Distribution Characteristics of Sulfur and the Main Harmful Trace Elements in China’s Coal

To promote the rational development and use of clean coal resources in China, data on the regional and age distribution of sulfur, arsenic and other harmful elements in Chinese coal was broadly collected, tested for content, and analyzed. Coal in northwestern China is characterized by low to extremely low levels of sulfur; the coal of the Taiyuan Formation in northern China mainly has high-sulfur content; that of the Shanxi Formation is mainly characterized by low sulfur coal; and the Late Permian coal in southern China has overall higher sulfur content; other regions have low sulfur coal. The average content of harmful trace elements in the bulk of China＇s coal is similar to the corresponding content in the coal of the North America and the rest of the world, whereas the content of various elements （Hg, Sb and Se） is different in magnitude to the corresponding percentage in the crust. The average content of the elements Cr, Se, Co, Be, U, Br in Late Permian coal in S China ranks first in the country whereas the average content of Hg and CI in the coals of Late Carboniferous to Early Permian age in N China are the highest. The average content of Mn in Early and Middle Jurassic coal is higher in NW China. The high content of harmful elements in some coal should cause particular concern both in the development and utilization of coal.     

Distribution Characteristics of Sulfur and the Main Harmful Trace Elements in China's Coal

To promote the rational development and use of clean coal resources in China,data on the regional and age distribution of sulfur,arsenic and other harmful elements in Chinese coal was broadly collected,tested for content,and analyzed.Coal in northwestern China is characterized by low to extremely low levels of sulfur;the coal of the Taiyuan Formation in northern China mainly has high-sulfur content;that of the Shanxi Formation is mainly characterized by low sulfur coal;and the Late Permian coal in southern China has overall higher sulfur content;other regions have low sulfur coal.The average content of harmful trace elements in the bulk of China's coal is similar to the corresponding content in the coal of the North America and the rest of the world,whereas the content of various elements(Hg,Sb and Se)is different in magnitude to the corresponding percentage in the crust.The average content of the elements Cr,Se,Co,Be,U,Br in Late Permian coal in S China ranks first in the country whereas the average content of Hg and Cl in the coals of Late Carboniferous to Early Permian age in N China are the highest.The average content of Mn in Early and Middle Jurassic coal is higher in NW China.The high content of harmful elements in some coal should cause particular concern both in the development and utilization of coal.     

Archean Mass-independent Fractionation of Sulfur Isotope:New Evidence of Bedded Sulfide Deposits in the Yanlingguan-Shihezhuang area of Xintai, Shandong Province

Multiple sulfur isotope ratios （^34S/^33S/^32S） of Archean bedded sulfides deposits were measured in the Yanlingguan Formation of the Taishan Group in Xintai, Shandong Province, East of China; 633S = -0.7%o to 3.8‰,δ^34S = 0.1‰-8.8‰, △^33S = -2.3‰ to -0.7‰. The sulfur isotope compositions show obvious mass-independent fractionation （MIF） signatures. The presence of MIF of sulfur isotope in Archean sulfides indicates that the sulfur was from products of photochemical reactions of volcanic SO2 induced by solar UV radiation, implying that the ozone shield was not formed in atmosphere at that time, and the oxygen level was less than 10-5 PAL （the present atmosphere level）. The sulfate produced by photolysis of SO2 with negative △^33S precipitated near the volcanic activity center; and the product of element S with positive △^33S precipitated far away from the volcanic activity center. The lower △^33S values of sulfide （-2.30‰ to --0.25‰） show that Shihezhuang was near the volcanic center, and sulfur was mostly from sulfate produced by photolysis. The higher △^33S values （-0.5‰ to -‰） indicate that Yanlingguan was far away from the volcanic center and that some of sulfur were from sulfate, another from element S produced by photolysis. The data points of sulfur isotope from Yanlingguan are in a line parallel to MFL （mass dependent fractionation line） on the plot of δ^34S--δ^33S, showing that the volcanic sulfur species went through the atmospheric cycle into the ocean, and then mass dependent fractionation occurred during deposition of sulfide. The data points of sulfur isotope from Shihezhuang represent a mix of different sulfur source.     

Soil carbon stock of the Central-East Asia in the climate warming

Water samples from the Wujiang River, a typical karst river system, were analyzed for major ion concentrations and δ^34S values of dissolved sulfate in order to identify the sources of sulfate, quantify the sulfate export flux and understand the role of sulfur cycling in chemical weathering rate of carbonate. Spatial variations in sulfate concentration and sulfur isotopic composition of tributaries over the catchment area are obvious, allowing to decipher S sources between rocks and atmosphere. According to the variations in sulfate concentration and isotopic composition, it is inferred that sulfate ions in the upper-reach river waters may have three sources, rain water, sulfate resultant from oxidation of pyrite in coal, and sulfate from sulfide deposits. In the lower reaches, the S isotopic composition of the samples lies mainly on a mixing trend between evaporite sulfate and rainwater sulfate, the contribution of sulfate from oxidation of pyrite being lesser. A pronounced seasonal variation in both content and isotopic composition of sulfate characterizes the Wujiang River. The average sulfate concentration of the waters is 0.65 mmol/L in winter, 0.17 mmol/L higher than that in summer. River water δ^34S values range from -15.7‰ to 18.9‰ in winter, while the δ^34S values of river waters in summer vary to a lesser extent than in winter, from -11.5‰ to 8.3‰. The δ^34S values of the main stream range from -6.7‰ to -3.9‰ in summer, averaging 3‰ lower than in winter. This indicates that in summer, when the discharge increases, the contribution of a source enriched in light isotopes to the atmosphere or the oxidation of pyrite in coal is more important.     

Occurrence and Geological Genesis of Pyrites in Late Paleozoic Coals in North China

The occurrence and geological genesis of pyrites in Late Paleozoic colas of North china have been systematically studied in terms of coal petrology,coal chemistry,elemental geochemistry and sulfur isotope geochemistry.The results suggest that eight types of pyrite,i.e.,framboidal,automorphic graular,oolitic,massive,homogeneous spherical,allotriomorphic,nodular,joint-and fisure-filling pyrintes can be subdivided under the microscope,Four generations of pyrite are also reconized according to the shape,size,coexisting assemblage,spacial distribution relationship with macerals,the contents of sulfur and iron.atomic S/Fe ratios and associated elements in pryites.Sulfur in Late Palozoic colas of North China is of diverse source as evidenced by sulfur isotope variations in the pyrites.The δ34S values of pyrite generated at the early stage ted to be negative,and at the late stage,positive.     

Sulfur in Coal and Its Environmental Impact from Yanzhou Mining District,China

Sulfur is one of the havardous elements in coal The concentrations of sulfur are relatively high in coal.The major forms of sulfur in coal are pyritic,organic and sulfate.Pyritic and organic sulfur generally account for the bulk of sulfur in coal.Elemental sulfur also occurs in coal,but only in trace to minor amounts.When coals are burned,leached and washed,sulfur will be released in the form of sulfide and H2S,which then reach with O2,water and other substances to change into vitriol,and in some places it may form acid rain.And they will impact water environment,acidify the soil and do great harm to plants and human health.In this paper,on the basis of the data from the Yanzhou mining district,the distribution and concentrations of sulfur are analyzed and the existing forms of sulfur are studied.The variation of sulfur and its impact on the environments also are described when coal is used.     

Sulfur isotopic composition of the Tianqiao Pb-Zn ore deposit,Northwest Guizhou Province,China：Implications for the source of sulfur in the ore-forming fluids

The Tianqiao Pb-Zn ore deposit of Guizhou Province, China, is located in the mid-east of the Si-chuan-Yunnan-Guizhou Pb-Zn-Ag multi-metallic mineralization area, which is representative of the Pb-Zn ore de-posits in this area. It consists of three main orebodies, whose Pb+Zn reserves are more than 0.2 million ton. This paper analyzes the sulfur isotopic composition of these orebodies. The data show that the ore minerals (galena, sphalerite, pyrite) in these orebodies are enriched in heavy sulfur, with δ34SV-CDT values varying between 8.35‰ and 14.44‰, i.e. the δ34SV-CDT values of pyrite are between 12.81‰ and 14.44‰, the mean value is 13.40‰; the δ34SV-CDT values of sphalerite are range from 10.87‰ to 14.00‰, the mean value is 12.53‰; the δ34SV-CDT values of galena are range from 8.35‰ to 9.83‰, the mean value is 8.84‰, and they have the feature of δ34Spyrite>δ34Ssphalerite>δ34Sgalena, which indicates the sulfur isotope in ore-forming fluids has attained equilibrium. The δ34S V-CDT values of the deposit are close to those of sulfates from carbonate strata of different ages in the ore-field (15‰), which suggests that the sulfur in the ore-forming fluids should be derived from the thermo-chemical sulfate reduction of sulfates from the sedimentary strata.     

Sulfur Isotope Fractionation in Magmatic Systems：Models of Rayleigh Distillation and Selective Flux

The effect of Rayleigh distillation by outgassing of SO2 and H2S on the isotopic composition of sulfur remaining in silicate melts is quantitatively modelled.A threshold mole fraction of sulfur in sulfide component of the melts is reckoned to be of critical importance in shifting the δ^34S of the melts mith respect to the original magmas.The partial equilibrium fractionation in a magmatic system is evaluated by assuming that a non-equilibrium flux of sulfur occurs between magmatic volatiles and the melts,while an equilibrium fractionation is approached between sulfate and sulfide within the melts.The results show that under high fo2 conditions,the sulfate/sulfide ratio in a melt entds to increase,and the δ^34S value of sulfur in a solidified rock might then be shifted in the positive direction.This may either be due to Rayleigh outgassing in case the mole fraction of sulfide is less than the threshold,or due to a unidirectional increase in δ^34S value of the sulfate with decreaing temperature,Conversely,at low fo2,the sulfate/sulfide ratio tends to decrease and the δ^34S value of total sulfur could be driven in the negative direction,either because of the Rayleigh outgassing in case the mole fraction of sulfide is greater than the threshold,or because of a unidirectional decrease inδ^34S value of the sulfide.To establish isotopic equilibrium between sulfate and sulfide,the HM,QFM or WM buffers in the magmatic system are suggested to provide the redox couple that could simultaneously reduce the sulfate and oxidize the sulfide.CaO present in the silicatte Melts is also called upon to participate in the chemical equilibrium between sulfate and sulfide,Consequently,the δ^34S value of an igneous rock could considerably deviate from that of its original magma due to the influence of oxygen fugacity and temperature at the time of magma solidification.     

Sulfur isotopic geochemistry of the huize Pb-Zn ore field in yunnan province北大核心CSCD

In order to constrain sulfur isotope compositions of ore-forming fluids, ore-forming temperature, source of sulfur and mechanism of sulfur reduction in the Huize lead-zinc ore field, based on sulfur isotope compositions from previous studies, new data of sulfur isotopic composition of primary sulfide of upper ore-bodies in Qilinchang and newly-found sulfate outside the deposits were utilized in this study. It show that 5 values of primary sulfide vary from 8. Oft∗ to 17. 68 ft∗ , and sulfur isotopes in ore-forming fluid have reached equilibrium; S'lS values of sulfur out side the deposits vary from 17. 95ft∗ to 24. 30ft∗ with average value of 20. 14ft∗ , yielding sulfur isotopic composition of ore-for ming fluids as 14. 14ft∗ by the Pinekney method for mineral association. The value is close to 5'4S of marine sulfate. Ore-forming temperature is calculated as 1 34 - 388by isotope geological thermometer. The results of fluid inclusion thermometer indicate that barites were crystallized from hydrothermal fluid, which is suggested that sulfur in ore-forming fluid probably originates from marine sulfate of stratum in and outside the deposits or hydrothermal barites found in ore district. Reduction mechanism of sulfate is likely to be themio-chemical sulfate reduction.     

Modes of Occurrence and Geological Origin of Beryllium in Coals from the Pu＇an Coalfield, Guizhou, Southwest China

The concentration, modes of occurrence and geological origin of beryllium in five workable coal beds from the Pu＇an Coalfield of Guizhou were studied using the inductively coupled-plasma mass spectrometry （ICP-MS）, floating and sinking experiments （FSE） and sequential chemical extraction procedures （SCEP）. The results show that the average concentration of beryllium in coals from the Pu＇an Coalfield is 1.54 μg/g, much lower than that in most Chinese and worldwide coals. Beryllium in the Pu＇an coals was not significantly enriched. However, it should be noted that the No. 8 coal bed from the study area has a high concentration of beryllium, 6.89 μg/g, three times higher than the background value of beryllium in coal. Beryllium in coal mainly occurs as organic association and has predominantly originated from coal-forming plants when its concentration is relatively low. The concentration of beryllium occurring as organic association is close to that distributed in inorganic matter when beryllium concentration of coal is similar to its background value, and in addition to coal-forming plants, beryllium is mainly derived from detrital materials of terrigenous origin. When beryllium is anomalously enriched in coal, it mainly occurs as organic association and is derived from volcanic tonsteins leached for a long geological time and then adsorbed by organic matter in peat mire.     

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in δ³⁴S for sulfur species within and between the low-sulfur and high-sulfur coal. The δ³⁴S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the δ³⁴S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the δ³⁴S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of δ³⁴S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in δ³⁴S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition.The δ³⁴S values for fly ash from the high-sulfur Springfield coal (averaging 9.7‰) are greatly enriched in ³⁴S relative to those in the parent coal (averaging 2.2‰). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the δ³⁴S values for fly-ash samples from the low-sulfur Danville coal average 10.2‰, only slightly enriched in ³⁴S relative to those from the parent coal (average 7.5‰). The δ³⁴S values for bulk S determined directly from the fly-ash samples show close correspondence with the δ³⁴S values for SO₄^− 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion.     

The isotopic composition of plant sulfur

The isotopic composition of sulfur has been studied in plants representative of various regions of the U.S.S.R., two oceanic islands, and atmospheric precipitations on land and in marine areas. In soils, the isotopic composition of sulfur in the atmospheric water varies as a result of sulfate reduction (increase of δ³⁴S of the soil sulfate) and sulfate regeneration from hydrogen sulfide. The sulfur in plants from the oceanic islands has characteristically higher values of δ³⁴S than the sulfur in the plants and in the atmospheric water of the continents. Compared to sea water, the sulfur from the island plants that were studied contains a considerably lesser proportion of the ³⁴S isotope. This can be explained by the significant role in such plants of the sulfur of the atmospheric air masses coming from the continents.     

Mechanisms of sulfur introduction chemically controlled: δS imprint

Organic sulfur in marine sediment is ³⁴S enriched relative to the co-existing pyrite. This phenomenon is still enigmatic. Timing of the sulfur incorporation, immobilization and different sulfur species involved are part of the explanations. The reduced sulfur species incorporation into organic matter (OM) is generally assumed to have negligible δ³⁴S fractionation. This assumption has never been confirmed by laboratory experimental data. The present study measures the δ³⁴S changes resulting from reduced sulfur species (sulfides and polysulfide anions) incorporation into organic model compounds in an aquatic and low temperature (25 °C) system that simulates diagenetic marine environment. In addition, we also investigate the δ³⁴S fractionation and the isotope chemical mixing in the formation of polysulfide anions produced from elemental sulfur and sulfide anions. The results showed total isotope mixing between the two species in the formation of polysulfides. Acidification of the polysulfides solution caused δ³⁴S fractionation between the released elemental sulfur and H₂S. The incorporation of polysulfides and sulfides into carbonyl groups, caused ³⁴S enrichment relative to the starting polysulfides and sulfide of 4–5‰. The ³⁴S enrichment of the sulfurized carbonyl groups showed a minimal effect by temperature (0–70 °C) and is not affected by salinity, polysulfides composition, reaction time or solubility in water. The incorporation of polysulfides and sulfides into brominated organic compounds was negligibly ³⁴S enriched. The chemical mechanisms controlling the polysulfides incorporation into OM depend mostly on the functional groups and determine the ³⁴S enrichment of the sulfurized OM. The results presented in this study can explain part of the difference between pyrite δ³⁴S and sulfurized OM δ³⁴S in natural marine sediments.     

Evaluating the sulfur isotopic composition of biodegraded petroleum: The case of the Western Canada Sedimentary Basin

The sulfur isotopic composition (δ³⁴S) of petroleum is believed to be affected mainly by sulfur incorporation reactions into the sedimentary organic matter during the early diagenesis. However, secondary processes could affect the original δ³⁴S of oil under the effect of thermal maturity or of the microbial activity of biodegraded reservoirs. In this study, the different processes that may affect the δ³⁴S of in-reservoir oils were assessed based on the sulfur content and isotopes of a series of oil and core samples coming from various reservoirs of the Lower Cretaceous Mannville Group, Western Canada Sedimentary Basin (WCSB). Based on the molecular study, these samples appear to have reached various levels of maturity and biodegradation, ranging from 0 to 6.5 on the biodegradation scale of Peters and Moldowan. In addition, mixing of organic matter coming from different source rocks was identified based on the comparison with extensive correlation studies performed in the WCSB.Investigation of the δ³⁴S shows a trend that seems a priori correlated to the level of biodegradation. However, a careful interpretation of molecular and sulfur isotope data leads to the conclusion that the observed δ³⁴S variations have rather to be ascribed to contributions of oils generated by various source rocks. Alternatively, variations of δ³⁴S could neither be related to maturity differences nor to kinetic effects during organic sulfur compounds biodegradation. In the case of some specific core samples showing a common origin based on biomarker study, δ³⁴S variations might not be related to different sources but to secondary sulfur incorporation/exchange processes occurring within the reservoir. These processes would involve reduced sulfur species from bacterial sulfate reduction formed in situ or migrated into Mannville reservoirs. This hypothesis is supported by laboratory experiments showing sulfur exchange/incorporation under plausible conditions for shallow reservoirs.     

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.     

三叠纪海的硫同位素

前言自Ault和Kulp(1959)发表第一批海相硫酸盐岩的硫同位素分析数据以来,海相硫酸盐岩(石膏、硬石膏)的硫同位素研究工作已进行了二十余年。     

Sulfur isotopic compositions of the Huize super-large Pb–Zn deposit, Yunnan Province, China: Implications for the source of sulfur in the ore-forming fluids

The Huize Pb–Zn deposit of Yunnan Province, China, is located in the center of the Sichuan–Yunnan–Guizhou Pb–Zn–Ag district. Four primary orebodies (orebody No. 1, No. 6, No. 8 and No. 10), with Pb + Zn reserves from 0.5 Mt to 1 Mt, have been found at depth in this deposit. This paper provides new data on the sulfur isotopic compositions of the four orebodies. The data show that the principal sulfide minerals (galena, sphalerite and pyrite) in the four orebodies are enriched in heavy sulfur, the δ³⁴S values between 10.9‰ and 17.7‰ and where δ³⁴S_pyrite > δ³⁴S_sphalerite > δ³⁴S_galena. The δ³⁴S values of sulfide are close to that of the sulfates from the carbonate strata within the region. The similarity in sulfur isotope composition between sulfides and sulfates indicates the sulfur in the ore-forming fluids was likely derived by thermochemical sulfate reduction of sulfates contained within carbonate units.     

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.     

Micro-scale sulfur isotope and chemical variations in sphalerite from the Bleiberg Pb-Zn deposit,Eastern Alps,Austria

The Bleiberg Pb-Zn deposit in the Drau Range is the type locality of Alpine-type carbonate-hosted Pb-Zn deposits. Its origin has been the subject of on-going controversy with two contrasting genetic models proposed: (1) the SEDEX model, with ore forming contemporaneously with sedimentation of the Triassic host rocks at about 220 Ma vs. (2) the epigenetic MVT model, with ores forming after host rock sedimentation at about 200 Ma or later. Both models assume that, on a deposit or even district scale, a fixed paragenetic sequence of ore minerals can be established. The results of our detailed petrographic, chemical and sulfur isotope study of two key ore-samples from two major ore horizons in the Wetterstein Formation at Bleiberg (EHK02 Erzkalk horizon and Blb17 Maxer Bänke horizon) demonstrate that there is no fixed paragenetic sequence of ore minerals. Small-scale non-systematic variations are recorded in textures, sphalerite chemistry and δ³⁴S. In each sample, texturally different sphalerite types (colloform schalenblende, fine- and coarse-grained crystalline sphalerite) co-occur on a millimeter to centimeter scale. These sphalerites represent multiple mineralization stages/pulses since they differ in their trace element inventory and in their δ³⁴S. Nonetheless, there is some correspondence of sphalerite micro-textures, sulfur isotope and chemical composition between the two samples, with microcrystalline colloform schalenblende being Fe-rich, having high Fe/Cd (15 and 9, respectively) and a light sulfur isotope composition (δ³⁴S −26.0 to −16.2‰). Cadmium-rich and Fe-poor sphalerite in both samples has relatively heavier sulfur isotope composition: in sample EHK02 this sphalerite has Fe/Cd of ∼0.5 and δ³⁴S from −6.6 to −4.6‰; in sample Blb17 Fe/Cd is ∼0.1 and δ³⁴S ranges from −15.0 to −1.5‰. Barite, which is restricted to sample EHK02, has δ³⁴S ≈ 17‰. The large variations in δ³⁴S recorded on the mm to cm-scale is consistent with variable contributions of reduced sulfur from two different sulfur reservoirs. The dominant reservoir with δ³⁴S values <−20‰ likely results from local bacteriogenic sulfate reduction (BSR), whereas the second reservoir, with δ³⁴S about −5‰ suggests a hydrothermal source likely linked with thermochemical sulfate reduction (TSR). Based on this small- to micro-scale study, no simple, deposit-wide paragenetic and sulfur isotope evolution with time can be established. In the Erzkalk ore (sample EHK02) an earlier Pb-Zn-Ba stage, characterized by heavy sulfur isotope values, is succeeded by a light δ³⁴S-dominated Zn-Pb-F stage. In contrast, the several mineralization pulses identified in the stratiform Zn-Pb-F Maxer Bänke ore (sample Blb17) define a broad trend to heavier sulfur isotope values with time. The interaction documented in these samples between two sulfur reservoirs is considered a key mechanism of ore formation.     

On the isotopic sulfur composition of some Precambrian strata

A study of minerals from Proterozoic and Archean series of various regions has been carried out. Sulfate and sulfide sulfur, having doubtlessly passed through the cycle of isotopic fractionation, has been determined in Archean rocks of the Baikal region. In the lazurite deposit of Malaya Bystraya, the country rocks are Precambrian stinking (fetid) dolomites which contain ancient hydrogen sulfide with ³⁴S from +19.0 to +33.4, and sulfate with ³⁴S=+44.9. Carbonate rocks have served as sources of sulfide and sulfate sulfur for a number of minerals (lazurite, scapolites, apatite, pyrrhotite, pyrite, a. o.). A connection between the enrichment of sulfides of metamorphic strata in the ³²S isotope or the ³⁴S isotope and the presence in rocks of increased amounts of graphite — the product of metamorphism of the organic matter of ancient sediments — is established. A conclusion has been drawn regarding the isotopic fractionation about 3·10⁹ y. ago.

---

Zusammenfassung Schwefelisotopenfraktionierung durch den Sulfid-Sulfat-Zyklus findet nur dort statt, wo freier Sauerstoff vorhanden ist. Diese Tatsache wird benutzt, um das Eintreten von freiem Sauerstoff und den Beginn organischen Lebens im Präkambrium festzusetzen. Fraktionierter Sulfid- und Sulfatschwefel in archäischen Gesteinen vom Baikalsee wurde gemessen und ein Zusammenhang zwischen dem Schwefelisotopenverhältnis und einem zunehmenden Gehalt an Graphit festgestellt, der dem Gehalt an organischer Substanz entstammt. Diese Isotopenfraktionierung datiert ungefä hr 3:10⁹ M.J. her.