texas

Hydrocarbons, native sulfur, Mississippi Valley-type (MVT) deposits, and sulfuric acid karst in the Delaware Basin, southeastern New Mexico, and west Texas, USA, are all genetically related through a series of sulfur redox reactions. The relationship began with hydrocarbons in the basin that reacted with sulfate ions from evaporite rock to produce isotopically light ( ³⁴S = -22 to -12) H₂S and bioepigenetic limestone (castiles). This light H₂S was then oxidized at the redox interface to produce economic native sulfur deposits ( ³⁴S = -15 to +9) in the castiles, paleokarst, and along graben-boundary faults. This isotopically light H₂S also migrated from the basin into its margins to accumulate in structural (anticlinal) and stratigraphic (Yates siltstone) traps, where it formed MVT deposits within the zone of reduction ( ³⁴S = -15 to +7). Later in time, in th zone of oxidation, this H₂S reacted with oxygenated water to produce sulfuric acid, which dissolved the caves (e.g., Carlsbad Cavern and Lechuguilla Cave, Guadalupe Mountains). Massive gypsum blocks on the floors of the caves ( ³⁴S = -25 to +4) were formed as a result of this reaction. The H₂S also produced istopically light cave sulfur ( ³⁴S = -24 to -15), which is now slowly oxidizing to gypsum in the presence of vadose drip water.     

Relationship between Se/S and sulfur isotope ratios of hydrothermal sulfide minerals

The pH and f_{O 2} dependences of the [Se^2–]/[S^2–] ratio in chloride solutions at 100°, 200° and 300°C are predicted thermodynamically. Under the high f_{O 2} conditions where sulfate species are dominant in solution, the [Se^2–]/[S^2–] ratio always increases with increasing pH and/or f_{O 2}. Under the low f_{O 2} conditions where sulfide species are dominant in solution, the pH and f_{O 2} dependences of the [Se^2–]/[S^2–] ratio are seriously affected by the presence of native selenium. With native selenium present, the [Se^2–]/[S^2–] ratio decreases with increasing f_{O 2}, but almost independent of pH in geologically important pH regions. When native selenium is absent, the [Se^2–]/[S^2–] ratio is solely a function of pH and independent of f_{O 2}. Combining the above with the pH and f_{O 2} dependences of ³⁴S value of aqueous sulfur species, we discuss the possible influences of the pH and f_{O 2} of ore-forming solutions on the relationship between the Se/S ratio and ³⁴S value of hydrothermal sulfide minerals. The results are applied to some Japanese sulfide ore deposits.     

Particulate sulfur species in the water column of the Cariaco Basin

The biogeochemistry of iron sulfide minerals in the water column of the Cariaco Basin was investigated in November 2007 (non-upwelling season) and May 2008 (upwelling season) as part of the on-going CARIACO (CArbon Retention In A Colored Ocean) time series project. The concentrations of particulate sulfur species, specifically acid volatile sulfur (AVS), greigite, pyrite, and particulate elemental sulfur, were determined at high resolution near the O₂/H₂S interface. In November 2007, AVS was low throughout the water column, with the highest concentration at the depth where sulfide was first detected (260 m) and with a second peak at 500 m. Greigite, pyrite, and particulate elemental sulfur showed distinct concentration maxima near the interface. In May 2008, AVS was not detected in the water column. Maxima for greigite, pyrite, and particulate elemental sulfur were again observed near the interface. We also studied the iron sulfide flux using sediment trap materials collected at the Cariaco station. Pyrite comprised 0.2-0.4% of the total particulate flux in the anoxic water column, with a flux of 0.5-1.6 mg S m⁻² d⁻¹.Consistent with the water column concentration profiles for iron sulfide minerals, the sulfur isotope composition of particulate sulfur found in deep anoxic traps was similar to that of dissolved sulfide near the O₂/H₂S interface. We conclude that pyrite is formed mainly within the redoxcline where sulfur cycling imparts a distinct isotopic signature compared to dissolved sulfide in the deep anoxic water. This conclusion is consistent with our previous study of sulfur species and chemoautotrophic production, which suggests that reaction of sulfide with reactive iron is an important pathway for sulfide oxidation and sulfur intermediate formation near the interface. Pyrite and elemental sulfur distributions favor a pathway of pyrite formation via the reaction of FeS with polysulfides or particulate elemental sulfur near the interface. A comparison of thermodynamic predictions with actual concentration profiles for iron sulfides leads us to argue that microbes may mediate this precipitation.