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1.
We present a 3-year study of concentrations and sulfur isotope values (δ34S, Δ33S, and Δ36S) of sulfur compounds in the water column of Fayetteville Green Lake (NY, USA), a stratified (meromictic) euxinic lake with moderately high sulfate concentrations (12-16 mM). We utilize our results along with numerical models (including transport within the lake) to identify and quantify the major biological and abiotic processes contributing to sulfur cycling in the system. The isotope values of sulfide and zero-valent sulfur across the redox-interface (chemocline) change seasonally in response to changes in sulfide oxidation processes. In the fall, sulfide oxidation occurs primarily via abiotic reaction with oxygen, as reflected by an increase in sulfide δ34S at the redox interface. Interestingly, S isotope values for zero-valent sulfur sampled at this time still reflect production and recycling by phototrophic S-oxidation. In the spring, sulfide S isotope values suggest an increased input from phototrophic oxidation, consistent with a more pronounced phototroph population at the chemocline. This trend is associated with smaller fractionations between sulfide and zero-valent sulfur, suggesting a metabolic rate control on fractionation similar to that for sulfate reduction. Comparison of our data with previous studies indicates that the S isotope values of sulfate and sulfide in the deep waters are remarkably stable over long periods of time, with consistently large fractionations of up to 58‰ in δ34S. Models of the δ34S and Δ33S trends in the deep waters (considering mass transport via diffusion and advection along with biological processes) require that these fractionations are a consequence of sulfur compound disproportionation at and below the redox interface in addition to large fractionations during sulfate reduction. The large fractionations during sulfate reduction appear to be a consequence of the high sulfate concentrations and the distribution of organic matter in the water column. The occurrence of disproportionation in the lake is supported by profiles of intermediate sulfur compounds and by lake microbiology, but is not evident from the δ34S trends alone. These results illustrate the utility of including minor S isotopes in sulfur isotope studies to unravel complex sulfur cycling in natural systems.  相似文献   

2.
The effect of dissolved barium on biogeochemical processes at cold seeps   总被引：2，自引：0，他引：2  
A numerical model was applied to investigate and quantify the biogeochemical processes fueled by the expulsion of barium and methane-rich fluids in the sediments of a giant cold-seep area in the Derugin Basin (Sea of Okhotsk). Geochemical profiles of dissolved Ba2+, Sr2+, Ca2+, SO42−, HS−, DIC, I− and of calcium carbonate (CaCO3) were fitted numerically to constrain the transport processes and the kinetics of biogeochemical reactions. The model results indicate that the anaerobic oxidation of methane (AOM) is the major process proceeding at a depth-integrated rate of 4.9 μmol cm−2 a−1, followed by calcium carbonate and strontian barite precipitation/dissolution processes having a total depth-integrated rate of 2.1 μmol cm−2 a−1. At the low seepage rate prevailing at our study site (0.14 cm a−1) all of the rising barium is consumed by precipitation of barite in the sedimentary column and no benthic barium flux is produced. Numerical experiments were run to investigate the response of this diagenetic environment to variations of hydrological and biogeochemical conditions. Our results show that relatively low rates of fluid flow (<∼5 cm a−1) promote the dispersed precipitation of up to 26 wt% of barite and calcium carbonate throughout the uppermost few meters of the sedimentary column. Distinct and persistent events (several hundreds of years long) of more vigorous fluid flow (from 20-110 cm a−1), instead, result in the formation of barite-carbonate crusts near the sediment surface. Competition between barium and methane for sulfate controls the mineralogy of these sediment precipitates such that at low dissolved methane/barium ratios (<4-11) barite precipitation dominates, while at higher methane/barium ratios sulfate availability is limited by AOM and calcium carbonate prevails. When seepage rates exceed 110 cm a−1, barite precipitation occurs at the seafloor and is so rapid that barite chimneys form in the water column. In the Derugin Basin, spectacular barite constructions up to 20 m high, which cover an area of roughly 22 km2 and contain in excess of 5 million tons of barite, are built through this process. In these conditions, our model calculates a flux of barium to the water column of at least 20 μmol cm−2 a−1. We estimate that a minimum of 0.44 × 106 mol a−1 are added to the bottom waters of the Derugin Basin by cold seep processes, likely affecting the barium cycle in the Sea of Okhotsk.  相似文献   

3.
Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits   总被引：2，自引：0，他引：2  
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 δ34S versus δ18O 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 δ34S versus δ18O 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.  相似文献   

4.
Biogenic barium (Baxs) was measured in suspended particles at the DYFAMED site in the northwestern Mediterranean Sea, on a monthly basis between February and June 2003. The barium content of barite (BaSO4) micro-crystals was investigated using Scanning Electron Microscopy (SEM). Suspended particles were collected by filtration of small volumes of seawater (∼10 L), as well as large volumes up to 2400 L in March and in May. The Baxs profiles obtained from small-volume filtration display the typical mesopelagic maximum reported by earlier studies at ∼200 m depth, with concentrations up to 595 pmol L−1. In addition, suspended Baxs was found almost exclusively in the form of micro-crystalline barite, except in February. The Baxs profiles obtained from large-volume filtration are consistent with the small-volume filtration findings, but reveal a significant Baxs peak of 1698 pmol L−1 in the surface waters in May. Seasonal sampling at the DYFAMED site shows a net increase in barite concentration during phytoplanktonic blooms, confirming the involvement of biological systems in barite formation, as well as the potential role of barite as a primary productivity tracer. In addition, the coincidence between the mesopelagic barite maximum and the oxygen minimum layer suggests that barite is primarily found at depths of intense remineralization, in agreement with the hypothesis that barite forms within microenvironments of decaying organic matter.  相似文献   

5.
Bacteria from lake mud grown under anaerobic conditions with powdered barite present significantly increase the amount of barium that dissolves in the culture medium. Innocula of lake mud were added to a growth medium specified for sulfate-reducing bacteria. Powdered barite was added to each culture flask and flasks were purged with nitrogen, sealed and maintained at 20°C for 17 days. When the cultures were opened for analysis, hydrogen sulfide and iron sulfide had formed in all growing cultures. In cultures containing barite as the only sulfate, the barium content of the culture solutions had risen to an average of 3.3 ppm (maximum = 3.8 ppm, minimum = 1.8 ppm). Cultures containing ferrous sulfate and barite showed less than 0.1 ppm barium in solution. Cultures that had been sterilized by poisoning or autoclaving showed approximately 0.5 ppm barium in solution. Sulfate-reducing bacteria may be responsible for the high barium concentrations recorded in streams draining barite mining areas.  相似文献   

6.
岩石露头和矿山废弃物中的金属硫化物在地表、近地表条件下的氧化作用往往导致多种环境问题,因此,金属硫化物的地表风化一直是备受关注的表生过程之一。越来越多的证据表明微生物对矿物的氧化在金属硫化物风化过程中发挥着重要作用。实验研究发现:微生物在金属硫化物表面附着并形成微生物膜,在矿物-微生物膜界面微环境中存在着强烈的微生物氧化和化学氧化作用,两种氧化作用相互协同、共同促进。在此过程中,金属硫化物的S、As、Fe等元素经历了复杂的电子传递、逐级氧化的动力学过程,最终形成稳定的高铁硫酸盐或氧化物,并形成大量的酸性排水。该过程受多种因素的影响,包括细菌种类、光照和溶液Fe~(2+)浓度等。金属硫化物的微生物氧化直接导致重金属大量释放和严重的环境危害,释放的酸性排水还引发碳酸盐矿物分解和CO_2排放,会对全球碳循环产生不可忽视的影响。在地球演化的早期阶段,金属硫化物氧化消耗大气氧气可能导致大氧化进程滞后。尽管关于金属硫化物-微生物相互作用研究取得了长足的进展,但金属硫化物微生物氧化的分子机制和全球尺度的元素地球化学循环还有待深入研究,原位纳米观测技术的引入和全球物质循环模型研究具有必要性和紧迫性,同时也对生物冶金技术的发展有着重要的意义。  相似文献   

7.
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.  相似文献   

8.
Stratiform and stratabound barite ± magnetite beds are intimately associated with the polymetallic Broken Hill-type (BHT) massive sulfide deposits of the Aggeneys-Gamsberg Pb–Zn–Cu ± Ag–Ba district in the Northern Cape Province, South Africa. Barite samples were collected and studied from four localities in the district. Although metamorphic water–rock interaction processes have partially altered the chemical and to a lesser degree the isotopic composition of barite, samples identified as being the least altered display distinctly different isotopic compositions that are thought to reflect different modes of origin. All barite samples are marked by low concentrations of SrO (0.5 ± 0.2 wt%), highly radiogenic 87Sr/86Sr ratios, elevated δ 34S and δ 18O values compared to contemporaneous Mesoproterozoic seawater. Radiogenic 87Sr/86Sr signatures (0.7164 ± 0.0028) point to an evolved continental crustal source for Sr and Ba, while elevated δ 34S values (27.3 ± 4.9‰) indicate that contemporaneous seawater sulfate, modified by bacterial sulfate reduction, was the single most important sulfur reservoir for barite deposition. Most importantly, δ 18O values suggest a lower temperature of formation for the Gamsberg deposit compared with the occurrences in the Aggeneys area, i.e. Swartberg-Tank Hill and Big Syncline. The obvious differences in temperature of formation are in good agreement with the Cu-rich, Ba-poor nature of the sulfide mineralization of the Aggeneys deposits vs the Cu-poor, Ba-rich character of the Gamsberg deposit. In conjunction with this, isotopic and petrographic arguments favor a sub-seafloor replacement model for the stratabound barite occurrences of the Aggeneys deposits, while at Gamsberg, deposition at the sediment–water interface as a true sedimentary exhalite appears more likely.  相似文献   

9.
The precipitation of extremely 34S-rich barite in the late stage of mineralization in the Mississippi Valleytype deposits of the Illinois-Kentucky district (U.S.A.) may be explained by reactions involving thiosulfate (S2O 3 = ). Inorganic processes are known to concentrate 34S in the sulfonate site of thiosulfate and 32S in the sulfate site. In the mineralizing solution, these inorganic processes may have fractionated sulfur between the two sites by about 40 per mil. At the low temperatures of the late barite stage of mineralization, bacteria are known to metabolize thiosulfate by various reactions. In one of these, dissimilatory reduction, hydrogen sulfide and sulfite are produced. Isotopically light sulfite is preferentially reduced to sulfide by bacteria to leave a residual sulfite enriched in 34S. Part of the residual sulfite may be oxidized to form isotopically heavy sulfate; part may recombine with hydrogen sulfide to form thiosulfate. The recombination also enriches the sulfonate site in 34S and the sulfane site in 32S. Recycling the newly formed thiosulfate through the above steps further enriches sulfite and sulfate from oxidation of sulfite in 34S. During genesis of the ores, the aggregate effect of these reactions may have been the precipitation of extremely 34S-rich barite. The sequence of reactions suggested above requires the presence of organic matter. Previously proposed reactions to account for the precipitation of sulfide minerals and fluorite and for the carbonate paragenesis also require the presence of organic matter. Thus, organic matter in the host rocks may cause the various ore-zone reactions and account for the localization of the ores.  相似文献   

10.
A relict mound of Holocene barite (BaSO4) tufa underlies the Flybye Springs, a small, barium‐rich, cold sulphur spring system in the Northwest Territories of Canada. The tufa is composed of relatively pure barite with ≤0·34 wt% Ca2+ and ≤0·77 wt% Sr2+. The mound is made up of coated bubble, raft, undulatory sheet, stromatolitic, coated grain and detrital conglomerate barite tufa. Although previously unreported in barite, these lithotypes are akin to facies found in many carbonate spring deposits. Raft and ooid‐coated grain tufa was formed via ‘inorganic’ barite precipitation in spring water ponds and tributaries where rapid oxidation of sulphide to sulphate established barite supersaturation. Undulatory sheet tufa may have formed by the reaction of dissolved barium with sulphate derived from the oxidation of extracellular polysaccharide‐rich colloidal sulphur films floating in oxygenated, barite‐saturated spring water ponds. Coated bubble, oncoid‐coated grain and stromatolitic tufa with filamentous microfossils was formed in close association with sulphur‐tolerant microbes inhabiting dysoxic and oxygenated spring water tributaries and ponds. Adsorption of dissolved barium to microbial extracellular polysaccharide probably facilitated the development of these ‘biogenic’ lithotypes. Detrital conglomerate tufa was formed by barite cementation of microdetrital tufa, allochthonous lithoclasts and organic detritus, including caribou hair. Biogenic textures, organic artefacts and microfossils in the Flybye barite tufa have survived diagenetic aggradational recrystallization and precipitation of secondary cements, indicating the potential for palaeoecological information to be preserved in barite in the geological record. Similarities between the Flybye barite tufa and carbonate spring deposits demonstrate that analogous textures can develop in chemical sedimentary systems with distinct mineralogy, biology and physiochemistry.  相似文献   

11.
The barium deposits in Ankang and Xunyang counties,Shaanxi Province,China,occur in the northernmost part of the world-class barium metallogenic belt in south Qinling.The deposits are hosted by the Lower Silurian carbonaceous siliceous rocks,with a unique combination of barite and witherite.The homogenization temperatures of fluid inclusions in the barite are mainly concentrated between 135 and 155 ℃,whereas those from the witherite have two peaks of 165-175 ℃,and 215-225℃,respectively.Laser Raman analysis of fluid inclusions indicates that the vapor phase of fluid inclusions in barite is dominated by H_2O,although some contains N_2,H_2S,and CH_4.The compositions of the vapor and liquid phases of fluid inclusions in witherite can be divided into two end-members,one dominated by H_2O without other volatiles,and the other containing CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6 in addition to H_2O.CO_2,H_2S,and some CH_4 are interpreted as products of chemical reactions during mineralization.Organic gases(CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6) in the fluids were critical in the formation of barium sulfate versus carbonate.The δ~(34)S values of barite range from 38.26‰ to54.23‰(CDT),the δ~(34)S values of sulfides coexisting with barium minerals vary from 22.44‰ to25.11‰(CDT),and those in the wall rock from 11.60‰ to 19.06‰(CDT).We propose that the SO_4~(2-)generally experienced bacterial sulfate reduction in seawater before mineralization,and some SO_4~(2-)also experienced thermochemical sulfate reduction in hydrothermal system during mineralization.The δ~(13)C values of witherite range from-27.30‰ to-11.80‰(PDB),suggesting that carbon was sourced from organic substances(like CH_4,C_2H_4,and C_2H_6).The formation of witherite was possibly associated with thermochemical sulfate reduction,which caused the consumption of the organic gases and SO_4~(2-) in the hydrothermal solutions,consequently inhibiting barite formation.The important conditions for forming witherite include high fluid temperatures,high Ba~(2+) concentrations,CO_2 in the fluids,low HS~- concentrations,and the subsequent rapid diffusion of H_2S during thermochemical sulfate reduction of the fluids.  相似文献   

12.
Fatty acids isolated in sedimentary black barite (BaSO4) from Arkansas and Nevada were identified by gas chromatography-mass spectroscopy. The dominant or major fatty acids found in these beds of barite are C16:0, C18:0, and C18:1. The occurrence and distribution of these acids in this type of rock may serve as “molecular fingerprints” of microbial biogeochemical processes. The organic matter and associated microorganisms are shown to be trapped within the finely crystalline barite, thus forming a closed system for microbial diagenesis.Important differences that occur in the distribution of the lesser or minor fatty acids probably result from: (1) the nature of the progenitor organic detritus in the environment of barite deposition: and (2) the subsequent degree of microbiological alteration of the parent organic debris swept into and trapped in the depositional environment.Three general models of sedimentary environments are proposed in which anoxic conditions may prevail and where barium sulfate (BaSO4) may precipitate: (1) in a silled basin with semi-restricted circulation; (2) on an outer continental shelf where the slope is encroached upon by water of the oxygen minimum layer; (3) on a low-energy, inner shelf or semi-restricted embayment impinged by a wedge of anoxic water.The major geochemical and geological parameters which are believed to be the significant factors controlling the formation and high grade of these organic-rich, black bedded barites are: (1) a unique source of barium-rich fluid that only contains trace amounts of other elements; (2) the presence of an anoxic bottom environment within the depositional basin; (3) a reflux source of sulfate ion; (4) an adequate source of organic matter.The results of this study may serve as guidelines for future exploration in similar, untested sedimentary basins, especially those with rocks of middle Paleozoic age.  相似文献   

13.
大河边重晶石矿床是一个世界级的超大型重晶石矿床。最近在该区重晶石矿床下部的震旦系陡山沱组碳酸盐岩(白云岩)和碎屑岩中,新发现一套规模较大、层位产出稳定的铅锌矿化。铅锌矿体和重晶石矿床具有"上部为重晶矿,下部为铅锌硫化物矿床"的矿化特征。铅锌矿段矿石矿物主要为闪锌矿、黄铁矿及方铅矿,含少量白铁矿、黄铜矿及磁黄铁矿;脉石矿物主要为石英和重晶石,少量白云石、热液磷灰石、炭沥青及钡冰长石。成矿流体特征类似于形成沉积喷流型铅锌矿床的流体特征。铅锌矿化中的硫源自局限海盆内早寒武世海水经硫酸盐还原作用提供。此种类似于喷流沉积型铅锌矿床在南华裂谷盆地一带矿化层位稳定、分布范围较广泛,体现早寒武世时在裂谷盆地内存在一次大规模的热液事件。天柱大河边铅锌矿床的发现具有重要的资源意义及区内该种矿床的勘查意义。  相似文献   

14.
A transport-reaction model was designed to identify the combination and importance of biogeochemical processes operating in four sites drilled during ODP Leg 207 (Demerara Rise, Equatorial Atlantic). Almost 100 Ma after their deposition, deeply buried Cretaceous black shales still act as active bioreactors in great sediment depths and control the biogeochemical reaction network of the whole sediment column. According to a model calibrated at the four drill sites through inverse modeling techniques, methanogenesis could be identified as a key process that dominates not only organic matter degradation but also sulfate availability through the anaerobic oxidation of methane above the black shales. A complete depletion of sulfate within the black shale sequences promotes the remobilization of biogenic barium that reprecipitates as authigenic barite at the top of the sulfate depletion zone. Temporal dynamics of degradation processes caused continuous shifts of the barite precipitation zone during burial, thus inhibiting the formation of an authigenic barite front or causing the dissolution of earlier formed fronts. Major deviations of pore water sulfate profiles from a linear gradient coincide with depths of decelerated or accelerated transport caused by local porosity minima or maxima. Model-determined reaction rates are by far lower than those found in shallower sediments due to the low metabolic activities that are characteristic for the Deep Biosphere. But even after almost 100 Ma, changing organic matter quality still influences the degradation within the black shale sequences, as it is indicated by model results.  相似文献   

15.
The coastal upwelling system off central Namibia is one of the most productive regions of the oceans and is characterized by frequently occurring shelf anoxia with severe effects for the benthic life and fisheries. We present data on water column dissolved oxygen, sulfide, nitrate and nitrite, pore water profiles for dissolved sulfide and sulfate,35S-sulfate reduction rates, as well as bacterial counts of large sulfur bacteria from 20 stations across the continental shelf and slope. The stations covered two transects and included the inner shelf with its anoxic and extremely oxygen-depleted bottom waters, the oxygen minimum zone on the continental slope, and the lower continental slope below the oxygen minimum zone. High concentrations of dissolved sulfide, up to 22 mM, in the near-surface sediments of the inner shelf result from extremely high rates of bacterial sulfate reduction and the low capacity to oxidize and trap sulfide. The inner shelf break marks the seaward border of sulfidic bottom waters, and separates two different regimes of bacterial sulfate reduction. In the sulfidic bottom waters on the shelf, up to 55% of sulfide oxidation is mediated by the large nitrate-storing sulfur bacteria, Thiomargarita spp. The filamentous relatives Beggiatoa spp. occupy low-O2 bottom waters on the outer shelf. Sulfide oxidation on the slope is apparently not mediated by the large sulfur bacteria. The data demonstrate the importance of large sulfur bacteria, which live close to the sediment-water interface and reduce the hydrogen sulfide flux to the water column. Modeling of pore water sulfide concentration profiles indicates that sulfide produced by bacterial sulfate reduction in the uppermost 16 cm of sediment is sufficient to account for the total flux of hydrogen sulfide to the water column. However, the total pool of hydrogen sulfide in the water column is too large to be explained by steady state diffusion across the sediment-water interface. Episodic advection of hydrogen sulfide, possibly triggered by methane eruptions, may contribute to hydrogen sulfide in the water column.  相似文献   

16.
Sulfate reduction and sulfur-iron geochemistry were studied in 5-6 m deep gravity cores of Holocene mud from Aarhus Bay (Denmark). A goal was to understand whether sulfate is generated by re-oxidation of sulfide throughout the sulfate and methane zones, which might explain the abundance of active sulfate reducers deep below the main sulfate zone. Sulfate penetrated down to 130 cm where methane started to build up and where the concentration of free sulfide peaked at 5.5 mM. Below this sulfate-methane transition, sulfide diffused downwards to a sulfidization front at 520 cm depth, below which dissolved iron, Fe2+, accumulated in the pore water. Sulfate reduction rates measured by 35S-tracer incubations in the sulfate zone were high due to high concentrations of reactive organic matter. Within the sulfate-methane transition, sulfate reduction was distinctly stimulated by the anaerobic oxidation of methane. In the methane zone below, sulfate remained at positive “background” concentrations of <0.5 mM down to the sulfidization front. Sulfate reduction decreased steeply to rates which at 300-500 cm depth were 0.2-1 pmol SO42− cm−3 d−1, i.e., 4-5 orders of magnitude lower than rates measured near the sediment surface. The turn-over time of sulfate increased from 3 years at 12 cm depth to 100-1000 years down in the methane zone. Sulfate reduction in the methane zone accounted for only 0.1% of sulfate reduction in the entire sediment column and was apparently limited by the low pore water concentration of sulfate and the low availability of organic substrates. Amendment of the sediment with both sulfate and organic substrates immediately caused a 10- to 40-fold higher, “potential sulfate reduction” which showed that a physiologically intact community of sulfate reducing bacteria was present. The “background” sulfate concentration appears to be generated from the reaction of downwards diffusing sulfide with deeply buried Fe(III) species, such as poorly-reactive iron oxides or iron bound in reactive silicates. The oxidation of sulfide to sulfate in the sulfidic sediment may involve the formation of elemental sulfur and thiosulfate and their further disproportionation to sulfide and sulfate. The net reaction of sulfide and Fe(III) to form pyrite requires an additional oxidant, irrespective of the formation of sulfate. This could be CO2 which is reduced with H2 to methane. The methane subsequently diffuses upwards to become re-oxidized at the sulfate-methane transition and thereby removes excess reducing power and enables the formation of excess sulfate. We show here how the combination of these well-established sulfur-iron-carbon reactions may lead to the deep formation of sulfate and drive a cryptic sulfur cycle. The iron-rich post-glacial sediments underlying Holocene marine mud stimulate the strong sub-surface sulfide reoxidation observed in Aarhus Bay and are a result of the glacial to interglacial history of the Baltic Sea area. Yet, processes similar to the ones described here probably occur widespread in marine sediments, in particular along the ocean margins.  相似文献   

17.
The distribution of mineral deposits, characterised as barite deposits, hematite-rich auriferous deposits and auriferous tourmaline–sulfide deposits, displays a regional sulfate–hematite–sulfide zoning along the thrust-delineated limbs of the Mariana anticline, in the south-eastern part of the Quadrilátero Ferrífero of Minas Gerais, Brazil. Cross-cut relationships of barite veins and sulfide lodes indicate that sulfidation occurred in a late-tectonic context, which is here attributed to the collapse of the ～0.6-Ga Brasiliano thrust front. Reconnaissance S-isotopic data from barite and pyrite (Antônio Pereira barite deposit and its adjacent gold deposit, respectively), and arsenopyrite (Passagem de Mariana gold deposit), suggest a new interpretation for the hydrothermal fluid overprint in the Mariana anticline. The Antônio Pereira barite has Δ33S values that are near zero, constraining the sulfate source to rocks younger than 2.45 Ga. The barite-δ34S values are between +19.6 and +20.8?‰. The Passagem arsenopyrite and tourmaline have Co/Ni ratios that define a positive linear trend with the Antônio Pereira pyrite. The latter has homogenous δ34S values, between +8.8 and +8.9?‰, which are compatible with thermochemical reduction of aqueous sulfate with the S-isotopic composition of the Antônio Pereira barite.  相似文献   

18.
Substantial isotopic fractionations are associated with many microbial sulfur metabolisms and measurements of the bulk δ34S isotopic composition of sulfur species (predominantly sulfates and/or sulfides) have been a key component in developing our understanding of both modern and ancient biogeochemical cycling. However, the interpretations of bulk δ34S measurements are often non-unique, making reconstructions of paleoenvironmental conditions or microbial ecology challenging. In particular, the link between the μm-scale microbial activity that generates isotopic signatures and their eventual preservation as a bulk rock value in the geologic record has remained elusive, in large part because of the difficulty of extracting sufficient material at small scales. Here we investigate the potential for small-scale (∼100 μm-1 cm) δ34S variability to provide additional constraints for environmental and/or ecological reconstructions. We have investigated the impact of sulfate concentrations (0.2, 1, and 80 mM SO4) on the δ34S composition of hydrogen sulfide produced over the diurnal (day/night) cycle in cyanobacterial mats from Guerrero Negro, Baja California Sur, Mexico. Sulfide was captured as silver sulfide on the surface of a 2.5 cm metallic silver disk partially submerged beneath the mat surface. Subsequent analyses were conducted on a Cameca 7f-GEO secondary ion mass spectrometer (SIMS) to record spatial δ34S variability within the mats under different environmental conditions. Isotope measurements were made in a 2-dimensional grid for each incubation, documenting both lateral and vertical isotopic variation within the mats. Typical grids consisted of ∼400-800 individual measurements covering a lateral distance of ∼1 mm and a vertical depth of ∼5-15 mm. There is a large isotopic enrichment (∼10-20‰) in the uppermost mm of sulfide in those mats where [SO4] was non-limiting (field and lab incubations at 80 mM). This is attributed to rapid recycling of sulfur (elevated sulfate reduction rates and extensive sulfide oxidation) at and above the chemocline. This isotopic gradient is observed in both day and night enrichments and suggests that, despite the close physical association between cyanobacteria and select sulfate-reducing bacteria, photosynthetic forcing has no substantive impact on δ34S in these cyanobacterial mats. Perhaps equally surprising, large, spatially-coherent δ34S oscillations (∼20-30‰ over 1 mm) occurred at depths up to ∼1.5 cm below the mat surface. These gradients must arise in situ from differential microbial metabolic activity and fractionation during sulfide production at depth. Sulfate concentrations were the dominant control on the spatial variability of sulfide δ34S. Decreased sulfate concentrations diminished both vertical and lateral δ34S variability, suggesting that small-scale variations of δ34S can be diagnostic for reconstructing past sulfate concentrations, even when original sulfate δ34S is unknown.  相似文献   

19.
During the production of hydrocarbons from subterranean reservoirs, scaling with calcium carbonate and barium sulfate causes flux decline and dangerous problems in production facilities. This work is intended to study the effect of calcium ions on the precipitation of barium sulfate (barite); then, the effect of the formed barite on calcium carbonate crystallization. The conductometric and pH methods were used to follow the progress of the precipitation reaction in aqueous medium. The obtained precipitates were characterized by FTIR, RAMAN, SEM, and XRD. It was shown that Ca2+ in the reaction media does not affect the microstructure of barite even for higher calcium–barium molar ratio. It influences the precipitation kinetics and the solubility of barite by the formation of CaSO4° ion pairing as a predominant role of complex formation (CaSO4) and the increase of the ionic strength. In Ca(HCO3)2-BaSO4-NaCl aqueous system, experiments have showed that added or formed barite in the reaction media accelerates calcite precipitation. No effect on the microstructure of heterogeneous formed calcite which remain calcite shape. However the presence of carbonate ions affects slightly the microstructure of barite.  相似文献   

20.
The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S0 was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H2S. At the shelf stations, on the other hand, pyrite was significantly depleted in 34S relative to its potential precursors FeS and S0. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ34S-values of pyrite down to −38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the bottom water composition due to intracellular isotope exchange reactions during microbial sulfur transformations.  相似文献   

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