Light Sulfur Research Articles

The Cambrian microfossil Qingjiangonema reveals the co-evolution of sulfate-reducing bacteria and the oxygenation of Earth’s surface

Sulfate reduction is an essential metabolism that maintains biogeochemical cycles in marine and terrestrial ecosystems. Sulfate reducers are exclusively prokaryotic, phylogenetically diverse, and may have evolved early in Earth’s history. However, their origin is elusive and unequivocal fossils are lacking. Here we report a new microfossil, Qingjiangonema cambria, from ∼518-million-year-old black shales that yield the Qingjiang biota. Qingjiangonema is a long filamentous form comprising hundreds of cells filled by equimorphic and equidimensional pyrite microcrystals with a light sulfur isotope composition. Multiple lines of evidence indicate Qingjiangonema was a sulfate-reducing bacterium that exhibits similar patterns of cell organization to filamentous forms within the phylum Desulfobacterota, including the sulfate-reducing Desulfonema and sulfide-oxidizing cable bacteria. Phylogenomic analyses confirm separate, independent origins of multicellularity in Desulfonema and in cable bacteria. Molecular clock analyses infer that the Desulfobacterota, which encompass a majority of sulfate-reducing taxa, diverged ∼2.41 billion years ago during the Paleoproterozoic Great Oxygenation Event, while cable bacteria diverged ∼0.56 billion years ago during or immediately after the Neoproterozoic Oxygenation Event. Taken together, we interpret Qingjiangonema as a multicellular sulfate-reducing microfossil and propose that cable bacteria evolved from a multicellular filamentous sulfate-reducing ancestor. We infer that the diversification of the Desulfobacterota and the origin of cable bacteria may have been responses to oxygenation events in Earth’s history.

Geochemical transformations of sulfur and their role in the formation of different types and subtypes of saline lakes in Southeastern Transbaikalia

This study focused on the chemistry and isotopes of sulfur in lakes. The bottom sediments and water columns of lakes were found to contain reduced forms of sulfur, including hydrogen sulfide ions, elemental sulfur, and thiosulfate ions, along with sulfate ions. It was determined that elemental sulfur in lakes is present mainly in the form of suspensions and colloids, and the proportion of elemental sulfur in polysulfides increases with increasing water pH. It was shown that sulfate reduction results in the greatest isotope fractionation, with a light sulfur isotope accumulating in hydrogen sulfide ions and a heavy sulfur isotope accumulating in sulfate ions. It was confirmed that the abiotic reaction of hydrogen sulfide with oxygen yields a mixture of products that are depleted in 34S and enriched in 34S in hydrogen sulfide. In contrast, the microbial oxidation of HS− → S0 yields zerovalent sulfur, which is 2–4‰ heavier than the initial product. It was shown that the loss of sulfate ions due to bacterial reduction is most significant in subtype-I and subtype-III chloride and soda lakes. In contrast, in subtype-II sulfate and soda lakes, an increase in sulfate ions was noted due to the oxidation of hydrogen sulfides in water-bearing rocks and bacterial hydrogen sulfide. This finding indicated that in addition to evaporation, the formation of a particular type and subtype of saline lake involves the processes of aluminosilicate hydrolysis, sulfate reduction and hydrogen sulfide oxidation.

Low temperature alteration of massive sulphides below the weathering front

Alteration of magmatic sulphides within the regolith, or soil profile, is well documented, but alteration at depth, where meteoric fluids may infiltrate fresh rock adjacent to faults, is less studied and poorly understood. Yet such alteration may affect the mineralogy of the magmatic sulphides, and the characteristics of this alteration provide insights into the distribution and timescales of fluid flow and redox processes within the upper crust.Pentlandite [(Fe,Ni)9S8] is a Ni-rich sulphide mineral, found in magmatic sulphide assemblages with chalcopyrite (CuFeS2) and pyrrhotite (Fe1−xS). Pentlandite associated with massive sulphides from apparently fresh rock at the Mawson Deposit, Western Australia, shows in-situ partial replacement by violarite (nominally FeNi2S4), whereas pentlandite associated with adjacent disseminated sulphides is unaltered. Petrographic, geochemical, and in-situ sulphur isotope analysis reveals that violarite has variable Fe:Ni ratios. Constant volume and constant sulphur mass balance calculations indicate an overall loss of Ni and other metal cations during violarite formation. In addition, newly formed violarite has a 34S-depleted isotopic composition compared to precursor pentlandite. Altered pentlandite (δ34S = 1.02 ‰) is isotopically fractionated relative to co-existing pyrrhotite (3.44 ‰) and chalcopyrite (3.15 ‰), in contrast to the unfractionated sulphur isotope ratios expected for co-crystallising magmatic sulphides. These features are interpreted as a consequence of electrochemical alteration within electrically connected massive sulphides and addition of isotopically light sulphur derived by bacterial sulphate reduction. Based on previous evidence of deep-seated fluid flow along long-lived regional faults, the alteration is plausibly associated with Cenozoic neotectonic deformation and short-lived pulses of fluid flow with durations of hundreds to thousands of years. Similar petrographic evidence of deep alteration in apparently fresh sulphides from samples across the regional study area indicate this could be an under-reported feature in magmatic sulphides globally.

Chalcogen Bonding Catalysis: Tellurium, the Last Frontier?

: Chalcogen bonding (ChB) is the non-covalent interaction occurring between chalcogen atoms as Lewis acid sites and atoms or groups of atoms able to behave as Lewis bases through their lone pair or p electrons. Analogously to its sister halogen bonding, the high directionality of this interaction was implemented for the precise structural organization in the solid state and in solution. Regarding catalysis, ChB is now accepted as a new mode of activation as demonstrated by the increased number of examples in the last five years. In the family of ChB catalysts, those based on tellurium rapidly appeared to overcome their lighter sulfur and selenium counterparts. In this review, we highlight the Lewis acid properties of tellurium-based derivatives in solution and summarize the start-of-the-art of their applications in catalysis.

Selenium enrichment in the Dingtoushan carbonate-hosted epigenetic Pb-Zn deposit in the western Yangtze Block, SW China

Selenium (Se) is a typical dispersed element (crust Clarke value only 0.05 × 10-6) and is mainly enriched in black shales (>20 × 10-6). Selenium can also be associated with Pb-Zn and U deposits. In carbonate-hosted epigenetic hydrothermal Pb-Zn deposits, the selenium contents in sulfides are commonly < 50 × 10-6, and the selenium is mainly enriched in galena, whereas the selenium contents in sphalerite are often < 10 × 10-6. There are few studies on Se-rich carbonate-hosted epigenetic hydrothermal Pb-Zn deposits, and the origin of such deposits needs more in-depth exploration. In this study, we selected the Dingtoushan Se-rich Pb-Zn deposit in the western Yangtze Block, SW China, and utilized in-situ trace elements and S-Pb isotopes of Se-rich sphalerite to investigate this issue. There are two textures of sphalerite formed in the Dingtoushan deposit, of which subhedral sphalerite (Sp-I) precipitated during the early stage, whereas euhedral sphalerite (Sp-II) generated during the late stage. The results of trace elements show that the Dingtoushan deposit is significantly enriched in selenium (>22 × 10-6) compared with other carbonate-hosted Pb-Zn deposits (<22 × 10-6, generally < 10 × 10-6) in the Sichuan-Yunnan-Guizhou (SYG) Pb-Zn metallogenic province. In detail, a positive correlation between Se, Cd, In and Cu contents and sulfur isotopes of sphalerite is identified at the deposit scale, but no relationship is observed at the grain scale. In addition, the late stage Sp-II with δ34S values of −7‰ to −3‰ is rich in selenium and other trace elements, whereas the early stage Sp-I with isotopically light sulfur (δ34S = -29 ‰ to −8‰) is depleted of them. This indicates that in the early stage, insufficient addition of hydrothermal fluid resulted in relatively low temperature, and sulfur formed by bacterial sulfate reduction (BSR) was mainly involved in mineralization. With the addition of a large amount of hydrothermal fluid, thermochemical sulfate reduction (TSR) was induced, which leads to the formation of sphalerite in the late stage with relatively high δ34S values. Furthermore, the Pb isotopes reveal that the ore-forming metals were likely derived from the Cambrian black shales. Hence, we infer that fluid mixing is the main sulfide precipitation mechanism and may cause the positive correlation of selenium concentrations and δ34S values. On the other hand, at the grain scale of sphalerite, the variation of selenium contents shows a negative correlation with temperature, suggesting that temperature may play a critical role in selenium enrichment in sphalerite. This study highlights that selenium enrichment in sphalerite is jointly controlled by fluid mixing and temperature. The degree of fluid mixing dominated the selenium concentration in hydrothermal fluid, but high temperature may not be conducive to selenium incorporation into sphalerite. Our new results indicate that sphalerite in the carbonate-hosted epigenetic hydrothermal deposits is also a major host for selenium and such type deposits may have a great economic potential for selenium resource.

Trace element release from Bowland Shale into spring water in Lancashire

Abstract A sulfurous spring emerges at an outcrop of Bowland Shale Formation on Crimpton Brook, Lancashire. The spring is marked by the precipitation of white and yellow jarosite. Comparable light sulfur isotope compositions suggest that the jarosite was derived from surface oxidation of pyritic shale. The shale contains anomalous concentrations of selenium and other trace elements, in common with other exposures of the Bowland Shale Formation in the north of England. The selenium is resident in the pyrite, and was released during oxidation and incorporated into the jarosite in Crimpton Brook. The small scale of the water flow at the site and the remote situation pose no environmental problem, but the data exemplify the potential danger of pyrite weathering into groundwater on a larger scale.

S, Pb, and Fe isotope compositions of sulfides in middle and southern Okinawa Trough: Implying the complicated hydrothermal systems in back-arc spreading centers

Sulfur, lead, and iron isotopic systematics of sulfides from the Iheya North hydrothermal field in middle Okinawa Trough and the Yonaguni Knoll IV hydrothermal field in southern Okinawa Trough were investigated to understand the origin of ore-forming material and isotope fractionation during sulfide precipitation in back-arc spreading centers. The δ34S values (from 8.60‰ to 9.68‰) of sulfide minerals in Iheya North field suggest sulfur was derived from the leaching of basement rocks and the reduction of seawater sulfate. But an additional light sulfur source from the dissolution of biogenic sulfides in sediments is indispensable for the observed low δ34S values (between 4.78‰ and 4.97‰) of Yonaguni Knoll IV sulfides. Lead isotope compositions of all sulfides vary in a relatively wide range (206Pb/204Pb = 18.432 to 18.563, 207Pb/204Pb = 15.579 to 15.671, and 208Pb/204Pb = 38.539 to 38.979, respectively) which involves the mixing of mantle-derived and sediment-derived lead in varying proportions. Unusually high radiogenic lead isotope ratios of Yonaguni Knoll IV sulfides (207Pb/204Pb = 15.628 to 15.671, and 208Pb/204Pb = 38.854 to 38.979) imply the presence of old crustal fragments beneath southern OT. The hydrothermal fluids in OT are characterized by extremely low calculated δ56Fe values (−1.00‰ to −1.32‰) which is attributed to reducing sediments. The paired Fe-isotope compositions of pyrite and chalcopyrite revealed significantly different iron isotope compositions of hydrothermal fluids in study areas and extremely complicated ore-forming processes. Rapid precipitation of pyrite from FeS precursors accompanying iron isotopic disequilibrium moves from FeS-fluid equilibrium to pyrite-fluid equilibrium during pyrite recrystallization. The combination of sulfur, lead, and iron isotopic data suggests that hydrothermal systems in back-arc spreading centers related to plate subduction are generally affected by mantle, overlying sediments as well as potential old continental crust fragments, which results in various hydrothermal fluids and complicated mineralization processes.

A Role for Crustal Assimilation in the Formation of Copper-Rich Reservoirs at the Base of Continental Arcs

Abstract Understanding the behavior of chalcophile elements during the evolution of arc magmas is critical to refining models for the formation and distribution of porphyry copper deposits used in mineral exploration. Because magmas in continental arcs undergo copper depletion during their early differentiation, a widely held hypothesis posits that the removed copper is locked at the base of the crust in copper-rich cumulates that form due to early sulfide saturation. Testing this hypothesis requires direct evidence for such copper-rich reservoirs and a comprehensive understanding of the mechanisms driving sulfide saturation. Interaction between oxidized magmas and reducing crustal material in island arcs has been shown to be an efficient process causing sulfide saturation. However, the extent to which crustal assimilation impacts the flux of chalcophile elements during magmatism in thick continental arcs remains to be established. Here, we provide a deep perspective into these problems by studying a suite of subarc cumulate rocks from the Acadian orogen, New England (USA). These cumulates record the imprint of subduction zone magmatism and represent the residues left behind during the genesis of intermediate to evolved Acadian magmas (ca. 410 Ma). We find that the most primitive Acadian cumulates are enriched in copper (up to ~730 µg g–1) hosted by sulfide phases, providing direct evidence for the formation of lower crustal copper-rich reservoirs. The Acadian cumulates reveal a wide range of δ34S values, from –4.9‰ in the ultramafic rocks to 8‰ in the most evolved mafic rocks. The negative δ34S values observed in the most primitive and copper-rich cumulates (avg –3‰) reflect the assimilation of isotopically light sulfur from surrounding sulfidic and graphite-bearing metasedimentary rocks (δ34S of –19 to –12‰), whereas the more evolved cumulates with positive δ34S signatures may have formed from different magma batches that experienced less sediment assimilation. The assimilation of these reducing metasedimentary rocks caused a critical drop in oxygen fugacity (~DFMQ –2.5 to –1.9; FMQ = fayalite-quartz-magnetite buffer) in the evolving magmas, ultimately leading to extensive sulfide saturation and the consequent formation of copper-rich subarc cumulates. Assimilation-driven sulfide saturation may be a common process at the root of thickened arc crusts that triggers the formation of lower crustal copper-rich reservoirs, which play a pivotal role in the fate of copper during arc magmatism. Thus, deeply buried reducing metasedimentary crustal material at the base of continental arcs can act as a barrier to the magmatic flux of chalcophile elements and may play a crucial role in the genesis and distribution of porphyry copper deposits.

Минералого-геохимические особенности руд золото-кварц-сульфидного проявления Верхнелекелецкое на Полярном Урале (кряж Манитанырд)

The Verkhnelekeletskoye gold occurrence of gold-quartz-sulfide type is localized in the marginal part of the gabbro-dolerite dike of the Lower Ordovician Lekvozhsky complex. The ore zone is composed of pyrite-sericite-quartz metasomatites with quartz-vein and vein-disseminated mineralization. The gold-sulfide ores are represented by pyrite with a subordinate amount of arsenopyrite and, to a lesser extent, sphalerite. Galena and chalcopyrite are present as microinclusions in pyrite and arsenopyrite. Characteristic impurity elements in sulfides are arsenic and antimony, nickel is also found. We identified rare minerals — tetrahedrite, lead sulphosalts, ulmannite, gersdorfite. The main form of gold occurrence is submicron and micron segregations in pyrite and arsenopyrite. Impurity elements in gold are silver, mercury is rare. Gold is moderately high-grade and medium-grade, in the presence of mercury — low-grade. In terms of the mineral composition of ores, including rare minerals, the Verkhnelekeletskoye ore occurrence is very similar to the Verkhneniyayuskoye 2 deposit. The sulfides of the Verkhnelekeletskoye occurrence are characterized by a light sulfur isotopic composition (34S = –0.2 ÷ –3.5 ‰), close to the meteorite standard, which indicates the participation of deep sulphur sources in ore formation and its association with magmatic processes.

Radiation damage and defect dynamics in 2D WS2: a low-voltage scanning transmission electron microscopy study

Modern low-voltage scanning transmission electron microscopes (STEMs) have been invaluable for the atomic scale characterization of two-dimensional (2D) materials. Nevertheless, the observation of intrinsic structures of semiconducting and insulating 2D materials with 60 kV-microscopes has remained problematic due to electron radiation damage. In recent years, ultralow-voltage microscopes have been developed with the prospects of minimizing radiation damage of such 2D materials, however, to date only ultralow-voltage TEM investigations of semiconducting and insulating 2D materials have been reported, but similar results using STEM, despite being more widely adopted, are still missing. Here we report a quantitative analysis of radiation damage and beam-induced defect dynamics in semiconducting 2D WS2 during 30 kV and 60 kV-STEM imaging, particularly by recording atomic resolution electrostatic potential movies using integrated differential phase contrast to visualize both the light sulfur and heavy tungsten atoms. Our results demonstrate that electron radiation damage of 2D WS2 aggravates by a factor of two when halving the electron beam energy from 60 keV to 30 keV, from which we conclude electronic excitation and ionization to be the dominant mechanism inducing defects and damage during low-voltage STEM imaging of semiconducting 2D materials.

Mineralogical and geochemical evidence for biogenic uranium mineralization in northern Songliao Basin, NE China

The sandstone-hosted uranium mineralization areas in the Sanzhao Sag of the northern Songliao Basin have been newly identified. The target stratum is the Upper Cretaceous Sifangtai Formation and the uranium mineralization mainly occurs in the bottom of Sifangtai Formation, corresponding to channel sand bodies in meandering river system, characterized by medium to fine-grained sandstone. This study proposes the uranium metallogenic model through petrographic observation, whole rock geochemistry, mineralogical study of uranium occurrence form (SEM), organic matter rock–eval pyrolysis analysis (REP) and in-situ sulfur isotope determination of different generations of pyrite by LA-MC-ICP-MS. Compared with the sandstones collected in barren reduction and oxidization zones, the mineralized sandstones show obvious increase in the contents of TOC, total sulfur, Y and U. Petrographic observations indicate that organic matters are mainly inherited from land plants. REP data display that the organic matter (OM) disseminated in the sandstone has very low hydrogen index (HI) from around 0 to 21 mg HC/g TOC and varied oxygen index (OI) from 44 to 115 mg CO2/g TOC, corresponding to Type Ⅳ kerogen (degraded kerogen). There are two types of coffinite with different grain size, micro-particles (μm-sized) and large aggregates (generally up to 100 μm) respectively. The coffinite micro spherules exhibit short rod-like or worm-like morphology occurring in clay matrix and cell cavities in degradofusinite or around subidiomorphic-idiomorphic pyrite. The coarse-grained coffinite contains other mineral facies (e.g. pyrite, quartz) and some of large coffinite aggregates display thrombolite-type microbial structures. The irregular pyrite relict particles in coarse-grained colloidal coffinite have light sulfur isotope compositions characterized by δ34S values from –39.96‰ to –49.89‰. The δ34S values of colloidal pyrite in replacement of OM or of the sub-idiomorphic FeS2 cement filling in the cavities of OM range from –52.77‰ to –13.88‰. Some of sub-idiomorphic pyrite cement and idiomorphic crystal have the heavier signature from – 27.06‰ to + 14.23‰. The light sulfur isotope signature suggests that the sulfur originates from bacterial sulfate reduction (BSR). The OM replacement by pyrite and the highest OI values recorded by REP in uranium mineralized samples are lines of evidence of biodegradation. Bacteria use the organic matter as food source and produce isotopically light reduced sulfur species. Oxygenated uranium-bearing waters infiltrated through the denudated windows at Daqing placanticline into the porous reduced sandstones deposited in the Sanzhao Sag. Uranium was indirectly reduced by BSR-derived iron disulfides or directly reduced by sulfate-reducing bacteria.

Genesis of interlayer oxidation zone-type uranium deposit in the channel conglomerates, Beisantai area, Junggar Basin: An insight into uranium mineralization

The Beisantai deposit is a newly discovered typical interlayer oxidation zone-type uranium deposit mainly hosted in distributary channel conglomerates of the Neogene Shawan Formation in East Junggar Basin, northwest China. This study aims to reveal the genetic process of the Beisantai deposit and constrain the mineralization characteristics conducted through petrographic observation, Rock-Eval pyrolysis, high-resolution microscopic mineralogical observation based on BSE, C-O isotopes of calcite cement, and in-situ measurements on pyrite of trace elements and S isotope. There are two types of calcite cements, including diagenetic microcrystalline calcite and epigenetic sparry calcite, dominantly occurring in the redox transition zone and the oxidation zone, respectively. The broad heterogeneity of δ13C values, ranging from −29.2‰ to −6.52‰, indicates the mixed sources of carbon. Given the poor organic content in sediments (0.05% in sandstone and from 0.11% to 0.26% in mudstones), the large amount of organic carbon in the transition zone conglomerates, revealed by the super low δ13C values, is attributed to extrinsic hydrocarbons. Besides, the widespread dissolution of microcrystalline calcite also indicates a weakly acidic environment in the formation. The heavy carbon isotopes are sourced from surface freshwater and the dissolved CO2, which causes the epigenetic metasomatism of early-stage calcite. Thus, the infiltrated groundwater is characterized as alkaline with carbonate dissolved. Pyrites are highly enriched in ore-bearing rocks, with complex morphologies. The extremely negative sulfur isotopic signatures (δ34S values from −48.38‰ to −35.65‰) indicate that these pyrites precipitate through bacterial sulfate reduction (BSR). Combined with the morphology features, distribution patterns, and the decrease in light sulfur isotope and several trace elements, including As, Se, Ni, and Co between individual pyrites and ore-related pyrites, a successive process of pyritization can be revealed. Ore-related pyrites are formed at the late stage. The pervasive coffinite replacement of pyrite suggests that uranium mineralization should occur after the cessation of pyritization, resulting from the consumption of organic matter. Distinctive bio-oxidation features of pyrite can also be observed, characterized as deep and oriented holes. Thus the role of microbes such as Acidithiobacillus thiooxidans is non-negligible, which enhances the dissolution rate of pyrite and the reduction of U(Ⅵ). Overall, as the major reducing material during the ore stage, the large amount of pyrite has played the predominant role in the precipitation of coffinite, with the catalysis and acceleration of microbes.

Sulfur isotopic signature of Earth established by planetesimal volatile evaporation

How and when Earth’s volatile content was established is controversial with several mechanisms postulated, including planetesimal evaporation, core formation and the late delivery of undifferentiated chondrite-like materials. The isotopes of volatile elements such as sulfur can be fractionated during planetary accretion and differentiation and thus are potential tracers of these processes. Using first-principles calculations, we examine sulfur isotope fractionation during core formation and planetesimal evaporation. We find no measurable sulfur isotope fractionation between silicate and metallic melts at core-forming conditions, indicating that the observed light sulfur isotope composition of the bulk silicate Earth relative to chondrites cannot be explained by metal–silicate fractionation. Our thermodynamic calculations show that sulfur evaporates mostly as H2S during planetesimal evaporation when nebular H2 is present. The observed bulk Earth sulfur isotope signature and abundance can be reproduced by evaporative loss of about 90% sulfur mainly as H2S from molten planetesimals before nebular H2 is dissipated. The heavy sulfur isotope composition of the Moon relative to the Earth is consistent with evaporative sulfur loss under 94–98% saturation condition during the Moon-forming giant impact. In summary, volatile evaporation from molten planetesimals before Earth’s formation probably played a key role in establishing Earth’s volatile element content. Earth’s volatile element content was established largely by volatile evaporation from molten planetesimals before Earth’s formation, according to first-principles calculations and examination of sulfur isotope fractionation.

Evaluation of the Different Compatibility Indices to Model and Predict Oil Colloidal Stability and Its Relation to Crude Oil Desalting

Thirty crude oils, belonging to light, medium, heavy, and extra heavy, light sulfur, and high sulfur have been characterized and compatibility indices defined. Nine crude oil compatibility indices have been employed to evaluate the compatibility of crude blends from the thirty individual crude oils. Intercriteria analysis revealed the relations between the different compatibility indices, and the different petroleum properties. Tetra-plot was employed to model crude blend compatibility. The ratio of solubility blending number to insolubility number was found to best describe the desalting efficiency, and therefore could be considered as the compatible index that best models the crude oil blend compatibility. Density of crude oil and the n-heptane dilution test seem to be sufficient to model, and predict the compatibility of crude blends.

Sulfur isotope composition during heterogeneous oxidation of SO2 on mineral dust: The effect of temperature, relative humidity, and light intensity

Sulfate as the major constituent of atmospheric aerosol plays a key role in aerosol formation and aging processes. However, little attention has been paid to the impacts of mineral dust on the oxidation of SO2, along with the effects of temperature, moisture, and light intensity. In this study, the influences of these parameters on the formation of sulfate and sulfur isotope composition were investigated in detail. Temperature promoted the heterogeneous oxidation of SO2 on the surface of hematite (α-Fe2O3), while excessive temperature was unfavorable for sulfate formation. Besides, the effect of temperature on sulfur isotope fractionation was not apparent. In addition, relative humidity (RH, < 40%) boosted the oxidation of SO2 with the concurrent enrichment of heavy isotope. Meanwhile, light with high intensity inhibited the formation of sulfate due to the photo-induced reductive dissolution of hematite, and had little effects on the sulfur isotope compositions. Furthermore, compared with other minerals, α-Fe2O3 exhibited greater uptake capacity of SO2, favoring the enrichment of light sulfur isotopes, whereas the enrichment of heavy sulfur isotopes existed on the surface of MgO. This study contributes to the investigation of the heterogeneous oxidation of SO2 and provides useful parameters for atmospheric modeling studies.

Trace elemental and sulfur-lead isotopic variations in metamorphosed volcanogenic massive sulfide (VMS) mineralization systems: An example from the Keketale Pb-Zn(-Ag) deposit, NW China

The effects of post-VMS (volcanogenic massive sulfide) deformation/metamorphism on sulfide trace element and sulfur-lead isotopic compositions remain unclear. The greenschist to lower amphibolite facies metamorphosed Keketale VMS Pb-Zn(-Ag) deposit, located in the Devonian Maizi volcanic-sedimentary basin in the Chinese Altay, NW China, provides an opportunity to resolve the abovementioned issue. Two mineralization stages are recognized at Keketale, including (1) primary banded, massive and disseminated ores derived from sea-floor hydrothermal mineralization and (2) ore remobilization, as represented by intensively-deformed ores and quartz-polymetallic sulfide ore veins that crosscut the primary ores. Sulfide trace elements data suggest that Stage II pyrite and pyrrhotite have higher contents of Cu, Zn, Ag, Sb and Pb, whereas contents of these elements are higher in Stage I sphalerite and galena than their Stage II counterparts. Such elemental remobilization was probably caused by the rapid intragrain diffusion and subsequent fluid-mediated liberation with trace elements re-precipitated as particles within the same grain and nearby minerals, respectively. The δ34SCDT values in both stages show a trimodal distribution (−25.9 to −22.7‰, −17.0 to −10.6‰ and 0.6 to 2.1‰). Sulfide mineral pairs formed during primary VMS mineralization are not in sulfur isotopic equilibrium, and only localized re-equilibration occurs during deformation and metamorphism. In addition, the lead isotopic values of galena from remobilized sulfide veins overlap with those of the Stage I galena and pyrite. These data indicate that regional deformation and metamorphism of the Keketale deposit can be approximated as a closed system in terms of sulfur-lead isotopes. Whilst the presence of the anomalously low δ34S values (minimum −25.9‰) and the distinct lead isotopic ratios of sulfides from the calcite-quartz veins argue for that in the late part of the metamorphic event, some exotic lead and light sulfur were sourced from outside the ore field. In situ δ34S values of Stage I sulfides vary widely (−17.0 to +2.1‰), suggesting that the sulfur was originated from bacterial sulfate reduction (BSR) of marine sulfates with probably some magmatic input. Lead isotopes of the sulfides and mineralized meta-sedimentary-volcanic rocks display a linear distribution between the mantle and upper crust line in the 206Pb/204Pb vs. 207Pb/204Pb diagram. The lead source may be derived from both felsic volcanic rocks and mafic igneous rocks (and/or magmatic volatiles), and the sulfur-lead isotopes may result from a shallow-level seawater circulating process. An additional group of lead isotopic compositions of the meta-volcanic rocks show elevated present-day 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values, probably due to decay of Th and U carried by deeply-penetrative circulation (~13 km) of CO2-F-Cl-rich hydrothermal (metamorphic) fluids. Both syn-VMS shallow (seawater) and post-VMS deep (metamorphic fluids) circulation processes are critical for the metal concentration at Keketale.

The origin of pyrite mineralization: Implications for Late Cambrian geology of the Holy Cross Mountains (south-central Poland)

This paper presents results of a petrographic, mineralogical and geochemical study of ore, gangue and rock-forming minerals that occur within the Upper Cambrian (Furongian)-age siliciclastic rocks of the Wiśniówka massif (western part of the Main Range, Holy Cross Mountains, south-central Poland). This area is characterized by the presence of ubiquitous pyrite that makes up two stratiform mineralization zones assigned to the early and middle Late Cambrian, giving rise to acid mine drainage. The oldest zone comprises additionally sedimentary breccias with intraclast-supported pyrite cement. The predominant microscopic (colloform) and partly framboidal pyrite typically shows high concentrations of As (up to 8.23 wt%) and a distinct enrichment in the light sulfur isotope (δ34S from −41.4 to −23.6‰). The occurrences of large amounts of As-rich pyrite showing strongly negative δ34S values are rather uncommon in Paleozoic sedimentary formations worldwide that exhibit distinctly smaller amounts of As and mostly enrichments in heavier sulfur isotope (δ34S up to 63‰). Another specific feature of the Wiśniówka rock series is the presence of REE-bearing aluminophosphate and phosphate minerals that occur primarily in clayey-silty shales and bentonites. Based on the results obtained, a sequence of hydrothermal index minerals was discriminated, including pyrite (whose grains are usually made of alternating arsenic-rich and arsenic-poor bands), as well as paragenetic assemblages of dickite, nacrite, xenotime and the crandallite series of aluminum-phosphate-sulfate minerals. Both mineral composition and specific microtextures are indicative of multistage hydrothermal activity that took place in the Wiśniówka depositional basin during the Late Cambrian time. This is in distinct contrast to the remaining part of the Main Range, which is devoid of the hydrothermal pyrite imprint. Moreover, the results of this study give insight into the complex sedimentary and early diagenetic history of the southwestern passive margin of the Baltica craton. This currently makes up a part of the Łysogóry Block (Terrane) that borders on the Trans-European Suture Zone separating the Precambrian East-European Craton from the Paleozoic Platform of Central Europe. This study is important because we still lack the full knowledge about the hydrothermal processes that took place in Early Paleozoic depositional basins.

In situ sulfur isotope analysis by laser ablation MC-ICPMS and a case study of the Erlihe Zn-Pb ore deposit, Qinling orogenic belt, Central China

Sulfur isotopic composition is useful for tracing sources of ore-forming materials. In situ sulfur isotope analysis by laser ablation coupled with multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) has an advantage over traditional bulk analysis in tracing sources of sulfur in an ore deposit that has complex mineral types and multiple ore-forming processes. However, in using this method, matrix effects exist widely for sulfides from ore deposits. In this work, matrix effects of different sulfides were examined by matrix-unmatched tests, in which the δ34S values of different types of sulfides were calibrated against a laboratory pyrite standard. The results show that the δ34S values of pyrrhotite, chalcopyrite, molybdenite, sphalerite, and arsenopyrite are in agreement with the reference values, suggesting that the matrix effect was negligible. However, a significant matrix effect occurred in the analyses of Ag2S and galena, leading to significant deviations in δ34S values of up to 1.2‰ and 3.2‰, respectively. The matrix effect occurred not only during the laser ablation stage but also during the transition of ions into the mass spectrometer, resulting in significant space charge effects caused by heavy-mass elements. Thus, pyrite can be used as an external bracketing standard for sulfides that do not have a heavy-mass matrix.Based on our matrix-effect study, the following available external standards were selected for the in situ sulfur isotope analysis of complex-type minerals from the Erlihe Zn-Pb deposit. The coarse-grained sphalerite grains (Sph1) and euhedral to subhedral pyrite grains (Py1) from massive ores have δ34S values ranging from 9.2‰ to 18.1‰. Such heavy sulfur isotopic compositions indicate the derivation of sulfur from the deposits of seawater sulfate, related to a thermochemical reducing process. Fine-grained sphalerite (Sph2) and pyrite (Py2) from vein and disseminated ores coexist with pyrrhotite and chalcopyrite, and have relatively light sulfur isotopic compositions, with δ34S values of about 7‰. The slightly positive δ34S values are similar to those of sulfides from sulfide-rich quartz veins, which contain δ34S values of about 4‰, and granodiorite rocks, with δ34S values of about 6‰. Based on previous studies, the light sulfur of the late-stage sulfides may have resulted from a metamorphic or magmatic hydrothermal event during the Indosinian orogeny. In situ sulfur analysis by LA-MC-ICPMS provides new evidence for sources of sulfur from each stage of mineralization in the Erlihe deposit, suggesting that this is a promising method for studying complex ore deposits.

Geochemical studies of thermal waters from Kanlaon Volcano, Negros Island, Philippines

Kanlaon is a stratovolcano situated in central Negros Island, Philippines. It has a record of 30 eruptions since 1866 ranging from phreatic to phreatomagmatic (VEI = 1–2) events. Geothermal manifestations in Kanlaon Volcano are evidenced by the presence of hot springs, boiling mud pools, and warm rivers with temperatures up to 95 °C. It has developed a significant hydrothermal system within the volcanic edifice. Through time, it evolved into two distinct hydrothermal systems independent of each other. A mature hydrothermal system, represented by Pataan thermal area is characterized by neutral Na + K chloride (bicarbonate) fluids and an immature system, represented by Hagdan spring is characterized by the presence of acid-sulfate waters.Representative water samples were collected between 2014 and 2017 to further characterize the two systems. Chemical and sulfur isotopic analyses were performed on thermal waters to classify the samples that are linked to the co-existence of these two hydrothermal systems. Results show that thermal spring's pH ranges between 2.5 and 8.1 and conductivity ranges between 88 μS/cm to 3930 μS/cm. Based on their Cl-SO4-HCO3 relative abundances, the thermal waters are classified as acid sulfate, acid-sulfate chloride, neutral chloride and neutral bicarbonate waters.Temperatures of deep-water hydrothermal reservoirs were calculated using fluid-mineral geothermometers and correlated with available borehole temperatures. The Na-K-Mg geothermometer was used to evaluate equilibrium between water and reservoir rocks. Results show that the samples are not in equilibrium with the minerals in the reservoir. Temperature of equilibrium for the mature hydrothermal system was extrapolated to 270 °C based on available borehole temperatures. The linear trend towards the equilibrium temperature in the Na-K-Mg geothermometer can be explained by either groundwater/meteoric dilution. This is consistent with the light sulfur isotopic signatures between δ34S = −3.4‰ and + 1.2‰ of the mature hydrothermal system (Mambucal), which imply that the origin of sulfates is linked to surficial oxidation of H2S or dilution and mixing of meteoric water. On the other hand, immature hydrothermal system (Hagdan) shows a significantly higher sulfur isotopic composition (δ34S = +8.2‰), which could either result from the disproportionation of magmatic SO2 or from the hydrolysis of elemental sulfur at high temperature between 100 and 350 °C.

The source of sulfur in sulfide deposits in the Siberian Platform traps (from isotope data)

The source of sulfur in giant Norilsk-type sulfide deposits is discussed. A review of the state of the problem and a critical analysis of existing hypotheses are made. The distribution of δ34S in sulfides of ore occurrences and small and large deposits and in normal sedimentary, metamorphogenic, and hypogene sulfates is considered. A large number of new δ34S data for sulfides and sulfates in various deposits, volcanic and terrigenous rocks, coals, graphites, and metasomatites are presented. The main attention is focused on the objects of the Norilsk and Kureika ore districts. The δ34S value varies from -14 to +22.5‰ in sulfides of rocks and ores and from 15.3 to 33‰ in anhydrites. In sulfide-sulfate intergrowths and assemblages, δ34S is within 4.2-14.6‰ in sulfides and within 15.3-21.3‰ in anhydrites. The most isotopically heavy sulfur was found in pyrrhotite veins in basalts (δ34S = 21.6‰), in sulfate veins cutting dolomites (δ34S = 33‰), and in subsidence caldera sulfates in basalts (δ34S = 23.2-25.2‰). Sulfide ores of the Tsentral’naya Shilki intrusion have a heavy sulfur isotope composition (δ34S = +17.7‰ (n = 15)). Thermobarogeochemical studies of anhydrites have revealed inclusions of different types with homogenization temperatures ranging from 685 °C to 80 °C. Metamorphogenic and hypogene anhydrites are associated with a carbonaceous substance, and hypogene anhydrites have inclusions of chloride-containing salt melts. We assume that sulfur in the trap sulfide deposits was introduced with sulfates of sedimentary rocks (δ34S = 22-24‰). No assimilation of sulfates by basaltic melt took place. The sedimentary anhydrites were “steamed” by hydrocarbons, which led to sulfate reduction and δ34S fractionation. As a result, isotopically light sulfur accumulated in sulfides and hydrogen sulfide, isotopically heavy sulfur was removed by aqueous calcium sulfate solution, and “residual” metamorphogenic anhydrite acquired a lighter sulfur isotope composition as compared with the sedimentary one. The wide variations in δ34S in sulfides and sulfates are due to changes in the physicochemical parameters of the ore-forming system (first of all, temperature and Pch4) during the sulfate reduction. The regional hydrocarbon resources were sufficient for large-scale ore formation.