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1.
Aleksander Jokic Elena Ponomarenko Darwin W Anderson 《Geochimica et cosmochimica acta》2003,67(14):2585-2597
X-ray absorption near-edge structure (XANES) and nuclear magnetic resonance (NMR) spectroscopy were used in combination to characterize organic carbon structures in a series of wetland soils in Saskatchewan, and XANES spectroscopy was also used to examine sulphur speciation in the soils. The organic C contents of most of the wetland soils are consistently higher by a factor of two to five times compared to adjacent well-drained soils. NMR analyses indicate that the organic matter in the wetland soils consists of predominantly aliphatic structures such as carbohydrates and long chain poly(methylene) units which are refractory structures found in plant waxes. The poly(methylene) structures have a significant capacity to sorb nonpolar organic molecules. The phenolic OH and carboxyl group content of the wetland soils studied is an additional significant factor in their sequestering ability for heavy metals or pesticides. Carbon XANES spectroscopy shows that the surface (∼10 nm) layer of particulate organic matter has a structure dominated by aromatic, carbohydrate and carboxylic acid-like material apparently derived from partially degraded lignin and cellulose polymers which are adsorbed onto clay minerals. The aliphatic structures remaining in this surface layer are probably recalcitrant (poly)methylene units. At a depth of ∼100 nm, the aliphatic content significantly increases suggesting the presence of more labile structures. The presence of these more labile aliphatic compounds may be due to slow decomposition rates in the wet, often cool environments present and to the protective action of the more refractory components in the surface ∼10 nm of the organic matter. Drying of the wetlands, either by draining or as a result of climate change, is likely to result in the rapid decomposition of these labile organic structures releasing carbon dioxide. Our data indicate that the preservation of the organic carbon compounds in these soils is a result of their presence as surface adsorbed layers on the soil mineral particles. The soils contain three different classes of sulphur compounds: reduced organic sulphur such as sulphides, low valent oxidized sulphur such as sulphoxides, and high valent oxidized sulphur such as sulphonate and sulphate. Of these, reduced sulphur species constitute between one-third and two-thirds of the total. Sulphonate structures comprise between a fifth and a third of the total. Sulphates exhibit a wide variation in content, and sulphoxides are either not detected or are present to a lesser extent (<5%). Drying of the wetlands would cause oxidation of sulphides to sulphates. 相似文献
2.
Theodore M. Present Melissa Gutierrez Guillaume Paris Charles Kerans John P. Grotzinger Jess F. Adkins 《Sedimentology》2019,66(7):2605-2626
Late Palaeozoic‐age strata from the Capitan Reef in west Texas show facies‐dependent heterogeneity in the sulphur isotopic composition of carbonate‐associated sulphate, which is trace sulphate incorporated into carbonate minerals that is often used to reconstruct the sulphur isotopic composition of ancient seawater. However, diagenetic pore fluid processes may influence the sulphur isotopic composition of carbonate‐associated sulphate. These processes variously modify the sulphur isotopic composition of incorporated sulphate from syndepositional seawater in shelf crest, outer shelf, shelf margin and slope depositional settings. This study used a new multicollector inductively‐coupled plasma mass spectrometry technique to determine the sulphur isotopic composition of samples of individual depositional and diagenetic textures. Carbonate rocks representing peritidal facies in the Yates and Tansill formations preserve the sulphur isotopic composition of Guadalupian seawater sulphate despite alteration of the carbon and oxygen isotopic compositions by meteoric and dolomitizing diagenetic processes. However, sulphur isotopic data indicate that limestones deposited in reef and slope facies in the Capitan and Bell Canyon formations largely incorporate sulphate from anoxic marine‐phreatic pore fluids isotopically modified from seawater by microbial sulphate reduction, despite generally preserving the carbon and oxygen isotopic compositions of Permian seawater. Some early and all late meteoric calcite cements have carbonate‐associated sulphate with a sulphur isotopic composition distinct from that of Permian seawater. Detailed petrographic and sedimentary context for carbonate‐associated sulphate analyses will allow for improved reconstructions of ancient seawater composition and diagenetic conditions in ancient carbonate platforms. The results of this study indicate that carbonate rocks that diagenetically stabilize in high‐energy environments without pore fluid sulphate gradients can provide a robust archive of ancient seawater's sulphur isotopic composition. 相似文献
3.
《Journal of African Earth Sciences》2005,41(1-2):1-23
Field, petrographic and stable isotopic evidence indicate the former presence of widespread evaporites in the Neoarchaean Campbellrand Subgroup of South Africa. Calcitization of the vanished but once laterally-extensive evaporites was apparently driven by bacterial sulphate reduction of solid sulphate in association with organic diagenesis and pyrite precipitation within platform-wide microbialites and sapropels. This counters current interpretations that much of the calcite was precipitated directly on the seafloor or in primary voids in open marine conditions controlled by regional seawater chemistry. Rather, large-scale microbial mediation of ambient waters across a shallow to emergent platform raised carbonate alkalinity and removed kinetic inhibitors to carbonate formation.The low preservation potential of Precambrian solid sulphate is related in part to bacterial sulphate reduction within the microbially-dominated ecosystems of which cyanobacteria were a major component. Evidence for the former presence of solid sulphate in shallow Neoarchaean seas includes pseudomorphs after selenite, also recorded from the contemporaneous Carawine Dolomite of Australia, together with rock fabrics and textures typical of evaporite dissolution. Importantly, sulphur isotopes of pyrite samples from the Cambellrand carbonates show a wide range of values indicating biogenic fractionation of sulphate, a signature also seen in the Neoarchaean Belingwe Greenstone Belt of Zimbabwe, and the Mt McRae and Jeerinah shales of Western Australia.Mass microbial colonization across extensive Neoarchaean epeiric seas witnessed the microbiogeochemical transformation of the Earth’s hydrosphere, atmosphere and biosphere. The consequences for a reducing ocean would be the progressive oxidation of the major dissolved species in surface seawater, most notably of reduced sulphur and iron. Cyanobacterial photosynthetic oxidation of surface seawater drove formation of aqueous sulphate and permitted the precipitation of extensive evaporites in restricted basins, perhaps beginning the process of ridding the oceans of reduced sulphur. The first dramatic explosion of carbonate precipitation can be related to intense bacterial sulphate reduction in association with anoxic organic diagenesis and pyrite formation within the decaying interiors of microbialites and in sapropels. 相似文献
4.
The middle Permian Chihsia Formation of south China accumulated on a shallow shelf, and consists mainly of black to dark grey micritic limestone rich in chert nodules and organic matter. A unique type of nodular crystal cluster is distributed widely in the carbonate succession. Most crystal clusters consist of calcite. Some, however, are composed of celestite, and geochemical, microscopic and crystal morphological data suggest that celestite was the precursor of the calcite. The celestite developed displacively within the sediments during early diagenesis, before compaction and before local dolomitization of the host rock. Similar strontium isotopic values were obtained from the celestite clusters, replacement calcite, vein calcite and host rock. The values are within the range of middle Permian sea water. The strontium in the celestite was furnished chiefly by either diagenetic alteration of strontium‐rich marine aragonite to strontium‐poor calcite, or aragonite dissolution induced by aerobic oxidation of organic matter, or both. The sulphur isotopic values of the celestite are about 6–11‰ heavier than the sulphur isotopic value of sulphate in coeval sea water. Based on geological context, this difference is attributed to microbial reduction of porewater sulphate in the Chihsia sediments. 相似文献
5.
Nuia是早奥陶世备受争议的一种疑难钙化微体化石,其分类位置长期以来因内部构造常被成岩作用破坏而未得到解决。本文在薄片镜下观察的基础上,结合拉曼光谱和扫描电镜分析技术,对黔北桐梓地区下奥陶统红花园组生物礁中的Nuia化石进行形态解剖分析并探讨其钙化机制。研究结果显示,Nuia由发射状丝状体(filaments)聚集而成的胶群体(colony)以及外围的钙化外鞘(calcified encrustation)组成,丝状体基部往往有异形胞和(或)厚壁孢子聚集成暗色的中央区。据此,Nuia 可能是蓝藻门念珠藻目胶须藻科(Rivulariaceae, Nostocales, Cyanophyta)的早期代表。通过类比现代蓝藻的钙化机制模型,Nuia 可能具有比较复杂的钙化过程：原植体通过二氧化碳聚集机制(carbon dioxide concentrating mechanisms, CCMs)进行光合作用的过程中,碳酸盐颗粒首先在原始丝状体的基部胶鞘内沉淀形成黑色的中央区;随着藻丝的生长和假分枝的出现,丝状体的相应位置可形成反映季节变化的钙化带,显示为特殊的分层现象,藻丝生长停止后,藻体表面形成一层公共胶鞘,并经浸染作用和(或)结壳作用形成钙化外鞘;丝状体在早期成岩阶段受到重结晶作用而被交代为方解石纤维。此外,Nuia的中央区和公共胶鞘可能有细胞降解残留的有机大分子,限制了矿物晶体的快速生长,钙化过程中只形成细小的方解石矿物,因而在薄片中呈现出比围岩和钙化丝状体更深的颜色。 相似文献
6.
The present work is an attempt to establish the stable isotope database for Mesozoic to Tertiary coals from the Pannonian Basin, Hungary. Maceral composition, proximate analysis, sulphur form, sulphur isotopes (organic and pyritic), and carbon isotopes were determined. This database supports the assessment of the environmental risks associated with energy generation, the characterization of the formation and the distribution of sulphur in the coals used.The maceral composition, the sulphur composition, the C, S isotopic signatures, and some of the geological evidences published earlier show that the majority of these coals were deposited in freshwater and brackish water environments, despite the relatively high average sulphur content. However, the Upper Cretaceous, Eocene, and Lower Miocene formations also contain coal seams of marine origin, as indicated by their maceral composition and sulphur and carbon chemistry.The majority of the sulphur in these coals occurs in the organic form. All studied sulphur phases are relatively rich in 34S isotopes (δ34Sorganic = + 12.74‰, δ34Spyrite = + 10.06‰, on average). This indicates that marine bacterial sulphate reduction played a minor role in their formation, in the sense that isotopic fractionation was limited. It seems that the interstitial spaces of the peat closed rapidly during early diagenesis due to a regime of high depositional rate, leading to a relative enrichment of the heavy sulphur isotopes. 相似文献
7.
近年来的油气勘探表明, 含硅热液是碳酸盐岩层系中一种重要的溶蚀性流体, 查明其与碳酸盐岩的水-岩反应机理是揭示“硅化碳酸盐岩”储层发育机制并实现储层分布预测的基础和关键问题之一。文章采用熔融毛细硅管和水热反应釜为反应腔,开展了200~375℃范围内方解石和含硅流体的水岩反应实验。利用原位拉曼光谱技术在线描述反应过程中体系组成的变化,对于淬火后的固相样品,则采用扫描电镜—能谱分析进行形貌观测和成分鉴定。首先,查明了含硅流体与方解石脱碳反应发生的温度条件。方解石和含硅流体在275℃以上反应形成CO2,固相为非硅灰石的钙硅酸盐,其结构有待进一步揭示。该结果表明单纯的硅质组分难以在储层温度条件下与灰岩发生反应;其次,提出高盐度、富CO2流体作用是造成灰岩溶蚀的重要因素;最后, CO2的存在能够促进硅质（含石英）沉淀。在上述实验认识的基础上,结合前人研究结果探讨了塔里木盆地顺托果勒地区“硅化碳酸盐岩”储层的发育机制。含硅热液沿深大断裂上移,途径震旦系—下奥陶统白云岩层系,其中的硅质组分将与白云石反应形成富镁硅酸盐和CO2。CO2是重要的酸性组分,有利于鹰山组碳酸盐的溶蚀和孔隙的保存。流体温度和压力的降低以及CO2的存在促进了石英沉淀,并形成了大量的石英晶间孔隙。 相似文献
8.
P Behera 《Journal of Earth System Science》2007,116(2):137-142
Volatile displacement, which measures the difference between calculated and experimental volatile matter, is indicative of
abnormality in coals which may be related to petrological or chemical parameters. The volatile displacement (δυ) values of Meghalaya coals were calculated from their chemical analyses. Correlations of volatile displacement (δυ) with parameters such as carbon, hydrogen, moisture, oxygen, oxygen plus sulphate sulphur, oxygen plus pyritic sulphur, oxygen
plus organic sulphur and total sulphur were studied. An approximately linear relationship exists only between δυ and moisture, and δυ and total sulphur, and not between other parameters. Plots on Seyler’s chart indicate the coals as perhydrous to orthohydrous.
The linear relationship with total sulphur indicates that the coals may have become abnormal mainly due to the marine environment
of deposition and weathering. 相似文献
9.
Rahul Choudhury Jyotilima Saikia Binoy K. Saikia 《Journal of the Geological Society of India》2017,90(3):329-334
The mineralogy and geochemical studies of the coal-mine shale collected from the Tirap opencast coal-mine (Makum coalfield, Northeast India) are reported in this paper. Thermo-chemical conversion (pyrolysis) of coal-mine shale has been studied to see its hydrocarbon potential. A combined approach using X-Ray diffraction (LTA-XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) equipped with an energy-dispersive X-ray spectrophotometer (EDS), X-ray fluorescence spectrometry (XRF), thermogravimetry-derivative and differential thermogravimetric (TG-DTG and DTA) analysis is made to obtain new information on the mineralogical and geochemical studies of a coal-mine shale (CMS) sample. Gas chromatography-mass spectrometry (GC-MS) analysis is performed to evaluate the quality of the liquid fraction (tar) obtained after pyrolysis at 600°C. The shale sample is dominated by quartz, clay minerals (kaolinite and illite), sulphate bearing phase like gypsum with minor proportion of anatase, probably as artifacts of the plasma-ashing process. GC-MS analysis illustrates the presence of highly oxygenated organic components (M.W. around 94-108) and high molecular weight (M.W. 256) cyclic sulphur (e.g. octathiocane with molecular formula S8) compounds along with the complex N-containing organic sulphur compounds (M.W. around 255-486) in the tar produced. 相似文献
10.
鸟眼构造是碳酸盐岩地层中一种特殊的构造,指示潮上-潮间带沉积环境。安徽巢湖地区三叠系东马鞍山组底部普遍发育一层鸟眼构造,但对其矿物学、地球化学特征及成因还缺乏基本的认识。通过光学显微镜、粉晶X-射线衍射(XRD)、拉曼光谱分析及LA-ICP-MS原位微区元素含量测定等方法,对东马鞍山组鸟眼构造的矿物学及元素地球化学特征进行探究。结果表明:鸟眼内部矿物组合以方解石为主,石英及黏土矿物含量较低,方解石晶粒较大且由核部到边部晶粒逐渐变小,富集Sr、REE等离子半径较大的元素;基质矿物组合以白云石为主,石英及黏土矿物含量多于鸟眼核部,有机质含量较高,主要富集Fe、Cu、Ti等离子半径较小或不易迁移的元素。这些综合信息反映了巢湖东鞍山组鸟眼构造是由成岩阶段基质白云岩化析出Ca,在沉积有机质分解聚集形成的气泡孔洞中重新沉淀形成方解石而成。 相似文献
11.
A comparative analysis of two sediment cores from perialpine lakes (L. Zürich and L. Geneva) helped to clarify pathways of sulphur fixation in freshwater sediments. Despite greater than three-fold differences in lake water sulphate concentration equal amounts of sulphur are fixed in the sediments. The maximum sedimentary sulphur concentrations attain 1% (dry weight) which is similar to the sulphur content of modem, near-shore marine sediments. This is also expressed in low C org /Stot ratios which range from 2.5–8.
An analysis of the sulphur pools showed that organic sulphur compounds are the main components of the sedimentary sulphur, accounting for ˜ 80% and ˜ 60% of the total sulphur in Lakes Zürich and Geneva, respectively. The largest single sulphur pool is the sulphate-esters, which comprise 40–60% of the total sedimentary sulphur. Substantial amounts of the organic sulphur compounds must be formed within the sediment by boundary-layer microbial communities at the oxic-anoxic transition zone. This possibly suggests rapid recycling of sulphur in suboxic zones. Because of low concentration of SO2 4 -- in the watermass, the zone of sulphate reduction is very thin. This coupled with the mobility of some sulphide oxidizing microbial colonies (e.g. Beggiutoa ) potentially results in an almost complete recycling of the sulphur pool near the sediment-water interface. Reduced sulphur caught in this cycling process is unavailable for sedimentary pyrite formation. The Corg /Spyrite ratios for these sediments are thus high. If organically bound sulphur is not completely transformed into pyrite during late diagenesis, the Corg / Spyrite ratio can serve as a sensitive indicator for the salinities of anaent depositional environments. 相似文献
An analysis of the sulphur pools showed that organic sulphur compounds are the main components of the sedimentary sulphur, accounting for ˜ 80% and ˜ 60% of the total sulphur in Lakes Zürich and Geneva, respectively. The largest single sulphur pool is the sulphate-esters, which comprise 40–60% of the total sedimentary sulphur. Substantial amounts of the organic sulphur compounds must be formed within the sediment by boundary-layer microbial communities at the oxic-anoxic transition zone. This possibly suggests rapid recycling of sulphur in suboxic zones. Because of low concentration of SO
12.
SIMON H. BOTTRELL ROBERT J.G. MORTIMER IAN M. DAVIES† S. MARTYN HARVEY‡ MICHAEL D. KROM 《Sedimentology》2009,56(4):1159-1173
In this study, the biogeochemical transformations of sulphur in organic‐rich marine sediments in a Scottish fjord are investigated by a combination of pore water and sediment geochemistry with sulphide diffusive gradient thin‐film probes and sulphate isotopic data (δ34S and δ18O). Particular attention is paid to sulphur cycling in the upper sediment profile where sulphate reduction occurs but free sulphide is below the detection limits of conventional pore water geochemical analysis but quantifiable by sulphide diffusive gradient thin film. In the uppermost part of the sediment core, δ18O sulphate decreased from near‐sea water values to +7‰, indicating that anoxic sulphide oxidation dominated during this interval. Sulphate δ34S remained unchanged as there was no net sulphate reduction (i.e. reduction was balanced by re‐oxidation). Below 4 cm depth, there was a slight increase in sulphate δ34S from 20‰ to 23‰ associated with minor accumulation of iron sulphide. The δ18O of the sulphate also increased, to around +10‰ at 10 cm depth, as a result of the isotopic exchange of sulphate–oxygen with pore water and/or sulphur disproportionation reactions mediated during sulphur cycling. These processes continued to increase the δ18O of the sulphate to 14‰ at 20 cm depth with no further change in the δ34S of the sulphate. Below 20 cm depth, free sulphide is detectable in pore waters and both the δ34S of the sulphate and sulphide increase with depth with an offset controlled by kinetic fractionation during bacterial sulphate reduction. The δ34S of the sedimentary organic fraction shifted towards lower, more bacteriogenic, values with depth in the profile, without any increase in the size of this sulphur pool. Thus, the organic sulphur fraction was open to interaction with bacteriogenic sulphide without the occurrence of net addition. Therefore, caution should be exercised when using sulphur isotopic compositions to infer simple net addition of bacteriogenic sulphide to the organic sulphur fraction. 相似文献
13.
The presence and localization of organic sulfate within coral skeletons are studied by using X-ray absorption near edge structure spectroscopy (XANES) fluorescence. XANES spectra are recorded from four reference sulfur-bearing organic molecules: three amino acids (H-S-C bonds in cysteine; C-S-C bonds in methionine; one disulfide bond C-S-S-C bonds in cystine) and a sulfated sugar (C-SO4 bonds in chondroitin sulfate). Spectral responses of three coral skeletons show that the sulfated form is extremely dominant in coral aragonite, and practically exclusive within both centres of calcification and the surrounding fibrous tissues of coral septa. Mapping of S-sulfate concentrations in centres and fibres gives us direct evidence of high concentration of organic sulfate in centres of calcification. Additionally, a banding pattern of S-sulfate is visible in fibrous part of the coral septa, evidencing a biochemical zonation that corresponds to the step-by-step growth of fibres. 相似文献
14.
海南岛红树林泥炭中硫及其成因研究 总被引：4，自引：2，他引：4
海南岛红树林泥炭普遍富硫。黄铁矿、硫酸盐和有机硫是泥炭中硫的三种主要赋存形态,其中,以黄铁矿硫高为特征。利用形态硫分析、硫同位素分析等手段结合硫的时空变化特征,研究了泥炭中硫的形成机理。泥炭中硫的富集与泥炭坪环境具紧密的成因联系,全硫和形态硫的时空变化受微环境的控制;潮坪水介质中的硫酸盐是泥炭中硫的最初来源;泥炭中硫的加入,主要发生于准同生价段,在加入过程中还原硫细菌起了决定性作用。定量沉积环境分析是查明古代富硫煤田硫分布的主要途径。 相似文献
15.
Pedogenic needle-fiber calcite was studied regarding its morphology, texture and stable isotope composition from the paleosol of the Quaternary Várhegy travertine (Budapest, Hungary). The needle-fiber calcite is composed of 40–200 μm long monocrystals. Smooth rods as well as serrated-edged crystals with calcite overgrowths were identified by SEM. Needles have several textural varieties: randomly distributed crystals in vugs and pores with calcite hypocoatings, bundles of subparallel crystals forming coatings around grains and alveolar structure with bridging needles in vugs.The morphological study of needle-fiber calcite suggests that needles are calcified fungal sheaths and produced by fungal biomineralization, a common process in recent and fossil soils and calcretes. The stable isotope composition of needle-fiber calcite (average: δ18O=-7.1‰ and δ13C=-7.3‰ vs. V-PDB) indicates significant incorporation of organically derived CO2 and probably biological influence on needle genesis. Dissolved host rock travertine and/or atmospheric CO2 could also contribute some carbon to the acicular calcite. 相似文献
16.
The organic matter-rich Toolebuc Formation of eastern Australia was deposited in a Lower Cretaceous epicontinental sea. Parameters from biological marker studies indicate that the organic matter is immature to marginally mature for hydrocarbon generation. The occurrence of abundant coccoliths and the distribution of alkane biomarkers suggest that the organic matter (Type II) is largely of planktonic origin and only in the southeastern part of the depositional area can a terrestrial influence be discerned. Variations in kerogen composition can be attributed to the extent of the oxidation of the source materials and the degree of incorporation of sulphur. The atomic H/C ratios (c. 1.1) are remarkably constant for most of the Toolebuc Formation. Atomic O/C ratios vary from 0.1 and 0.4 and can be related both to depth and paleogeographic position. Kerogen sulphur contents range up to 7%, and the highest values occur in the most carbonate-rich sediments. Total sulphur (inorganic + organic) to carbon ratios in the sediments vary from 1 to <0.2 and are a function of paleogeographic position and lithology. Most of the sulphur in the sediments is in the form of pyrite, but the proportion of sulphur in organic form increases as the total sulphur content decreases. The evidence for oxidation of the organic matter and incorporation of sulphur into it during deposition suggests that bituminite, which is the dominant organic maceral in the Toolebuc Formation, was formed from an organic gel derived by decay of predominantly algal material. These data support a modified gyttja model (Kauffman, 1981) for the deposition of organic matter in the Toolebuc Formation. 相似文献
17.
Pyrite is consistently found in modern seafloor vesicular basalts and has a sulphur isotopic composition consistent with microbial activity. We present S isotope data from pyrite in Ordovician pillow lavas at localities across the British Isles, which yield a range of δ34S compositions consistent with two components of sulphur: groundmass pyrite (~0 ± 4‰) and 32S‐enriched pyrite in the vesicles (−8‰ to −27‰). The latter are recorded from vesicular lavas in four different terranes, representing different settings at the margins of the Iapetus Ocean. Whereas a component of magmatic sulphate is recognized in the groundmass values, the isotopically light data in the vesicles are consistent with microbial reduction of seawater sulphate in sub‐seafloor lavas. This is consistent with modern examples and indicates considerable longevity for this sub‐seafloor microbial habitat. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
18.
A. Iu. Iurchenko N. Takahata K. Tanaka Y. Sano N. S. Balushkina G. A. Kalmykov 《Moscow University Geology Bulletin》2016,71(6):466-471
Dispersed and concretionary pyrite in chert–clay–carbonate and carbonate rocks of the Abalak Formation (Salym oil field) have been studied. The study was conducted using Scanning Electron Microscopy (SEM), Electron Probe Microanalysis (EPMA), and high spatial resolution Secondary Ion Mass Spectrometry (Nano-SIMS). As a result, three morphological groups of pyrite have been distinguished: large cubic crystals, framboidal pyrite, and fine-crystal aggregates that replace organic remnants. The sulphur isotope ratio allows one to distinguish two genetic types of pyrite. The source of the sulphur for the first genetic group was H2S produced by bacterial sulphate reduction, while the second group pyrite was formed with sulphur as a product of thermochemical sulphate reduction. 相似文献
19.
The Marl Slate, the English equivalent of the Kupferschiefer, has been studied with particular reference to the relationships between dolomitization and the origin of the metal sulphides. Dolomite occurs as: 1) discontinuous lenses of ferroan dolomicrite, 2) micronodules of finely crystalline dolospar in association with length-slow chalcedony and 3) discrete laminae of ferroan or non-ferroan dolospar. The ferroan dolomicrite has excess CaCO3, and is more abundant in the lower, sapropelic facies of the Marl Slate. It is considered to have formed by the penecontemporaneous alteration of calcium carbonate under hypersaline conditions. Small micronodules (typically about 0.3 mm in diameter) are also more abundant in the sapropelic Marl Slate. These frequently contain cores of length-slow chalcedony (quartzine) fibres and sometimes quartz megacrysts. Textural observations clearly indicate that this silica is of authigenic origin and the dolomite/chalcedony micronodules are interpreted as diagenetic replacements of a calcium sulphate mineral such as anhydrite. The discrete laminae of finely crystalline dolospar are often inter-laminated with calcite in the upper part of the Marl Slate. This dolomite is also calcium rich and represents a replacement, possibly of anhydrite, during a later phase of diagenesis. Metal sulphides occur in two distinct forms: as disseminated framboidal pyrite and as discrete lenses of pyrite, chalcopyrite, galena, sphalerite and rarer sulphides. The framboidal pyrite originated during early diagenesis by reaction of sulphide, produced by reduction of sulphate by organic material and micro-organisms, with iron also released in the reducing environment. The sulphide lenses are often in intimate association with dolospar, length-slow chalcedony and authigenic quartz megacrysts. This indicates that the lenses were produced during diagenesis by the reduction and replacement of calcium sulphate (anhydrite). Various sources, such as co-precipitation with dolomite precursors and the underlying Yellow Sands, may have supplied metals which were mobilized and transported by connate brines as diagenesis progressed. 相似文献
20.
Series of n-alkyl and isoprenoid thiophenes and thiolanes, most of which have not been previously reported, have been identified in an extract from a Messinian (Upper Miocene) marl layer deposited under hypersaline, euxinic conditions. The identifications were based on mass spectra and Chromatographic data of synthesized reference compounds and on comparison of mass spectra, relative retention times and response on the FPD. Their specific structures and their distribution patterns show similarities with those of the alkanes. Inorganic sulphur is therefore considered to be incorporated into specific lipid moieties from (archae)bacterial and/or algal input during diagenesis. A biosynthetic origin of these compounds is also possible, however. The organic sulphur compounds encountered are thought to be indicators of a hypersaline depositional environment. 相似文献