Carbon-sulphur-iron-variations and sulphur isotope patterns of Silurian Graptolite Shales

ABSTRACT Black shale horizons (Graptolithenschiefer) in Silurian and Lower Devonian strata of the Franconian-Thuringian Highlands (Frankenwald-Thüringer Wald) of Germany have high metal concentrations (e.g. U,V,Mo). Organic carbon, sulphur and iron contents, degree of pyritization (DOP) and sulphur isotope ratios from the Lower Graptolite Shales, along with faunal and sedimentological evidence show that the depositional environment was anoxic. Although some data (e.g. C/S plots) do not suggest completely euxinic conditions, the DOP versus C plot indicates a Black Sea-type environment. From the sulphur isotope data the environment fluctuated between'open'and'closed'with respect to sulphate supply, with higher carbon contents reflecting an increased bacterial reduction of the available sulphate. Diagenetic effects were responsible for somewhat unusual plots of C/S ratios, though iron availability may have been influential.     

Sulphur Enrichment in Organic Matter of Eastern Mediterranean Sapropels: A Study of Sulphur Isotope Partitioning

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.     

海南岛红树林泥炭有机组成特征及其地质意义

海南岛红树林泥炭形成于热带泥炭聚积区,成炭质料为适盐性的红树林植物群落,堆积环境为泥炭坪,与陆相沼泽泥炭相比,这些特殊性必然反映到泥炭的有机组成上。红树林泥炭有机成份的研究将为合理开发利用海南的泥炭资源提供依据。红树林泥炭有机组成特征及其在泥炭化过程中的变化也必然为探讨泥炭化机理提供大量地质信息。一、海南岛红树林泥炭的一般特征海南岛红树林泥炭以埋藏泥炭为主,主要分布于海南岛东北部沿海地区,以琼山县东寨港和琼海县福田地区发育最好,其成炭环境为泥炭坪。现在正在发育的泥炭坪仅见于文     

赤普铅锌矿床成矿物质来源研究

通过野外观察和铅、硫、碳同位素测定，稀土元素组成，微量元素和包裹体资料，对该矿床成矿物质的来源作了系统分析，表明金属元素主要来自围岩灯影组，硫具有地层硫与非生物还原硫的混合来源，脉石碳酸盐矿物中的碳来自围岩酸岩的溶解，重结晶，但混入有有机碳，介质（水）主要来自大气降水。     

Sources and preservation of organic matter in the Cretaceous Toolebuc Formation, eastern Australia

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.     

重庆地区上三叠统须家河组煤质特征规律初探

重庆地区须家河组为一套砂岩、泥岩、砂质泥岩、粉砂岩和煤层组成的湖滨-三角洲型沉积,煤质分级主要为中灰（特低灰-高灰）、低硫（特低硫-中高硫）、高热值（低热值-特高热值）煤;灰分与硫分等值线分布较为相似,总趋势为北东-南西向展布,呈不规则条带状和团块状分布;原煤灰分值与发热量值呈负相关性,浮煤灰分值与发热量值呈正相关性,初步得出同一采集点原煤和浮煤的灰分与发热量的相关性正好相反,煤类分布与挥发分等值线展布相似的结论。     

甘肃省礼县中川地区李坝式金矿床载金矿物地球化学特征及矿床成因意义

中川地区载金矿物硫同位素、氢氧同位素和碳氧同位素特征说明成矿作用与沉积建造有较大的亲缘性。载金矿物流体包裹体中大量的 Cl- 、SO4 2 - 和 Ca2 、Na 高含量及其特征比值显示出大气降水带入了大量的建造中的物质成分。热液期黄铁矿微量元素标型特征体现地下热卤水溶滤成因特征 ,同时也显示了岩浆活动对成矿作用影响的痕迹     

重大地质转折期的碳、硫循环与环境演变

碳、硫在表层储库和地质储库以不同的形式相互转换,在这个过程中都伴随着一定的同位素分馏。碳同位素的分馏主要受到光合作用以及海水溶解无机碳与大气CO2交换的控制,而硫同位素的分馏则主要受控于硫酸盐细菌还原作用。表层储库碳、硫同位素的组成通过地质作用被很好地保存在地质储库中,因此通过对地质储库中碳、硫同位素的分析和研究,可以很好地了解地球各圈层相互作用的规律,重塑地质历史特别是重大关键转折时期的演化过程。同时文中借助一些碳、硫同位素应用实例,进一步加深理解影响碳、硫同位素组成和变化的原因,以提高对不同时期全球环境变化的认知程度。     

Organic carbon and sulphur compounds in wetland soils: insights on structure and transformation processes using K-edge XANES and NMR spectroscopy

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.     

中国煤中有机硫的分布及其成因

对来自全国26个省、市、自治区的290个煤样中有机硫的质量分数测试及研究,发现煤中有机硫质量分数基本分布在0%1.0%范围内。在低硫煤中硫分以有机硫为主,在高硫煤中以无机硫为主。中、高硫煤中,广西、湖南等地区很大一部分煤中硫分以有机硫为主。在所采集的样品中,高有机硫煤(有机硫>1%)均分布在华南、华北两大聚煤区,属于石炭、二叠纪煤。高有机硫煤中有机硫质量分数的变化与变质程度无明显关系。煤炭形成过程中海水作用的影响,是导致煤中有机硫含量偏高的最主要原因。      

Diagenetic controls on the isotopic composition of carbonate‐associated sulphate in the Permian Capitan Reef Complex,West Texas

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.     

Sulphur contents of conifer needles in Great Britain

There is currently a lack of convincing evidence linking air pollution and tree health in Great Britain. Field surveys have not revealed a clear association between the spatial distribution of crown thinning and air pollution; the crown condition of some species is apparently better in more polluted areas. This has been attributed to the confounding effects of climate, which is known to have a marked effect on crown condition. In this study, analysis of total sulphur contents of needles ofPicea sitchensis ((Bong.) Carr.),P. abies ((L.) Karst.) andPinus sylvestris (L.) reveals marked patterns that are correlated with modelled atmospheric concentrations of sulphur dioxide. Correlations with other indices of sulphur pollution, including wet and dry deposition and sulphate aerosol concentrations, are less consistent. However, no association has been found between the sulphur contents of needles and the crown densities of trees in Britain.     

Contrasting sulphide contents of the Bushveld and Sudbury Igneous Complexes

The Sudbury Igneous Complex (SIC) contains abundant sulphides, especially near the base, and hosts one of the worlds largest nickel and copper deposits. The Bushveld Complex (BC) contains relatively little sulphide, but hosts the worlds largest platinum-group element deposits. The most recent calculations of the sulphur solubility in magmas that produced the BC are based on the sulphur solubility of mid-ocean ridge basalts that have less SiO₂ than Bushveld magmas. Such a difference may lead to an overestimation of sulphur solubility by as much as 25%. The revised sulphur solubility curve presented here for Bushveld magmas may also have relevance to the SIC in view of its siliceous nature. Sulphur solubility curves can be used to determine the proportion of sulphide expected in cumulate rocks once sulphur saturation is attained. These models are tested using observed sulphide contents in both intrusions. The observed decreasing sulphur contents (>0.3–0.05% S) from the base of the SIC upward are broadly consistent with these sulphur solubility curves, and are consistent with sulphide saturation through the entire mafic portion. In contrast, the lower half of the BC contains extremely little sulphur (generally <0.02% S), except for two thin layers, which is not consistent with sustained sulphide saturation at any level. Previous interpretations of the sulphur content of Bushveld rocks have suggested that the Lower and Critical Zones were sulphide saturated, but that they had then lost some of the sulphide due to various processes. The present sulphide content of the cumulates of the BC is so low that, if they had once been saturated, over 90% of all the sulphide must have been removed. Mass balance calculations indicate that these large amounts of displaced sulphur remain unaccounted for in such models. Instead, the observed sulphur contents are in reasonable agreement with that expected in a cumulate sequence forming from a sulphur-undersaturated magma. Whereas the Merensky Reef and Bastard pyroxenite contain minor sulphides, the compositions of the immediate hanging wall rocks indicate sulphide undersaturation. Such an abrupt return to sulphide undersaturation is not consistent with models involving sulphide formation from large volumes of magma. One possible explanation for these two observations is that intermittent sulphur degassing occurred through a fractured roof of the BC, so that the magma was never continuously sulphur-saturated with respect to an immiscible sulphide liquid.     

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.     

苯并噻吩系列化合物的成因模拟及其地球化学意义

在硫和β胡萝卜素反应产物中有丰富的苯并噻吩系列化合物,在硫与饱和链状化合物反应产物中既有噻吩系列化合物也有苯并噻吩系列化合物。所以推断苯并噻吩系列是硫作用于噻吩系列或含侧链的苯而形成的。噻吩系列和苯并噻吩系列的相对含量可以指示成熟度:在沉积条件相同的前提下,前者多后者少指示成熟度低,反之则指示成熟度高。     

Sulphur and carbon isotopic composition of power supply coals in the Pannonian Basin, Hungary

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 (δ³⁴S_organic = + 12.74‰, δ³⁴S_pyrite = + 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.     

Pyrite-organic matter relationships: Currant Bush Limestone,Georgina Basin,Australia

The relationship between the TOC (total organic carbon) and S (pyritic sulphur) contents of some organic-rich (TOC 3–14%) silty limestones and calcareous siltstones from the Cambrian Currant Bush Limestone of the Georgina Basin, Australia, is similar to that of euxinic sediments, but could also indicate deposition in a non-saline environment. However, such conditions are not easily reconciled with the shallow equatorial epeiric sea in which the formation is considered to have been deposited. The relationship can alternatively be explained by the relatively low Fe content of the sediment being the main limiting factor in pyrite generation, coupled with a slightly increased degree of pyritization with increased TOC. The relationship between the TOC and S contents of organic-poor (TOC 0.2–2.4%) samples from the same formation is similar to that of normal marine sediments, but the Fe content is probably also the major controlling factor on pyrite generation. These interpretations demonstrate that in using TOC and S contents to aid in reconstruction of depositional environments, it is important to check whether Fe content could have been the limiting factor in the formation of pyrite, even in sediments with only moderate carbonate contents.     

噻吩系列化合物的形成机理模拟

通过模拟实验发现硫能和各种链状化合物反应形成噻吩系列化合物。其反应机理可能是：硫先作用于链状化合物将其改造成共轭烯中间体,其他硫再从这个部位进入碳骨架从而形成该类化合物。硫还可进一步和噻吩系列反应形成更复杂的含硫芳烃,而温度升高会促进这种反应,所以噻吩系列的含量可以作为成熟度指标,在沉积条件相同的前提下,噻吩系列含量高指示成熟度低,反之则指示成熟度高。     

Chemical composition of macerals in bituminous coals of the Gunnedah Basin, Australia, using electron microprobe analysis techniques

The chemical composition of the organic matter in the principal macerals of high-volatile bituminous coals from the Gunnedah Basin, New South Wales (Rv_max of telocollinite between 0.6 and 1.1%) has been evaluated from polished section specimens using an electron microprobe technique. Highest proportions of carbon occur in the inertinite macerals, especially fusinite and secretinite (formerly resino-sclerotinite), as well as in sporinite; lowest proportions of carbon occur in the different macerals of the vitrinite group. Oxygen shows the reverse trend, being most abundant in vitrinite and least abundant in the inertinite components, whereas sulphur is lowest in the inertinites and highest in the liptinite (mainly sporinite) present. Evaluations of maceral composition, using the carbon content of telocollinite as a rank indicator, show that carbon is more abundant in both sporinite and semifusinite, relative to vitrinite, in low-rank high-volatile bituminous coals. The difference decreases with increasing rank, and the proportion of carbon in telocollinite becomes essentially the same as that in sporinite and semifusinite at carbon contents of about 89 and 91%, respectively. The carbon content of fusinite and secretinite, on the other hand, does not seem to vary appreciably with rank advance. No significant difference in composition occurs in the rank range studied between the three vitrinite varieties present, desmocollinite, telocollinite and a more highly reflecting telocollinite resembling pseudovitrinite. No evidence was found to indicate a higher hydrogen content, relative to telocollinite, for the vitrinite matrix of desmocollinite.     

Experimental evidence for rapid biotic and abiotic reduction of Fe (III) at low temperatures in salt marsh sediments: a possible mechanism for formation of modern sedimentary siderite concretions

Fe (III) reduction is a key component of the global iron cycle, and an important control on carbon mineralization. However, little is known about the relative roles and rates of microbial (biotic) iron reduction, which utilizes organic matter, versus abiotic iron reduction, which occurs without carbon mineralization. This paper reports on the capacity for salt marsh sediments, which typically are rich in iron, to support abiotic reduction of mineral Fe (III) driven by oxidation of sulphide. Sediment was reacted with amorphous FeS under strictly anaerobic conditions at a range of temperatures in biotic and abiotic microcosm experiments. Fe (III) reduction driven by sulphide oxidation occurs abiotically at all temperatures, leading to Fe (II) and elemental sulphur production in all abiotic experiments. In biotic experiments elemental sulphur is also the oxidized sulphur product but higher bicarbonate production leads to FeCO₃ precipitation. Abiotic reduction of Fe (III) occurs at rates that are significant compared with microbial Fe (III) reduction in salt marsh sediments. The solid phases produced by coupled abiotic and biotic reactions, namely elemental sulphur and FeCO₃, are comparable to those seen in nature at Warham, Norfolk, UK. Furthermore, the rates of these processes measured in the microcosm experiments are sufficient to generate siderite concretions on the rapid time scales observed in the field. This work highlights the importance of abiotic Fe (III) reduction alongside heterotrophic reduction, which has implications for iron cycling and carbon mineralization in modern and ancient sediments.