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1.
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.  相似文献   

2.
胶州湾李村河口沉积物中硫化物形成的控制因素   总被引：1，自引：0，他引：1  
在胶州湾李村河口,对多个短柱状岩芯沉积物中的有机质（有机碳和有机氮）、酸可挥发性硫化物（AVS）、黄铁矿及活性铁等进行了分析。结果表明,样品的有机质含量较高,有机碳含量为0．16％～3．21％,有机氮含量为0．002％-0．2％;6个短柱状样的AVS含量变化较大：198．4—0．4umol／g,平均35．6umol／g;活性铁含量为47．5～169．3umol／g,平均91．4umol／g;黄铁矿含量为14．8～41．0umol／g,平均28．7umol／g。通过计算沉积物中活性铁的黄铁矿化度（DOP）与硫化度（DOS）指标,及分析各参数间相关性,发现以下现象：（1）胶州湾李村河口沉积物中的活性铁被转化为硫化物的程度较高,被转化为黄铁矿的程度较低,沉积物中的黄铁矿得到了较好保存。DOP不适宜用作河口区氧化还原状态的判断指标,DOS对氧化还原状态的响应更加灵敏;（2）距河口较近的区域,受李村河河水的影响较大,易分解有机质供应充足,AVS大量形成,其向黄铁矿的转化并不充分,活性铁成为硫化物形成的控制因素。距河口较远的站位,活性铁含量相对充足,有机质含量相对不足,因此有机质含量成为硫化物形成的控制因素,AVS向黄铁矿的转化比较充分;（3）有机质尤其是易分解有机质含量是李村河口硫化物形成、活性铁富集及其黄铁矿化度的主要控制因素。AVS的形成主要受到有机氮的限制,而黄铁矿的形成主要受到有机碳的限制。因此,河流输入物质对河口区沉积物中C、S和Fe的循环具有显著的影响。  相似文献   

3.
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 FeSn (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.  相似文献   

4.
《Geochimica et cosmochimica acta》1999,63(19-20):3373-3378
Interactions of trace metals with sulfide in anoxic environments are important in determining their chemical form and potential toxicity to organisms. In recent years, a considerable body of observational data has accumulated that indicates very different behavior for various trace metals in sulfidic sediments. These differences in behavior cannot be entirely attributed to thermodynamic relationships, but also reflect differences in ligand exchange reaction kinetics, and redox reaction pathways.Pb, Zn, and Cd, which are generally pyritized to only a few percent of the “reactive” fraction, have faster water exchange reaction kinetics than Fe2+, resulting in MeS phases precipitating prior to FeS formation and subsequent pyrite formation, whereas, Co and Ni, which have slower H2O exchange kinetics than Fe2+, are incorporated into pyrite. Although Hg and Cu have faster reaction kinetics than Fe2+, both are incorporated into pyrite or leached from the pyrite fraction with nitric acid. Hg undergoes significant chloride complexation, which can retard reaction with sulfide, but can also replace Fe in FeS to form HgS, which can only be dissolved in the pyrite fraction. Cu2+ is reduced by sulfide and forms a variety of sulfides with and without Fe that can only be dissolved with nitric acid. Mn2+ does not form a MnS phase easily and is incorporated into pyrite at high iron degrees of pyritization (DOP).Oxyanions of Mo and As are first reduced by sulfide. These reduced forms may then react with sulfides resulting in incorporation into pyrite. However, the oxyanion of Cr is reduced to Cr3+, which is kinetically inert to reaction with sulfide and, therefore, not incorporated into pyrite.  相似文献   

5.
In sediments from the continental slope of the Northern Gulf of Mexico, generally,the degree of iron pyritization (DOP) is low (<0.1) and dissolved sulfide is belowdetection limits (5 M), whereas dissolved Fe is typically about 50 to100 M. Therefore, the dissolution of kinetically reactive iron minerals generallydominates over the rate of sulfide production in sediments throughout this region.However, in sediments where hydrocarbons have been added via seepage from thesubsurface, dissolved-Fe is undetectable, DOP can approach 1, and high concentrationsof dissolved sulfide (up to 11 mM) are commonly present. Even though thesesediments have high total reduced sulfide (TRS) concentrations (typically 150 to370 mol gdw-1), their average C/S ratio is about 4 times that of normal marine sediments reflecting the major input of hydrocarbons. DOP is significantly (20%) higher when calculated using reactive-Fe extracted by citrate dithionite than by cold 1N HCl. This difference is primarily due to the greater extraction efficiency of the cold HCl method for silicate-Fe. TRS tends to rise to a maximum, and remains close to constant even at high (mM) dissolved sulfide concentrations. These TRS concentrations, therefore, represent the size of the ``kinetically' reactive-Fe pool during early diagenesis.  相似文献   

6.
The concentrations of authigenic phases of Cd, Re, U, and Mo increase with depth in four 45-cm-long sediment box cores collected along the axis of the Laurentian Trough, Gulf of St. Lawrence. Average authigenic accumulation rates, estimated from element inventories, are similar to rates in other continental margin environments. Strong regional variations in sediment accumulation rate and sulfide concentration have little influence on the accumulation rates of Cd and Re. This suggests that slow precipitation kinetics controls the accumulation of Cd and Re in these sediments. The accumulation rate of authigenic U is more variable; it may be tied to the kinetics of microbially mediated U reduction and be controlled by the availability of reactive organic matter. Authigenic Mo is distinguished by a sharp subsurface concentration minimum, above which Mo cycles with manganese. Mo released to pore water upon reduction of Mn oxides diffuses downward and enriches the subsurface sediment. Mo accumulates most rapidly in the sediment with the highest sulfide content. Slow conversion of molybdate to thiomolybdate may explain the much slower Mo accumulation rate in the less sulfidic sediments. A component of authigenic Mo accumulates with pyrite in an approximately constant Mo:Fe ratio. The accumulation rate of pyrite and associated Mo is insensitive to AVS abundance. Pyrite formation may be limited by the reactivity of iron oxide minerals.  相似文献   

7.
The genesis of local compact segregations of iron sulfide (pyrite) in mudstones at the roof of some coal seams in the Donets Basin (Donbas) is examined. Arguments presented in the work show that sulfides were formed as a result of bacterial sulfate reduction and hydrogen sulfide generation in zones of organic matter concentration. The lack of any signs of influx of alien components testifies to in situ sulfide accumulations at the syngenetic or early diagenetic stage in bottom sediments of the basin. The shape and structure of pyrite segregations suggest that they could be sulfide bioherms occasionally subjected to mechanical deformation in a liquid mud under the influence of gravitational force or external mechanical (possibly seismic) loads. The obtained data can serve as an additional source of information pertaining to the formation conditions of sulfide ore deposits.  相似文献   

8.
《Applied Geochemistry》1988,3(3):333-344
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.  相似文献   

9.
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 (RSx), 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.  相似文献   

10.
In galvanic cell arrangements gold is electrochemically deposited on semiconducting sulfide minerals (pyrite, arsenopyrite, chalcopyrite) from aerated as well as H2S-saturated, gold-bearing 1 M KCl solutions. Observed cell potential differences of about 0.4–0.6 V in setups with one sulfide in aerated (cathode) and the other in H2S-saturated (anode) solutions are comparable with known self-potentials of natural sulfide ore bodies. Gold preferentially accumulates on the cathode, i.e. under oxidizing conditions. Linked sulfides of variable composition in the same environment, either oxidizing or reducing, yield potential differences up to 20 mV. Such assemblages simulate conditions typically occurring at surfaces of chemically inhomogeneous single crystals (e.g. zonation). Depending on chemical composition, sulfide minerals show either n- or p-type conductivity. Visible gold is preferentially accumulated on individual domains of sulfide surfaces that act as cathodes, i.e. p-type conductors in n-p junctions. The experimental results are discussed in view of electrochemical accumulation of visible gold on sulfides in nature. Arsenic is the most important element in establishing p-type conductivity of pyrite and arsenopyrite. This feature may explain why As is such a powerful pathfinder in gold exploration.  相似文献   

11.
Groundwater and sediment samples (∼ 1 m depth) at sites representative of different groundwater pathways were collected to determine the aqueous speciation of sulfur and the fractionation of sulfur isotopes in aqueous and solid phases. In addition, selected sediment samples at 5 depths (from oxic to anoxic layers) were collected to investigate the processes controlling sulfur biogeochemistry in sedimentary layers. Pyrite was the dominant sulfur-bearing phase in the capillary fringe and groundwater zones where anoxic conditions are found. Low concentrations of pyrite (< 5.9 g kg− 1) coupled with high concentrations of dissolved sulfide (4.81 to 134.7 mg L− 1) and low concentrations of dissolved Fe (generally < 1 mg L− 1) and reducible solid-phase Fe indicate that availability of reactive Fe limits pyrite formation. The relative uniformity of down-core isotopic trends for sulfur-bearing mineral phases in the sedimentary layers suggests that sulfate reduction does not result in significant sulfate depletion in the sediment. Sulfate availability in the deeper sediments may be enhanced by convective vertical mixing between upper and lower sedimentary layers due to evaporative concentration. The large isotope fractionation between dissolved sulfate and sedimentary sulfides at Owens Lake provides evidence for initial fractionation from bacterial sulfate reduction and additional fractionation generated by sulfide oxidation followed by disproportionation of intermediate oxidation state sulfur compounds. The high salinity in the Owens Lake brines may be a factor controlling sulfate reduction and disproportionation in hypersaline conditions and results in relatively constant values for isotope fractionation between dissolved sulfate and total reduced sulfur.  相似文献   

12.
We examined the solubility, mineralogy and geochemical transformations of sedimentary Fe in waterways associated with coastal lowland acid sulfate soils (CLASS). The waterways contained acidic (pH 3.26-3.54), FeIII-rich (27-138 μM) surface water with low molar Cl:SO4 ratios (0.086-5.73). The surficial benthic sediments had high concentrations of oxalate-extractable Fe(III) due to schwertmannite precipitation (kinetically favoured by 28-30% of aqueous surface water Fe being present as the FeIII species). Subsurface sediments contained abundant pore-water HCO3 (6-20 mM) and were reducing (Eh < −100 mV) with pH 6.0-6.5. The development of reducing conditions caused reductive dissolution of buried schwertmannite and goethite (formed via in situ transformation of schwertmannite). As a consequence, pore-water FeII concentrations were high (>2 mM) and were constrained by precipitation-dissolution of siderite. The near-neutral, reducing conditions also promoted SO4-reduction and the formation of acid-volatile sulfide (AVS). The results show, for the first time for CLASS-associated waterways, that sedimentary AVS consisted mainly of disordered mackinawite. In the presence of abundant pore-water FeII, precipitation-dissolution of disordered mackinawite maintained very low (i.e. <0.1 μM) S−II concentrations. Such low concentrations of S−II caused slow rates for conversion of disordered mackinawite to pyrite, thereby resulting in relatively low concentrations of pyrite (<300 μmol g−1 as Fe) compared to disordered mackinawite (up to 590 μmol g−1 as Fe). This study shows that interactions between schwertmannite, goethite, siderite, disordered mackinawite and pyrite control the geochemical behaviour of sedimentary Fe in CLASS-associated waterways.  相似文献   

13.
Four cores of anoxic sediments were collected from the Seine estuary to assess the early diagenesis pathways leading to the formation of previously reactive phase. Pore waters were analyzed for dissolved iron (Fe) and manganese (Mn) and different ligands (e.g., sulfate, chloride, total inorganic carbon). The anoxic zone is present up to the first centimeter depth, in these conditions the reduction of Mn and Fe oxides and SO4 2− was verified. The sulfate reduction was well established with a subsequent carbon mineralization in the NORMAI94 core. The chemical speciation of Mn and Fe in the dissolved and solid phases was determined. For the dissolved phase, thermodynamic calculations were used to characterize and illustrate the importance of carbonate and phosphate phases as sinks for Fe and Mn. The ion activity product (IAP) of Fe and Mn species was compared to the solubility products (Ks) of these species. In the solid phase, the presence of higher concentration of calcium carbonate in the Seine sediments is an important factor controlling Mn cycle. The carbonate-bound Mn can reach more than 75% of the total concentration. This result is confirmed by the use of electron spin resonance (ESR) spectroscopy. The reduction of Fe is closely coupled to the sulfate reduction by the formation of new solid phases such as FeS and FeS2, which can be regarded as temporal sinks for sulfides. These forms were quantified in all cores as acid volatile sulfide (AVS: FeS+ free sulfide) and chromium reducible sulfide (CRS: FeS2+elemental sulfur S0).  相似文献   

14.
Kuroko-type massive sulfide deposits of the Eastern Black Sea province of Turkey are related to the Upper Cretaceous felsic lavas and pyroclastic rocks, and associated with clay and carbonate alteration zones in the footwall and hangingwall lithologies. A complete upward-vertical section of a typical orebody consists of a stringer-disseminated sulfide zone composed mainly of pyrite and chalcopyrite; a massive pyrite zone; a massive yellow ore consisting mainly of chalcopyrite and pyrite; a black ore made up mainly of galena and sphalerite with minor amounts of chalcopyrite, bornite, pyrite and various sulfosalts; and a barite zone. Most of the deposits in the province are associated with gypsum in the footwall or hangingwall. The paragenetic sequence in the massive ore is pyrite, sphalerite, chalcopyrite, bornite, galena and various sulfosalts, with some overlap between the mineral phases. Massive, stringer and disseminated sulfides from eight kuroko-type VMS deposits of the Eastern Black Sea province have a 34S range of 0–7 per mil, consistent with the 34S range of felsic igneous rocks. Sulfides in the massive ore at Madenköy (4.3–6.1 per mil) differ isotopically from sulfides in the stringer zone (6.3–7.2 per mil) suggesting a slightly increased input of H2S derived from marine sulfate with time. Barite and coarse-grained gypsum have a 34S range of 17.7–21.5 per mil, a few per mil higher than the 34S value of contemporaneous seawater sulfate. The deposits may, therefore, have formed in restricted basins in which bacterial reduction of sulfate was taking place. Fine-grained, disseminated gypsum at Kutlular and Tunca has 34S values (2.6–6.1 per mil) overlapping those of ore sulfides, indicating sulfide oxidation during waning stages of hydrothermal activity.  相似文献   

15.
The chemical composition of sediments of cores taken from different areas of the Barents Sea was studied. The study involves reactive iron (Fereact) and reduced sulfur. The surficial oxidized layer with a thickness of 0.5–25 cm is characterized by increased content of Fe(III) in the form of oxyhydroxides and possibly hydroxophosphates. This layer is locally enriched in Mn. Reactive iron in sediments of horizons, which underlie the oxidized layer, is probably present mainly in the composition of silicates. The role of sulfides (acid-soluble phases and pyrite) among Fereact forms is predominantly subordinate. The core of pre-Holocene sediments is characterized by a strong correlation between the total content of reduced sulfur and its isotopic composition. This testifies to authigenic origin of pyrite in the pre-Holocene mud.  相似文献   

16.
Voltammetric methods using direct insertion of a gold-amalgam microelectrode with a sensitive, computercontrolled voltammeter detected soluble iron(II) sulfide, [FeS]aq, in the porewaters of anoxic, sulfidic, fine-grained sediments from the Loughor Estuary, Wales. The voltammetric results are reproducible. Studies of cores stored in sealed, refrigerated containers for up to 21 d reveal no measurable oxidation. [FeS]aq forms in this estuarine environment as a result of the dissolution of amorphous FeS, and appears to be involved in the formation of pyrite. [FeS]aq makes no significant contribution to the total sulfide and iron contents of the sediment but could constitute an important component of the dissolved Fe(II) and S(−II) contents of the porewater. Mass balance calculations show pyrite forms in this system by the addition of sulfur to FeS rather than by the loss of iron from FeS. The overall process appears to involve [FeS]aq as an intermediary. Although the porewaters of the Loughor Estuary sediments are iron-rich relative to seawater, the iron sulfide-forming process is iron-limited rather than sulfide-limited. Reactive iron is bound to sulfide rapidly in the sediment. After the reactive iron is bound to sulfide, additional sulfide produced is fixed as pyrite.  相似文献   

17.
Sulfide minerals in amounts up to 3 vol% are found in basal, chilled marginal zones of two layered peridotite-pyroxenite-gabbro sills in the Early Precambrian Deer Lake Complex, northcentral Minnesota. The sulfides occur interstitially to silicate minerals, and consist of pyrrhotite with minor exsolved cobaltian pentlandite, chalcopyrite, gersdorffite, and marcasite±pyrite as an alteration product of pyrrhotite.The basal chilled units (3–6 m) of the sills are divisable into three zones based primarily on textures. The lowermost zone is an equigranular basalt, whereas the overlying zone is characterized by skeletal, spinifex-like actinolite after clinopyroxene. The upper zone of the basal margins contains elongate and swallow tail plagioclase, and is barren of sulfide minerals.Electron microprobe analyses of sulfide minerals and modal data suggest that sulfide bulk compositions at 1,100–1,000 ° C represent a pyrrhotite solid solution and a coexisting Cu-rich sulfide liquid. Cooling of the Cu-rich liquid and low temperature transformations are thought to have produced chalcopyrite or chalcopyrite plus pyrrhotite. The sulfide minerals have reequlibrated to temperatures near 300 ° C or less.Analyses of sulfur content and 34S values suggest that assimilation of sulfur from adjacent country rocks was the principal mechanism responsible for anomalous concentrations of sulfides in the basal chilled margins. The distribution of sulfides in the peridotite-pyroxenite-gabbro portions of the sills, and calculations of settling rate preclude an origin involving gravitational settling of immiscible droplets through the magma body.  相似文献   

18.
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   

19.
The Myall Creek copper prospect is in unmetamorphosed carbonaceous dolosiltstone and sandstone at the base of the late Proterozoic (Adelaidean) Tapley Hill Formation. It contains disseminated, fine-grained chalcopyrite, zincian tennanite, bornite, chalcocite, pyrite, sphalerite and galena, and irregular to straight chalcopyrite-rich veinlets. Some ore minerals rim and/or partially replace pyrite or clastic grains. There is no evidence of hydrothermal activity. The 34SCDT values of pyrite and the other sulfides fall in the wide range –3.6 to +44.2. Dolomite in both mineralised and unmineralised samples has 13CPDB values concentrated around –3, and 18OSMOW values around +25. It is concluded that the mineralising fluids were near-neutral brines which leached metals from the basement and early Adelaidean rocks. They entered the Tapley Hill sediments at moderately low temperatures via permeable strata and faults. The metals were precipitated by biogenic H2S, and also fixed by reaction with iron sulfides and, possibly, organic matter. Continuing ascent of brines into the mineralised strata caused breakdown of detrital feldspars and Fe-Ti oxides, and some solution-remobilisation of early-formed sulfides.  相似文献   

20.
Sulphur isotope compositions and S/C ratios of organic matter were analysed in detail by combustion-isotope ratio monitoring mass spectrometry (C-irmMS) in eastern Mediterranean sediments containing three sapropels of different ages and with different organic carbon contents (sapropel S1 in core UM26, formed from 5–9 ka ago with a maximum organic carbon content of 2.3 wt%; sapropel 967 from ODP Site 160-967C, with an age of 1.8 Ma and a maximum organic carbon content of 7.4 wt%; and sapropel 969 from ODP Site 160-969E, with an age of 2.9 Ma and a maximum organic carbon content of 23.5 wt%). Sulphur isotopic compositions (34S) of the organic matter ranged from -29.5 to +15.8 and the atomic S/C ratio was 0.005 to 0.038. The organic sulphur in the sediments is a mixture of sulphur derived from (1) incorporation of 34S-depleted inorganic reduced sulphur produced by dissimilatory microbial sulphate reduction; and (2) biosynthetic sulphur with an isotopic signature close to seawater sulphate. The calculated biosynthetic fraction of organic sulphur in non-sapropelic sediments ranges from 68–87%. The biosynthetic fraction of the organic sulphur of the sapropels (60–22%) decreases with increasing organic carbon content of the sapropels. We propose that uptake of reduced sulphur into organic matter predominantly took place within sapropels where pyrite formation was iron-limited and thus an excess of dissolved sulphide was present for certain periods of time. Simultaneously, sulphide escaped into the bottom water and into sediments below the sapropels where pyrite formation occurred.  相似文献   

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