Distribution of reduced inorganic sulfur compounds in lake sediments receiving acid mine drainage

The sediments of Lake Anna, Virginia, act as a major sink for incoming acid mine drainage (AMD) pollutants (Fe, SO₄²⁻, H⁺) due to bacterial sulfate reduction (SR). Acid-volatile sulfide (AVS), elemental S, and pyrite concentrations in the sediments of the polluted arm of the lake are significantly greater than those in unpolluted sections of the lake. Measurements of SR using ³⁵SSO₄²⁻ showed that AVS and S⁰ are the major short-term (48 h) products of SR in these sediments. Inorganic forms of S(AVS, S⁰, and FeS₂) made up from 60 to 100% of the total sediment S concentration. Pyrite concentrations in the sediment were high but decreased exponentially with distance from the AMD source, suggesting that the pyrite was deposited as stream detritus from the abandoned mines. Iron monosulfide and elemental S concentrations were highest at a station 1 km away from the AMD inflow, indicating formation in situ. There was no evidence for the formation of organic S species. The results suggest that in Fe- and S-rich locations such as those contaminated with acid mine drainage, the distribution of end products of SR may vary substantially from those reported for more moderate environments.     

Stable Sulfur Isotopic Evidence for Historical Changes of Sulfur Cycling in Estuarine Sediments from Northern Florida

Data on abundance and isotopic composition of porewater and sedimentary sulfur species are reported for relatively uncontaminated and highly contaminated fine-grained anoxic sediments of St. Andrew Bay, Florida. A strong contrast in amount and composition of sedimentary organic matter at the two sites allows a comparative study of the historical effects of increased organic loading on sulfur cycling and sulfur isotopic fractionation. In the contaminated sediments, an increase in organic loading caused increased sedimentary carbon/sulfur ratios and resulted in higher rates of bacterial sulfate reduction, but a lower efficiency of sulfide oxidation. These differences are well reflected in the isotopic composition of dissolved sulfate, sulfide, and sedimentary pyrite. Concentration and isotopic profiles of dissolved sulfate, organic carbon, and total sulfur suggest that the anaerobic decomposition of organic matter is most active in the upper 8cm but proceeds at very slow rates below this depth. The rapid formation of more than 90% of pyrite in the uppermost 2 cm which corresponds to about 3 years of sediment deposition allows the use of pyrite isotopic composition for tracing changing diagenetic conditions. Sediment profiles of the sulfur isotopic composition of pyrite reflect present-day higher rates of bacterial sulfate reduction and lower rates of sulfide oxidation, and record a profound change in the diagenetic cycling of sulfur in the contaminated sediments coincident with urban and industrial development of the St. Andrew Bay area.     

A theoretical model of the stable sulfur isotope distribution in marine sediments

A diffusion-diagenesis model of the sulfur cycle is developed to calculate theoretical distributions of stable sulfur isotopes in marine sediments. The model describes the depth variation in δ³⁴S of dissolved sulfate and H₂S. and of pyrite. The effects of sulfate reduction, sulfate and H₂S diffusion. and of sedimentation are considered as well as the bacterial isotope fractionation and the degree of pyrite formation. Under open system conditions of sulfur diagenesis the isotopic difference, ΔSO^2?₄ — H₂S, tends to increase with depth being smaller than the bacterial fractionation factor near the sediment surface and larger in deeper layers. The two isotopes in SO^2?₄ or in H₂S do not diffuse in the same proportion as they occur in the porewater. This explains why sulfur, which is incorporated from seawater sulfate by diffusion and precipitation as pyrite, can be enriched in ³²S relative to the seawater sulfate. The model calculations demonstrate the importance of taking the whole dynamic sulfur cycle into account before drawing conclusions about sulfur diagenesis from the stable isotope distribution.     

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile

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.     

Sulfur speciation in the upper Black Sea sediments

We report solid phase sulfur speciation of six cores from sediments underlying oxic, suboxic and anoxic-sulfidic waters of the Black Sea. Our dataset includes the five sulfur species [pyrite-sulfur, acid volatile sulfides (AVS), zerovalent sulfur (S(0)), organic polysulfides (RS_x), humic sulfur] together with reactive iron and manganese, as quantified by dithionite extraction, and total organic carbon. Pyrite – sulfur was the major phase in all cores [200-400 µmol (g dry wt)^- 1] except for the suboxic core. However, zerovalent sulfur and humic sulfur also reached very significant levels: up to about 109 and 80 µmol (g dry wt)^- 1, respectively. Humic sulfur enrichment was observed in the surface fluff layers of the eastern central basin sediments where Unit-1 type depositional conditions prevail. Elemental sulfur accumulated as a result of porewater sulfide oxidation by reactive iron oxides in turbidities from the anoxic basin margin and western central basin sediments. The accumulation of elemental sulfur to a level close to that of pyrite-S in any part of central Black Sea sediments has never been reported before and our finding indicates deep basin turbidites prevent the build-up of dissolved sulfide in the sediment. This process also contributes to diagenetic pyrite formation whereas in the non-turbiditic parts of the deep basin water column formed (syngenetic) pyrite dominates the sulfur inventory. In slope sediments under suboxic waters, organic sulfur (humic sulfur + organic polysulfides) account for 33-42% of total solid phase S, indicating that the suboxic conditions favor organosulfur formation. Our study shows that the interactions between depositional patterns (Unit 1 vs. turbidite), redox state of overlying waters (oxic-suboxic-sulfidic) and organic matter content determine sulfur speciation and enable the accumulation of elemental sulfur and organic sulfur species close to a level of pyrite-S.     

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.     

Short-term endproducts of sulfate reduction in a salt marsh: Formation of acid volatile sulfides,elemental sulfur,and pyrite

Rates of sulfate reduction, oxygen uptake and carbon dioxide production in sediments from a short Spartina alterniflora zone of Great Sippewissett Marsh were measured simultaneously during late summer. Surface sediments (0–2 cm) were dominated by aerobic metabolism which accounted for about 45% of the total carbon dioxide production over 0–15 cm. Rates of sulfate reduction agreed well with rates of total carbon dioxide production below 2 cm depth indicating that sulfate reduction was the primary pathway for sub-surface carbon metabolism. Sulfate reduction rates were determined using a radiotracer technique coupled with a chromous chloride digestion and carbon disulfide extraction of the sediment to determine the extent of formation of radiolabelled elemental sulfur and pyrite during shortterm (48 hr) incubations. In the surface 10 cm of the marsh sediments investigated, about 50% of the reduced radiosulfur was recovered as dissolved or acid volatile sulfides, 37% as carbon disulfide extractable sulfur, and only about 13% was recovered in a fraction operationally defined as pyrite. Correlations between the extent of sulfate depletion in the marsh sediments and the concentrations of dissolved and acid volatile sulfides supported the results of the radiotracer work. Our data suggest that sulfides and elemental sulfur may be major short-term end-products of sulfate reduction in salt marshes.     

Rare earth elements and sulfur and strontium isotopes of upper Cretaceous phosphorites in Egypt

Upper Cretaceous Phosphorites from different localities in Egypt were analyzed for their rare earth elements (REEs) contents and sulfur and strontium isotopes to examine the effect of depositional conditions versus diagenesis on these parameters.The negative Ce and Eu anomalies of the study phosphorites suggest its formation under reducing conditions. However, chondrite-normalized REEs patterns show relative enrichments of LREEs over the HREEs, which is obviously different from the seawater REEs pattern suggesting post-depositional modifications on the REEs distributions during diagenesis. The difference in the REEs concentrations and Ce anomalies among the study localities as well as the similarity between the REEs patterns of these phosphorites and associated black shales might support this interpretation.The concentration of structural SO₄²⁻ (0.6-3.7%) and their δ³⁴S values (+0.5 to -20‰) in the upper Cretaceous phosphorites in Egypt suggest the formation of these phosphorites in the zone of sulfate reduction. On the other hand, the sulfur isotopes in the pyrite from the study phosphorites (δ³⁴S = +4.6‰ − 23‰ with an average of −7.7‰) are attributed to the influence of seawater from which pyrite was formed during diagenesis. The difference between the δ³⁴S values in the phosphorites (all are positive values) and those in the associated pyrite (mostly negative values) reflect an asymmetric sulfate and sulfide sulfur isotopic composition due to the formation of francolite (source of sulfate) and pyrite (source of sulfide) in different conditions and/or process.The ⁸⁷Sr/⁸⁶Sr values of the upper Cretaceous phosphorites in Egypt are very close to the marine values during the Campanian-Maastrichtian time and their average (0.707622) is more or less comparable to the average ⁸⁷Sr/⁸⁶Sr values of the Cretaceous-Eocene Tethyan phosphorites. This suggests no post-depositional alteration (i.e. diagenetic effect) on the Sr isotopic composition of these phosphorites.     

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Reactions between reduced inorganic sulfur and organic compounds are thought to be important for the preservation of organic matter (OM) in sediments, but the sulfurization process is poorly understood. Sulfur isotopes are potentially useful tracers of sulfurization reactions, which often occur in the presence of a strong porewater isotopic gradient driven by microbial sulfate reduction. Prior studies of bulk sedimentary OM indicate that sulfurized products are ³⁴S-enriched relative to coexisting sulfide, and experiments have produced ³⁴S-enriched organosulfur compounds. However, analytical limitations have prevented the relationship from being tested at the molecular level in natural environments. Here we apply a new method, coupled gas chromatography – inductively coupled plasma mass spectrometry, to measure the compound-specific sulfur isotopic compositions of volatile organosulfur compounds over a 6 m core of anoxic Cariaco Basin sediments. In contrast to current conceptual models, nearly all extractable organosulfur compounds were substantially depleted in ³⁴S relative to coexisting kerogen and porewater sulfide. We hypothesize that this ³⁴S depletion is due to a normal kinetic isotope effect during the initial formation of a carbon–sulfur bond and that the source of sulfur in this relatively irreversible reaction is most likely the bisulfide anion in sedimentary porewater. The ³⁴S-depleted products of irreversible bisulfide addition alone cannot explain the isotopic composition of total extractable or residual OM. Therefore, at least two different sulfurization pathways must operate in the Cariaco Basin, generating isotopically distinct products. Compound-specific sulfur isotope analysis thus provides new insights into the timescales and mechanisms of OM sulfurization.     

Hydrothermalism in the Tyrrhenian Sea: Inorganic and microbial sulfur cycling as revealed by geochemical and multiple sulfur isotope data

The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry.Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ³⁴S range between ?29.8 and + 10.2‰ and Δ³³S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ³⁴S_CRS with less negative values between ?11.3 and ?1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea.Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ³⁴S and Δ³³S values for pyrite between ?32.8 and ?1.1‰ and between ?0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ³⁴S and Δ³³S values between ?26.7 and ?2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ³⁴S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro.Although a magmatic SO₂ contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface.     

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 δ³⁴S 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 δ³⁴S 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 δ³⁴S 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 δ³⁴S 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). δ³⁴S 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 δ³⁴S 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.     

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

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

Sulfur geochemistry of Jurassic high-sulfur coals from Egypt

Jurassic high-sulfur coals from the Maghara area in Egypt were analyzed for the abundance and isotopic composition of different forms of sulfur. Analyses indicated that the sulfur occurs in the form of organic, pyrite, and sulfate forms. Pyrite sulfur represents the major fraction, while sulfate sulfur is minor and could be formed during sample preparation for the analyses.The δ³⁴S CDT values of the organic sulfur are positive ranging between 1.0‰ and 13.5‰ with an average of 9.1‰. Pyrite δ³⁴S values are also positive ranging between 1.5‰ and 15.4‰ with an average of 6.6‰. The high δ³⁴S values of the organic sulfur in the Maghara coals suggest a freshwater origin of the organic components of these coals. The lack of correlation between pyrite and organic sulfur isotopes implies different incorporation mechanisms of sulfur. The high-sulfur contents along with the positive and high δ³⁴S values suggest a marine origin of pyrite sulfur and support the geological interpretation of marine invasion after the peat formation that was responsible for the incorporation of the pyrite sulfur.The occurrence of pyrite as euhedral crystals as well as the high and positive δ³⁴S values of the pyrite sulfur indicates the formation of pyrite during diagenesis as a result of marine water invasion of the preexisting peat in a brackish coastal plain environment.     

Fractionation of sulfur isotopes during laboratory synthesis of pyrite at low temperatures

The reaction products and the accompanying sulfur isotope fractionations during the reaction of H₂S with goethite in aqueous media at 22–24°C for periods from 0.5 hr to 65 days were studied. Fine-grained pyrite formed within two days and was isotopically 0.8‰ lighter than the H₂S source. After 65 days reaction time the pyrite had nearly the same isotopic value as the H₂S. Aqueous precipitation of pyrite from H₂S and goethite at room temperature involved three major steps, namely: (1) the rapid oxidation of H₂S and reduction of Fe³⁺ during which elemental S is formed; (2) the formation of acid-volatile sulfides and the disappearance of elemental S; and (3) the formation of pyrite at the expense of acid-volatile sulfides.     

沉积地层中的黄铁矿形态及同位素特征初探——以华南埃迪卡拉纪深水相地层为例

地质历史时期新元古代大气氧含量普遍较低。在硫酸盐还原细菌作用下,作为海洋重要的氧化性离子,陆源硫酸根离子有效促进了深层海水的氧化进程。在此过程中,硫元素在硫酸根和黄铁矿之间发生显著同位素分馏,其分馏程度可反推当时古海洋的氧化还原状态。沉积地层中的黄铁矿普遍具有多种形态,不同形态黄铁矿的形成环境多有不同。如草莓状黄铁矿多形成于底层缺氧水体或沉积物的浅表面,而大颗粒单晶黄铁矿或脉状黄铁矿则多沉积于成岩早期的沉积物孔隙或形成于成岩后期的热液改造。与草莓状黄铁矿不同,大颗粒单晶或脉状黄铁矿的硫同位素组成并不能反映沉积时期的古海洋氧化还原条件。判定沉积地层中不同形态的黄铁矿及形成过程,是获得有效反映海洋沉积环境硫同位素组成特征的基本前提。简要总结了地质历史时期沉积地层中的黄铁矿类型及矿物形成过程,并以华南埃迪卡拉纪蓝田组岩芯样品为例,识别出各个样品中的黄铁矿形态组成特征,对比分析了全岩黄铁矿与样品中大颗粒黄铁矿硫同位素组成差异。研究结果表明:不同岩性样品中黄铁矿的形态种类及含量均存在差异。页岩样品保存有更好形态的自形晶以及草莓状黄铁矿;碳酸盐岩样品中具有较多自形晶以及他形晶黄铁矿,并且其中的少量草莓状黄铁矿遭受后期成岩作用而发生不同程度的晶体蚀变。样品中大颗粒黄铁矿的硫同位素值（δ34S_L-pyr）通常显著高于全岩黄铁矿的硫同位素值（δ34S_T-pyr）,最大差值可达48.5‰。在利用黄铁矿的硫同位素组成来反推当时古海洋环境时,需要区分不同形态黄铁矿,仔细剔除大颗粒黄铁矿,降低成岩期黄铁矿对样品中硫同位素组成的影响。更细致的微区黄铁矿硫同位素分析工作将依赖于SIMS分析测试手段进行。     

Pyritization processes and greigite formation in the advancing sulfidization front in the upper Pleistocene sediments of the Black Sea

Pyritization in late Pleistocene sediments of the Black Sea is driven by sulfide formed during anaerobic methane oxidation. A sulfidization front is formed by the opposing gradients of sulfide and dissolved iron. The sulfidization processes are controlled by the diffusion flux of sulfide from above and by the solid reactive iron content. Two processes of diffusion-limited pyrite formation were identified. The first process includes pyrite precipitation with the accumulation of iron sulfide precursors with the average chemical composition of FeS_n (n = 1.10-1.29), including greigite. Elemental sulfur and polysulfides, formed from H₂S by a reductive dissolution of Fe(III)-containing minerals, serve as intermediates to convert iron sulfides into pyrite. In the second process, a “direct” pyrite precipitation occurs through prolonged exposure of iron-containing minerals to dissolved sulfide. Methane-driven sulfate reduction at depth causes a progressive formation of pyrite with a δ³⁴S of up to +15.0‰. The S-isotopic composition of FeS₂ evolves due to contributions of different sulfur pools formed at different times. Steady-state model calculations for the advancement of the sulfidization front showed that the process started at the Pleistocene/Holocene transition between 6360 and 11 600 yr BP. Our study highlights the importance of anaerobic methane oxidation in generating and maintaining S-enriched layers in marine sediments and has paleoenvironmental implications.     

Formation of 35S-labelled elemental sulfur and pyrite in coastal marine sediments (Limfjorden and Kysing Fjord,Denmark) during short-term 35SO42− reduction measurements

Analyses of the specific products of ³⁵SO₄^2? reduction measurements were made in marine sediments in Denmark. We injected tracer quantities of ³⁵SO₄^2? into cores, incubated the cores, and assayed for ³⁵S-labelled acid volatile sulfides. Additionally, we assayed for ³⁵S-labelled elemental sulfur by extraction with CS₂, and for ³⁵S-labelled pyrite by reduction with chromium (II). We separately determined that elemental sulfur which formed in situ and that which formed by oxidation during the acid distillation of acid volatile sulfides.In subtidal sediments in Limfjorden, ³⁵S-labelled elemental sulfur and pyrite make up 14–32% of the reduced sulfur formed in short-term (0–48 hours) ³⁵SO₄^2? reduction experiments, at all depths studied (0–15 cm). Labelled elemental sulfur which formed in situ during the incubations at depths below 1 cm made up a fairly constant 5–11% of the total labelled reduced sulfur, from 0–1 cm, it made up 27%. An additional small amount (1–2% from 1–15 cm and 5% from 0–1 cm) of labelled elemental sulfur was formed during the acid-distillation step in our assay for labelled acid-volatile sulndes. Pyrite contained 4–13% of the total labelled reduced sulfur at all depths. Rates of sulfate reduction in Limfjorden were linear over the period 0–48 hours, and ³⁵S-pyrite made up a nearly constant percentage of the ³⁵S-labelled reduced sulfur formed over this time period.Estimates of sulfate reduction rates for Limfjorden which do not include elemental sulfur and pyrite as products are 19% too low. At Kysing Fjord, estimates of sulfate reduction which do not include elemental sulfur and pyrite are 24% to 32% too low. Thus, while previously published data on sulfate reduction in similar environments are probably low, they are not greatly in error.     

南大西洋中脊26°S热液区成矿物质来源探讨

南大西洋中脊的26°S热液区广泛发育多金属硫化物、底泥、枕状熔岩、非活动性烟囱体和活动性烟囱体。为了有效探索硫、铜等成矿物质的来源以及成矿作用过程,分别以玄武岩、烟囱体残片及块状多金属硫化物为研究对象,开展了熔融包裹体、硫同位素和铜同位素研究。结果显示：区内玄武岩新鲜未蚀变且斑晶中产出大量熔融包裹体;熔融包裹体气泡壁附着黄铜矿、黄铁矿及磁铁矿等子矿物,说明在岩浆作用过程中可从熔浆中分离出成矿所需的金属元素和硫,这些成矿元素随着岩浆去气作用进入挥发分中,并随着脱气作用迁移出来。通过对烟囱体残片及块状多金属硫化物中黄铁矿的硫同位素组成进行比对分析,发现26°S热液区内硫化物的硫同位素与大西洋各热液区硫化物的硫同位素变化范围相一致,但δ³⁴S_V-CDT值略低（3.0‰~3.9‰）。低的δ³⁴S_V-CDT值指示硫以岩浆硫源为主,海水硫酸盐还原硫占比低。黄铜矿呈现略微富铜重同位素特征且分馏程度较低,其δ⁶⁵Cu值（0.171‰~0.477‰）趋近于大洋中脊玄武岩的铜同位素值（0）。综合硫同位素及铜同位素特征,表明热液流体经历了岩浆和海水的混合过程,成矿物质主要来自于岩浆热液,成矿作用过程中可能有少量海水混入。     

Isotopic evidence for the origin of sulfur in the Herrin (no. 6) coal member of Illinois

The sulfur isotopic composition of the Herrin (No. 6) Coal from several localities in the Illinois Basin was measured. The sediments immediately overlying these coal beds range from marine shales and limestones to non-marine shales. Organic sulfur, disseminated pyrite, and massive pyrite were extracted from hand samples taken in vertical sections.The $\text{δ}{}^{34}\text{S}$ values from low-sulfur coals (< 0.8% organic sulfur) underlying nonmarine shale were +3.4 to +7.3%₀ for organic sulfur, +1.8 to +16.8%₀ for massive pyrite, and +3.9 to +23.8%₀ for disseminated pyrite. In contrast, the $\text{δ}{}^{34}\text{S}\text{values from high-sulfur coals}$ (> 0.8% organic sulfur) underlying marine sediments were more variable: organic sulfur, ?7.7 to +0.5%₀, pyrites, ?17.8 to +28.5%₀. In both types of coal, organic sulfur is typically enriched in ³⁴S relative to pyritic sulfur.In general, δ ³⁴S values increased from the top to the base of the bed. Vertical and lateral variations in δ ³⁴S are small for organic sulfur but are large for pyritic sulfur. The sulfur content is relatively constant throughout the bed, with organic sulfur content greater than disseminated pyrite content. The results indicate that most of the organic sulfur in high-sulfur coals is derived from post-depositional reactions with a ³⁴S-depleted source. This source is probably related to bacterial reduction of dissolved sulfate in Carboniferous seawater during a marine transgression after peat deposition. The data suggest that sulfate reduction occurred in an open system initially, and then continued in a closed system as sea water penetrated the bed.Organic sulfur in the low-sulfur coals appears to reflect the original plant sulfur, although diagenetic changes in content and isotopic composition of this fraction cannot be ruled out. The wide variability of the δ ³⁴S in pyrite fractions suggests a complex origin involving varying extents of microbial H₂S production from sulfate reservoirs of different isotopic compositions. The precipitation of pyrite may have begun soon after deposition and continued throughout the coalification process.     

Sediment and hydro biogeochemistry of Lake Nainital, Kumaun Himalaya, India

The picturesque Nainital Lake, in the Uttarakhand state of India, is one of the major tourist attractions in the northern part of India. The increasing tourism and population around these lakes are a major concern for the ecology and good sustenance of the lakes. The present study is aimed to understand the behaviour of nutrients and metals in the sediment and their association with chemical forms in the lake. The study was accomplished by studying the water, interstitial water and sediments for major oxides, nutrients and metals in the lake. The different chemical forms of phosphorus and metals in the sediments were done using sequential extraction procedures. The water chemistry (Ca + Mg:Na + K) and the sediment chemistry (CIA and Al₂O₃/K₂O) show that the rocks in the catchment area play an important role in the geochemistry of the lake. The metals in the water also show that the Tallital basin is more polluted than the Mallital basin, may be due to the influence of Bus station. The high concentration of chloride, NH₄, SO₄ and metals in the sediment water interface and the interstitial water shows denitrification, sulfidisation and sulfide oxidation in the anoxic bottom water. The sediment composition shows that the phosphorus in the water is sequestered as carbonate flour apatite, and the metals precipitate as carbonate. The geo- accumulation index shows that the metals zinc, cobalt and nickel show moderate polluted nature than other metals. In general, the lake is less affected by anthropogenic activities. The chemical processes undergoing within the lake, like sulfidisation and sulfide oxidation, oxide dissolution and denitrification and organic matter degradation play an important role in the remobilization of the metals from the lake sediments.