Sulfur Isotopic Composition Of Pyrite Research Articles

Pyrite Characteristics in Lacustrine Shale and Implications for Organic Matter Enrichment and Shale Oil: A Case Study from the Triassic Yanchang Formation in the Ordos Basin, NW China.

Pyrite is widely distributed in lacustrine shales and has become a research focus in unconventional oil and gas exploration. Pyrite morphology is useful for identifying different types of organic matter and assessing shale oil enrichment in organic-rich shale. Abundant pyrite is developed in the source rocks from the Chang 7 Member of the Yanchang Formation in the Ordos Basin, NW China. However, the relationship between different pyrite types and the differential enrichment of shale oil still needs to be clarified. The organic geochemistry, petrology, and isotopic composition of the Chang 7 Member samples were analyzed. The significance of pyrite types and sulfur isotopic compositions as indicators of depositional environments and shale oil enrichment was emphasized. The Chang 7 shales contain three pyrite morphologies, framboidal pyrite (type A), spherulitic pyrite (type B), and euhedral and anhedral pyrite (type C), and their aggregates. The sulfur isotopic compositions of pyrite (δ34Spy) in Chang 7 shales with different pyrite types exhibited regular patterns. The δ34S values of types A, B, and C pyrites were sequentially positive overall (average values are -2.739, 2.201, and 7.487‰ in sequence), indicating that type A pyrite was formed during the syn-sedimentary to early diagenetic stage and types B and C pyrites were formed during the early to middle diagenetic stage. Types A, B, and C pyrites showed sequentially increasing kerogen type index values and kerogen carbon isotope values (mean values of -31.59, -28.70, and -26.45‰, successively), indicating that the horizons where types A, B, and C pyrites developed correspond to types I, II, and III organic matter, respectively. Strong correlations between the pyrite content and oil components reveal that pyrite indicates shale oil enrichment. Moreover, variations in pyrite type significantly influenced the enrichment behavior of shale oil. Types A and B pyrites contributing to reservoir space showed shale oil enrichment. They promoted saturated hydrocarbon enrichment at >15% pyrite content, whereas type C pyrite did not indicate shale oil enrichment. These findings provide new insights into the differential enrichment of organic matter and shale oil and valuable guidance for the large-scale exploration and development of shale oil resources.

The genesis of the Baguamiao orogenic gold deposit linked to multistage ore-forming processes in Triassic tectonic transition of South Qinling, China

The Baguamiao gold deposit represents one of the largest Triassic orogenic gold deposits in the South Qinling metallogenic belt of central China. Here we investigate Ar-Ar dating of sericite and muscovite, fluid inclusion of quartz, the trace element and sulfur isotopic composition of pyrite from different mineralization stage in the Baguamiao gold deposit to gain insights into the ore genesis. The Ar-Ar dating results yield 40Ar/39Ar plateau ages of 217.5 ± 2.1 Ma, 209.2 ± 0.2 Ma and 208.8 ± 0.2 Ma, indicating a two-stage gold mineralization during the tectonic transition from the early metamorphic deformation (at ca. 218 Ma) to the late extension (ca. 209 Ma) in the post-collision environment. Fluid inclusion, trace element and sulfur isotopic analyses reveal that the two stages gold mineralization show different sources. The early mineralization period developed CO2-rich inclusions with medium temperature (317–413 °C) and medium–low salinity (4.62–18.81 wt% NaCleqv.), and is characterized by formation of Py1 and Py2 with depleted Au, Cu, Pb, Zn, Ag, Te and Bi. The sulfur isotope data of Py1 and Py2 are between 3.6 ∼ 10.5 ‰, suggesting that the sulfur source was mainly derived from the surrounding rock (Xinghongpu Group). The late mineralization period developed medium–high temperature (321–453 °C), medium–high salinity (3.3–19.62 wt% NaCleqv.) CO2-rich inclusions and high-temperature and high-salinity daughter crystal inclusions, and is characterized by formation of Py3 and Py4 with obviously higher arsenic and metal contents, such as Au, As, Cu, Pb, Zn, Ag, Cr, Ti, Mn, Sb. The δ34S values of Py3 and Py4 are 8.3 ∼ 18.8 ‰, suggesting a mixed fluid of the Xinghongpu Group and Gudaoling Group with deep magmatic-hydrothermal fluids. We propose that the two periods of gold mineralization in the Baguamiao deposit, in response to the collision assembly of Qinling Orogenic Belt, preserve evidence for diverse metal sources with the early mineralization period sourced from the metamorphism of the upper crust (Xinghongpu Group) in the compressional stage (ca. 218 Ma), and the late mineralization period characterized by the contribution of the Xinghongpu Group, Gudaoling Group and deep magmatic-hydrothermal fluids in a post-collisional extensional setting (ca. 209 Ma). The role of metamorphism and magmatic activity during the Triassic Qinling orogenic processes is considered to be important in the remobilization, transport and enrichment of sulfur, arsenic and gold (and potentially other trace elements) from the earlier formed seafloor exhalation sequence.

Holocene climate regulates multiple sulfur isotope compositions of pyrite in the East China sea via sedimentation rate

Marine authigenic pyrite sulfur isotope (δ34Spyr) is one of the most important proxies for reconstructing remarkable changes of Earth's surface in deep time. Recent observations of unexpectedly large δ34Spyr variations in Quaternary sediments complicate the application of this isotopic proxy, and a mechanistic understanding of such variabilities is needed. In this study, we measured multiple sulfur isotopic compositions of pyrite in well dated sediments spanning the last 7500 years from the East China Sea (ECS) inner shelf to study the mechanism how Holocene climate controls pyrite sulfur isotopic compositions. We found that variabilities of pyrite multiple sulfur isotopes, δ34Spyr and Δ33Spyr (ranging from −38.3‰ to 2.3‰ and from −0.01‰ to 0.21‰, respectively) are significantly correlated with large fluctuations of sedimentation rates (0.03–2.09 cm/yr). In tandem with box model calculations and compiled data, the large δ34Spyr variations up to 40‰ are primarily ascribed to fluctuated anaerobic oxidation of methane coupled sulfate reduction (AOM-SR). Further analyses suggest that heightened distillation of interstitial sulfate, likely propelled by high methane flux coupled with increased sedimentation rates, can produce such negatively correlated δ34Spyr-Δ33Spyr pattern and large variations in δ34Spyr. Possible changes in isotope fractionation factors caused by varied cell-specific sulfate reduction rates result in a maximum δ34Spyr variation of <20‰ and therefore play a minor role in the large variation in δ34Spyr (>40‰). The major and minor isotopic compositions of pyrite align with sulfide produced through pure sulfate reduction, indicating little evidence of additional oxidative sulfur cycling. Sedimentation rates in the ECS are controlled by the East Asian winter monsoon that influences the sediment transport capacity from longshore currents on a multicentennial timescale, and also by the coupled East Asian summer monsoon that affects the sediment availability from the Yangtze River on a millennial timescale. Holocene climate changes alter sediment supplies at the ECS and therefore play a vital role in controlling multiple sulfur isotope compositions of sedimentary pyrite in this region. This study has the potential to provide new insights into δ34S excursions in seawater sulfate that occurred during periods of notable acceleration in sedimentation rates throughout the geological history.

Source of gold and ore-forming processes in the Zarshuran gold deposit, NW Iran: Insights from in situ elemental and sulfur isotopic compositions of pyrite, fluid inclusions, and O−H isotopes

The Zarshuran gold deposit (155 t Au, average grade: 2.63 g/t), NW Iran, provides a new paradigm for understanding the multicomponent ore-forming processes and metallogeny of gold during the evolution of hydrothermal fluids. It is characterized by auriferous quartz veins and gold coexisting with disseminated Fe-As-S sulfide minerals that are hosted in a sequence of Early Cambrian metasedimentary rocks. A complex paragenesis is defined by five sulfide stages: pre-ore stage pyrite (Py0), early ore-stage pyrite (Py1 and Py2), middle ore-stage pyrite (Py3a, Py3b, and Py3c), late ore-stage pyrite (Py4), and post ore-stage pyrite (Py5). Py0 with framboidal texture is characterized by relatively low concentrations of As, Au, Cu, and Sb, and has a broad range of negative δ34S values from −28.2 to −3.7 ‰, indicating microbial reduction of marine sulfate. Py1 and Py2 show porous texture with As-rich bright bands also having high Au (mean: 18.4 ppm). Similarly, narrow ranges in δ34S from −3.6 to +3.2 ‰ likely suggest a deep-seated magmatic sulfur source. In the middle ore-stage, Py3a cryptocrystalline cores have a range of positive δ34S (+5.4 to +26.7 ‰) values and high concentration of As(-Au), whereas later well-crystallized outer rim Py3c is Co(-Ni) rich, has a much more restricted δ34S range (−2.9 to +1.4 ‰), indicating an evolution of fluid composition from As-rich to Co-rich. Most of the gold (mean: 20.2 ppm) and trace elements (Hg, Ag, Sb, and Tl) were deposited in Py4, whose δ34S values (+5.4 to +26.7 ‰) show that ore fluid sulfur in this stage was mainly sourced from a mixture of magmatic sulfur with minor input of reduced sedimentary rocks. Low gold and trace element content with slightly negative δ34S values (–8.5 to –4.2 ‰) of Py5 show that they were likely formed from a metal-poor oxidizing fluid.The mineralizing fluid system can be described as carbonic-aqueous with low to moderate salinity (3.2–15.1 wt% NaCl equiv.) and medium temperature of 285 to 317 °C (early ore-stage) and 255 to 290 °C (late ore-stage), which suggests that phase separation was responsible for gold precipitation during late ore-stage As-Hg-Sb sulfide veins. The δ18Ofluid ranges from −7.8 to +4.2 ‰, and the δD values for fluid inclusions in mineral range from −105 to −65 ‰, suggesting involvement of meteoric water during late- to post ore-stages. Our results indicate that the Zarshuran is a distal disseminated gold deposit formed during southward subduction of the Proto-Tethys oceanic lithosphere beneath the northern margin of Gondwanan terranes through the early Cambrian.

Changing Hydrocarbon-Producing Potential of the Cambrian Niutitang Shale: Insights from Pyrite Morphology and Geochemical Characteristics.

The characteristics of shale gas enrichment conditions at different depositional positions of organic-rich shale in the Niutitang Formation of the Lower Cambrian of the Upper Yangtze in South China vary greatly. The study of pyrite provides a basis for the restoration of the ancient environment and a reference for the prediction of organic-rich shale. In this paper, the organic-rich shale of the Cambrian Niutitang Formation in the Cengong area is analyzed by means of the optical microscope, scanning electron microscope observation, carbon and sulfur analysis, X-ray diffraction whole rock mineral analysis, sulfur isotope test, and image analysis. The morphology and distribution characteristics, genetic mechanism, water column sedimentary environment, and influence of pyrite on the preservation conditions of organic matter are discussed. This study shows that the upper, middle, and lower sections of the Niutitang Formation are rich in pyrite (framboid, euhedral pyrite, subhedral pyrite, etc.). Meanwhile, the sulfur isotopic composition of pyrite (δ34Spy) shows a tight correlation with the framboid size distribution throughout the shale deposits of the Niutang Formation, and the average particle size (9.6 μm; 6.8 μm; 5.3 μm) and distribution range of framboids (2.7-28.1 μm; 2.9-15.8 μm; 1.5-13.7 μm) in the upper, middle, and lower sections show a downward trend. In contrast, the sulfur isotopic composition of pyrite shows a tendency to become heavier from above and below (mean = 0.25‰ to 5.64‰). Together with the covariant mode of pyrite trace elements (such as Mo, U, V, Co, Ni, etc.), the results showed significant differences in the oxygen levels in the water column. They show that the transgression led to long-term anoxic sulfide conditions in the lower water column of the Niutitang Formation. In addition, the main and trace elements in pyrite jointly indicated that there was hydrothermal action at the bottom of the Niutitang Formation, which led to the destruction of the preservation environment of organic matter and the decrease of TOC, which can also explain the reason why the TOC content in the middle part (6.59%) was higher than that in the lower part (4.29%). Finally, the water column became an oxic-dysoxic condition due to the decline of sea level, and the TOC content decreased (1.79%).

Cobalt enrichment mechanism in the Hengdong cobalt deposit, Northeast Hunan Province: Evidence from texture, chemical composition and sulfur isotopic composition of pyrite

Cobalt enrichment mechanism in the Hengdong cobalt deposit, Northeast Hunan Province: Evidence from texture, chemical composition and sulfur isotopic composition of pyrite

Depositional control on the sulfur content and isotope of sedimentary pyrite from the southeast coast of China since MIS5

The content and isotopic composition of pyrite sulfur are significantly affected by local depositional conditions and are sensitive to environmental evolution. Here, we use core QK11, collected from Xiapu Bay, southeast coast of China, to reveal how local depositional conditions constrained pyrite formation and sulfur isotopic composition since MIS5. Our results show that the content of pyrite sulfur is mainly controlled by the TOC content during interglacial intervals and is limited by the supplement of sulfate in glacial intervals. Therefore, the C/S ratios can effectively identify three transgressions since MIS5. The sulfur isotopic composition of pyrite ranges from -36.7 to 18.4‰ in the whole core. The occurrence of isotopically “heavy” pyrite is observed at the depth of 2.2~9.2, 27.2~33.8, and 43.5~62.5 mbsf, which is attributed to the influence of sulfate reservoir effect, depositional event, unsteady diagenetic environment, and other factors, highlighting the influence of local depositional and diagenetic processes on the isotopic composition of pyrite sulfur. Pyrite sulfur in other layers is generally depleted in 34S, as low as -36.7‰, indicating that the early-stage organiclastic sulfate reduction (OSR) plays an important role in sulfur isotopic fractionation. The results also suggest that organic carbon indicators (TOC/TN ratio and δ13C) combined with the C/S ratio can effectively distinguish between freshwater and marine environments, which is of great significance to reveal depositional evolution in deep time.

The Gold–Palladium Ozernoe Occurrence (Polar Urals, Russia): Mineralogy, Conditions of Formation, Sources of Ore Matter and Fluid

We studied the mineralization and sulfur isotopic composition of sulfides of gold–palladium ores in olivine clinopyroxenites from the Dzelyatyshor massif made up of a continuous layered series of rocks: olivine-free clinopyroxenite–olivine clinopyroxenite–wehrlite. The primary igneous layering of rocks, manifested as different quantitative ratios of clinopyroxene and olivine in them, controls the local trends of variability in the chemistry of mineral-forming medium and the concentrations of ore components, including noble metals, and sulfur in each separate layer during its cooling. The replacement of primary rock-forming minerals by secondary minerals, when the temperature decreases, is a characteristic trend for pyroxenites: (a) olivine → serpentine, secondary magnetite, and (b) clinopyroxene → amphibole, secondary magnetite → chlorite. The deposition of native gold in parageneses with PGM and sulfides at the Ozernoe occurrence took place during the replacement of earlier rock-forming minerals by chlorite. This process completed mineral formation at the deposit and took place at temperatures 150–250 °C and at the high activity of S, Te, Sb, and As of fluid. The variability of mineral formation conditions during chloritization is reflected in the change of native-sulfide forms of Pd by arsenide-antimonide forms and the sulfur isotopic composition of sulfides. The Pd content in native gold increases in the series—Au-Ag solid solution (&lt;1.5 wt.% Pd)—Au-Cu intermetallides (to 6 wt.% Pd)—Cu-Au-Pd solid solutions (16.2–16.9 wt.% Pd). The sulfur isotopic composition of pyrite, chalcopyrite, and bornite varies from −2.1 to −2.9‰. It is assumed that a deep-seated magmatic basic melt was the source of fluid, ore components, and sulfur.

Sulfur and Oxygen Isotope Records of Sulfate-Driven Anaerobic Oxidation of Methane in Diffusion-Dominated Marine Sediments

Organoclastic sulfate reduction (OSR) and sulfate-driven anaerobic oxidation of methane (SD-AOM) are the two major microbial pathways for sulfate consumption in marine sulfur cycle. The relative changes of sulfur and oxygen isotope ratios in pore water sulfate are affected by the mode of microbial sulfate reduction and have been applied as an indicator for assessing methane excess environments. However, so far, this isotope proxy fails to distinguish sulfate reduction processes fueled by the oxidation of organic matter or by diffusing methane. To better understand the mechanism of sulfur and oxygen isotope partitioning during OSR and SD-AOM, coupled sulfur and oxygen isotopic compositions of pore water sulfate (δ34SSO4 and δ18OSO4) were investigated from four methane diffusing sites (CL56, CL57, CL59, and CL60) of the South China Sea, supplemented by carbon isotopic composition of dissolved inorganic carbon (DIC) and sulfur isotopic composition of pyrite in bulk sediments. Pore water sulfate and DIC concentrations, as well as calculated net sulfate reduction rates suggest that the sulfate reduction at site CL57 was mainly dominated by OSR, whereas sites CL56, CL59, and CL60 were likely impacted by both OSR and SD-AOM. Furthermore, the trend of cross-plotting δ18OSO4 versus δ34SSO4 values from site CL57 was distinguishable from sites CL56, CL59, and CL60, although all study sites show similar patterns to those derived from methane limited environments. This further indicates the trajectory of sulfur and oxygen isotope partitioning was affected by the mode of sulfate reduction (i.e., OSR vs. SD-AOM). At site CL57, the low net sulfate reduction rate would lead to enhanced oxidation of intermediate sulfur species during OSR, thus leading to a higher slope in the δ18OSO4 vs. δ34SSO4 cross-plot (1.26). In contrast, the higher net sulfate reduction rates at sites CL56, CL59, and CL60 due to the impact from SD-AOM would lead to lower slopes in the δ18OSO4 vs. δ34SSO4 cross-plots (0.78 ± 0.11). This study provides new insights into the sulfur and oxygen isotope systematics during microbial sulfate reduction processes in methane diffusing environments.

Genesis of a Ag-Pb-Zn-F system: Insights from in situ sulfur isotope and trace elements of pyrite, and rare earth elements of fluorite in the Baiyine'lebu deposit, Inner Mongolia, China

The recently discovered Baiyine’lebu Ag-Pb-Zn-F deposit in the southern Great Xing’an Range is hosted by NNE-trending transgressional fractures within Late Permian granodiorite. The fluorite ore veins in the periphery of the mining area show close spatial association with the Ag-Pb-Zn ore bodies. A total of four mineralization stages are recognized based on the cross-cutting relationships and mineral assemblages, among which three types of pyrite are identified, including: i) coarse-grained pyrite (Py1) from stage I quartz-pyrite vein, ii) fine-grained cubic pyrite (Py2) from stage II quartz sulfide-rich vein, showing association with metallic sulfide minerals, and iii) anhedral, irregular pyrite (Py3) disseminated in Ag-bearing sulfide ore vein from stage III. The stage IV is quartz-fluorite-calcite vein with very rare distribution of pyrite. Here we investigate the texture, trace element and sulfur isotopic composition of pyrite and rare earth elements (REEs) of fluorite to gain insights into the genesis and mineralization process of the Baiyine’lebu Ag-Pb-Zn-F deposit. Systematic trace element analyses indicate that the compatible and some other elements (Co, Ni, Cr and As) were incorporated in the pyrite structure via isomorphism in all pyrite types, whereas ore metals such as Cu, Pb, Zn, and Sn entered pyrite as structurally bound elements or micro/nanosized mineral inclusions. The Ag concentrations significantly increase from Py1 to Py3 in the form of invisible nanoparticles of sulfides or micro- to nano-sized mineral inclusions during the decrease of temperature. The narrow range of sulfur isotopic compositions from −0.80 to 3.88 ‰ (average in 1.17‰) indicates a relatively homogeneous sulfur source. In combination with REE patterns of fluorite, we propose that the ore-forming fluids originated mainly from post-magmatic hydrothermal fluid mixed with meteoric water in stage IV. The hydrothermal fluorite veins in the periphery of the Baiyine’lebu deposit could be genetically linked to the Ag-Pb-Zn veins. The purple fluorites with enriched REEs and positive Eu anomaly can be used as a proxy for prospecting Ag-Pb-Zn deposits. In addition, the high Sn content of pyrite in hydrothermal Ag-Pb-Zn deposit indicates the potential of Sn mineralization in the surrounding area or deeper level of the ore field in the South Great Xing’an Range.

Micromorphologies and sulfur isotopic compositions of pyrite in sandstone-hosted uranium deposits: A review and implications for ore genesis

Serving as an adsorbent and a reductant for the dissolved U, pyrite is abundant and commonly found associated with U minerals in sandstone-hosted U deposits. Different nucleation and growth rates of crystals, sulfur sources and precipitation mechanisms (i.e., biogenic or chemical processes) result in a variety of micromorphologies and a wide range of δ34S values of pyrite under low-temperature conditions. A compilation of 793 published δ34S values ranging from -72.0 to +142.8‰ for pyrite mainly consisting of framboidal, euhedral and cement, and a series of evolved morphologies (i.e., early framboidal, followed by euhedral overgrowth, and finally cements) from sandstone-hosted U deposits across the world is presented here. For the different geographical locations of deposits (e.g., China, USA, Australia and Kazakhstan), the different ages of host sandstones (e.g., Triassic, Jurassic, Cretaceous and Paleogene) and the different morphologies of pyrite (e.g., framboidal pyrite and euhedral + cement pyrite), the distribution characteristics of δ34S values are distinct. Four case studies with comprehensive analyses of micromorphologies, in situ sulfur isotopic compositions as well as trace element contents are discussed to illustrate that pyrite has been employed successfully as a redox proxy to evaluate the genetic model of sandstone-hosted U deposits. The data also implies that during the translation of redox interface, the changes of geochemical characteristics well documented in micro-scale pyrite are responsible for U mineralization.

Non-evaporitic gypsum formed in marine sediments due to sulfate-methane transition zone fluctuations and mass transport deposits in the northern South China Sea

Gypsum (CaSO4·2H2O) of non-evaporitic origins has been observed in marine sedimentary environments over the past decade. Our understanding of related diagenetic processes has improved by analyzing the sulfur and oxygen isotopic compositions of gypsum, but, a comprehensive study of the isotopic composition of authigenic gypsum precipitated in methane-rich marine environments has not been performed to elucidate their implications for the sulfur cycle (e.g., sulfide oxidation). Furthermore, there are no studies of authigenic gypsum associated with submarine mass transport deposits, which are common sedimentary features on continental slopes. In this study, we analyzed the sulfur and oxygen isotopic compositions of gypsum and the sulfur isotopic composition of pyrite in drill cores collected from methane hydrate-bearing sites GMGS2–08, GMGS2–16, and GMGS4-W02B in the northern South China Sea to determine the formation mechanisms of authigenic gypsum. The stable sulfur isotopic analyses of gypsum and co-existing pyrite revealed that sulfate produced by pyrite oxidation contributed to gypsum precipitation. The low oxygen isotopic composition values of gypsum (−2.6 to 4.5‰ Vienna Standard Mean Ocean Water) suggest that pyrite is oxidized by metal oxides under anaerobic conditions, incorporating water oxygen, whose isotopic composition was modified by gas hydrate formation, into the produced sulfate. As pyrite oxidation also releases protons (H+) into the porewater, calcium concentrations may be elevated by the dissolution of carbonate minerals. At sites GMGS2–08 and GMGS2–16, authigenic gypsum was precipitated within paleo sulfate-methane transition zones, indicating that gypsum formation is probably associated with the downward migration of the sulfate-methane transition zone, which causes anaerobic pyrite oxidation at its original site of formation. However, at site GMGS4-W02B, most of the gypsum was distributed in a mass transport deposit characterized by a high abundance of reworked foraminiferas between the two paleo sulfate-methane transition zones. Given that seawater sulfate contributes more (>85%) than pyrite oxidation to the gypsum sulfate at site GMGS4-W02B, it is believed that authigenic gypsum formation is associated with mass transport deposits, which can rapidly trap overlying seawater sulfate within the pore space of the newly deposited sediments, combined with the sulfate and calcium from pyrite oxidation, leading to a local gypsum supersaturation.

Deciphering the geochemical link between seep carbonates and enclosed pyrite: A case study from the northern South China sea

Sulfate-driven anaerobic oxidation of methane (SD-AOM) is an important microbial process at methane seeps, which consumes most of the methane migrating from sediments and can lead to the formation of seep carbonate and pyrite. Geochemical proxies archived in seep carbonates have been long used to uncover the nature of seepage. Recently, the sulfur isotopic composition of enclosed pyrite shows ideal prospects for targeting the seepage dynamics, but it remains challenging due to a possible decoupled precipitation of carbonate and pyrite. In order to decipher the geochemical link between seep carbonates and enclosed pyrite, multiple geochemical proxies of both carbonate (major elements, rare earth elements, δ13C) and pyrite (contents and δ34Spy) were analyzed from two seep sites of the northern South China Sea. Multiple carbonate phases were identified via X-ray diffraction and transmission electron microscopy, including microcrystalline aragonite and botryoidal aragonite from Haima seeps, and micritic high-magnesium calcite (HMC), weakly ordered dolomite and botryoidal aragonite from site TVG11. The δ13C values for carbonates from both sites exhibit very light carbon isotopic signatures (from −59.2 to −35.8‰), confirming that the carbon source is mainly derived from the oxidation of biogenic methane. For pyrite enclosed in carbonates, their contents and sulfur isotopic compositions (δ34Spy) reveal generally positive correlations with Mg/Ca ratios, where HMC and dolomite show higher pyrite contents and δ34Spy values, but microcrystalline aragonite and botryoidal aragonite display lower pyrite contents and negative δ34Spy values. This is consistent with our knowledge that HMC and dolomite tend to precipitate at a deeper sulfate-methane transition zone (SMTZ) where the replenishment of seawater sulfate is limited, whereas microcrystalline aragonite and botryoidal aragonite tend to form at shallow SMTZ with enhanced seawater sulfate supplement. Thus, the δ34S values of pore water sulfate greatly affect the resulting sulfur isotopic composition of pyrite, i.e., the higher δ34Spy values in HMC and dolomite are attributed to the 34S enrichment in pore water sulfate at deeper SMTZ. This is supported by SIMS results that pyrite entrapped in botryoidal aragonite displays lower δ34SSIMS values than those in HMC. Our results suggest that geochemical proxies archived in both carbonate and pyrite point to the similar sedimentary environments, suggesting an intrinsic link between these two archives in our study sites.

Multiple sulfur isotope chemostratigraphy across the Permian–Triassic boundary at Chaotian, China: Implications for a shoaling model of toxic deep‐waters

AbstractPrevious studies on multiple sulfur isotopes (32S, 33S, and 34S) in sedimentary pyrite at the end‐Permian suggested a shoaling of anoxic/sulfidic deep‐water contributing to the extinction. This scenario is based on an assumption that the sedimentary sulfur cycle was largely controlled by benthos activity, though a stratigraphic correlation between the sulfur records and ichnofabrics of the sediments at the end‐Permian has not yet been examined. We report the multiple sulfur isotopic composition of pyrite in the Permian–Triassic boundary interval at Chaotian, South China. Our data can be generally explained by a mixing of sulfur in sulfide from two different sources: one produced via sulfate reduction in an open system with respect to sulfate and the other produced in a closed system. In particular, the former with the substantially low δ34S (&lt;−40 ‰) and high ∆33S (up to +0.100 ‰) values was likely produced via water‐mass sulfate reduction or via sulfate reduction in oxic sediments with common burrows. The frequent occurrence of small pyrite framboids (mostly &lt;5 μm in diameter) in the Lopingian (Late Permian) Dalong Formation of deep‐water facies supports the enhanced water‐mass sulfate reduction in an anoxic deep‐water mass. The negative ∆33S values are observed only in the oxic limestones, and no substantial ∆33S change is observed across the extinction horizon despite of the disappearance of bioturbation. Our results are apparently inconsistent with the previous shoaling model. We expand the model and infer that, when the deep‐water was sulfidic and its shoaling rate was high, a substantial amount of hydrogen sulfide (H2S) was supplied onto the shelf via the shoaling; that resulted in the positive ∆33S value of the bulk sediments. The observed ∆33S variation on a global scale suggests a substantial variation in H2S concentration and/or in upwelling rate of shoaling deep‐waters during the Permian–Triassic transition.

Variations in hydrocarbon generating potential of the Chang 7 shale: Evidence from pyrite morphology and sulfur isotope

Hydrocarbon generating potential in source rocks is influenced by various controlling factors. Bottom water redox condition during source rock deposition is an important one among these factors and can directly control the organic matter enrichments in source rocks. The study of pyrite morphology and sulfur isotopic compositions in pyrite provides useful information on depositional redox conditions in ancient marine and lacustrine systems. The results of our study in the Ordos Basin, North China show that pyrite morphology varies from framboid to euhedral crystals throughout the Chang 7 Shale. Further, the sulfur isotopic compositions of pyrite (δ34Spy) display a close linkage with the framboid size distributions of throughout the Chang 7 Shale deposition. The presence of relatively small pyrite size (average = 8.7 μm) and lighter sulfur isotopic compositions of pyrite (average = 4.9‰) in the Chang 73 suggests the bottom water redox conditions were anoxic to dysoxic. In contrast, pyrites in the Chang 72 and Chang 71 are relatively larger (average = 12.7 μm), and have heavier sulfur isotopic compositions (average = 7.1‰) as compared of those in the Chang 73 shales, suggesting a long-term oxic-dysoxic bottom water conditions. Previous paleontological and geochemical data suggest that marine incursion may have supplied ample sulfate into the basin water promoting bacterial sulfate reduction and led to the forming of anoxic-dysoxic lake bottom water redox conditions during Chang 73 shale deposition. In addition, the coupled organic matter enrichment in the Chang 73 and oxygen-depletion conditions is also reflected by the coincidence of higher total organic carbon content in the Chang 73 deposits. A decreasing marine influence with subsequent restriction of the lake basin led to distillation of sulfate, followed by a gradual return to oxic-dysoxic bottom waters during the deposition of the Chang 72 and Chang 71.

Early diagenesis of iron and sulfur in Bornholm Basin sediments: The role of near-surface pyrite formation

Pyrite formation in marine sedimentary environments plays a key role in the global biogeochemical cycles of carbon, sulfur and iron, regulating Earth’s surface redox balance over geological time scales. The sulfur isotopic composition of pyrite is one of the major geochemical tools for investigating early diagenetic processes in modern marine sediments and substantive changes to the Earth’s surface environment in ancient sedimentary rocks. We studied sulfur–iron diagenesis and the sulfur isotopic evolution in sediments of the Bornholm Basin, southwestern Baltic Sea, to track the formation of pyrite in the near-surface sediments. Pyrite accumulation is observed with depth over the uppermost 100 cm before the extent of pyritization of the highly reactive iron pool (Fepy/FeHR) stays constant at ca. 0.9, suggesting that the use of a single iron-speciation parameter as a proxy for anoxic and sulfidic conditions needs to be supported by other independent indicators in sedimentary records. Stable sulfur isotopic analysis demonstrates that the bulk pools of elemental sulfur and iron monosulfide do not exchange isotopes completely with aqueous sulfide. We suggest that the reactions with polysulfide and aqueous sulfide are probably restricted to the surface of the solid-phase sulfur and iron-sulfur aggregates. Although pyrite is growing throughout the uppermost sediment column, the pyrite at depth has a sulfur isotopic composition similar to that of pyrite formed near the sediment surface. To understand the isotopic discrepancy between pyrite and aqueous sulfide in the deeper sediments, we developed a simple diagenetic model, which reproduces the observed sulfur isotopic composition of pyrite well. Our results suggest that much of the pyrite is rapidly formed near the sediment–water interface, and its δ34S is not as influenced by the 34S-enriched pool of aqueous sulfide in the deeper part of the sediment, allowing 32S-enriched pyrite to be preserved in deeper sediments. This near-surface diagenesis and the associated isotopic pattern are possibly of relevance for many marine sediments with high organic matter content, and high aqueous sulfide but low reactive iron availability. Moreover, our sulfur isotopic data demonstrate that extremely slow pyritization is ongoing in the deep lacustrine clay sediments. These results have implications for the interpretation of sulfur–iron geochemical data in both modern and ancient settings as well as for improving reconstructions of ancient depositional environments and a better understanding of the marine sulfur cycle throughout Earth’s history.

Geology and genesis of the Early Paleozoic Zhengguang intermediate-sulfidation epithermal Au-Zn deposit, northeast China

Zhengguang is a partly eroded (about ≥500 m being eroded), structurally controlled intermediate sulfidation (IS) epithermal gold-zinc deposit, characterized by wide distribution of base metal sulfides, Fe-poor sphalerite and Mn-calcite, hosted by the Late Cambrian-Early Ordovician basaltic-andesitic volcanic and volcano-sedimentary rocks in northeast China. The deposit is located 4 and 8 km from the Early Ordovician Tongshan (including several IS veins about ~500 m away in the east called East Tongshan) and Duobaoshan porphyry copper deposits, respectively. A 484.8 ± 8.7 Ma (MSWD = 198) of Re-Os isochron age on pyrite indicates that it is the most ancient intermediate sulfidation deposit that has been dated.Four stages of veins have been discerned at Zhengguang. Early magnetite ± chalcopyrite ± epidote ± chlorite and K-feldspar ± pyrite ± chalcopyrite veins (stage I) were associated with restricted K-feldspar ± epidote (locally with chlorite) alteration and propylitic (epidote ± chlorite ± calcite) assemblages. Two primary epithermal gold stages developed at Zhengguang: pyrite-quartz ± Fe-poor sphalerite ± chalcopyrite ± galena ± electrum ± petzite ± hessite ± tetrahedrite/tennantite ± adularia veins (stage II) and (Mn-)calcite-quartz-pyrite ± Fe-poor sphalerite ± chalcopyrite ± galena ± hessite ± native gold (stage III), plus a late barren stage characterized by little sulfides (calcite ± chlorite ± hematite ± quartz, stage IV). Gold occurs chiefly as micro-inclusions of electrum and petzite in pyrite and sphalerite of stages II and III.Stable isotope analyses and fluid inclusion results indicate a magmatic-hydrothermal component in the ore fluids. Fluid inclusion data from stage I yielded the highest salinity (∼6.9 wt% NaCl) and homogenization temperature (average 264 °C). Calculated oxygen isotope composition of fluid (δ18Owater up to 4.9‰) equilibrated with quartz indicates a magmatic-hydrothermal source during stage I. A progressive addition of meteoric water component is suggested from stage I to IV of Zhengguang based on the average δ18Owater values equilibrated with quartz and homogenization temperatures (stage I: δ18Owater = 3.3‰, Th = 264 °C; stage II: δ18Owater = −1.4‰, Th = 182 °C; stage III: δ18Owater = −3.4‰, Th = 154 °C; stage IV: δ18Owater = −6.3‰, Th = 121 °C).Our new pyrite Re-Os dating result shows that Zhengguang formed at the same time with Tongshan and Duobaoshan within errors. Comparable sulfur isotopic compositions of pyrite from Zhengguang and Tongshan, analogous low-Fe content in sphalerite and similar mineral assemblage and alteration pattern between Zhengguang and East Tongshan IS veins collectively indicate a genetic connection between Zhengguang and Tongshan, which may derive from fluids exsolved from the same magma chamber. High-temperature assemblages (e.g., K-feldspr ± pyrite ± chalcopyrite) at Zhengguang indicate that there is potential for the discovery of porphyry copper–gold mineralization below the current level of diamond drilling. The confirmation of the Zhengguang as an Early Paleozoic epithermal deposit implies a good preservation and exploration potential of ancient epithermal deposits in eastern Central Asian Orogenic Belt.

Multiple Sulfur Isotope Records of the 3.22 Ga Moodies Group, Barberton Greenstone Belt

The Moodies Group, the uppermost unit in the Barberton Greenstone Belt (BGB) in South Africa, is a ~3.7-km-thick coarse clastic succession accumulated on terrestrial-to-shallow marine settings at around 3.22 Ga. The multiple sulfur isotopic composition of pyrite of Moodies intervals was newly obtained to examine the influence of these depositional settings on the sulfur isotope record. Conglomerate and sandstone rocks were collected from three synclines north of the Inyoka Fault of the central BGB, namely, the Eureka, Dycedale, and Saddleback synclines. The sulfur isotopic composition of pyrite was analyzed by Secondary Ion Mass Spectrometry (SIMS) for 6 samples from the three synclines and by Isotope Ratio Mass Spectrometry (IR-MS) for 17 samples from a stratigraphic section in the Saddleback Syncline. The present results show a signal of mass-independent fractionation of sulfur isotopes (S-MIF), although t-tests statistically demonstrated that the Moodies S-MIF signals (mostly 0‰ &lt; ∆33S &lt; +0.5‰) are significantly small compared to the signal of the older Paleoarchean (3.6–3.2 Ga) records. These peculiar signatures might be related to initial deposition of detrital pyrite of juvenile origin from the surrounding intrusive (tonalite–trondhjemite–granodiorite; TTG) and felsic volcanic rocks, and/or to secondary addition of hydrothermal sulfur during late metasomatism. Moreover, fast accumulation (~0.1–1 mm/year) of the Moodies sediments might have led to a reduced accumulation of sulfur derived from an atmospheric source during their deposition. As a result, the sulfur isotopic composition of the sediments may have become susceptible to the secondary addition of metasomatic sulfur on a mass balance point of view. The sulfur isotopic composition of Moodies pyrite is similar to the composition of sulfides from nearby gold mines. It suggests that, after the Moodies deposition, metasomatic pyrite formation commonly occurred north of the Inyoka Fault in the central BGB at 3.1–3.0 Ga.

Mineralogy and sulfur isotope characteristics of metalliferous sediments from the Tangyin hydrothermal field in the southern Okinawa Trough

We present and compare mineralogy and sulfur isotopic composition data of two surface metalliferous sediment samples, TVG11-2 and ROV11-R2, from the newly discovered Tangyin hydrothermal field in the southern Okinawa Trough (S-OT), and one surface metalliferous sediment sample 2-T4 from the Iheya North Knoll hydrothermal field in the middle Okinawa Trough (M–OT). The purpose of this study is to better understand the hydrothermal ore-forming environment and material source in the S-OT. Samples TVG11-2 and ROV11-R2 were derived from different types of chimneys. Sample TVG11-2 was derived from a black chimney which experienced formation process from high temperature to low temperature, with large gradients and fluctuations. ROV11-R2 was directly derived from a low-temperature white chimney or low-temperature diffuse flow. The sulfur isotopic compositions of sulfides and native sulfur in the S-OT are significantly lower than the sulfur isotopic compositions of pyrite and native sulfur in the M–OT, indicating there is another source with a lower sulfur isotopic composition. The low forming temperature and similar basement rocks of rhyolite in Iheya North Knoll, and dacite in Tangyin exclude phase separation and basement rock differences as the main reasons for low sulfur isotopic compositions in TVG11-2 and ROV11-R2. The occurrence of different bacterial communities between S-OT and M–OT may affect the sulfur isotopic compositions, but the influencing mechanism is still unclear. The addition of magmatic H2S may be the most possible reason for lower sulfur isotopic compositions in the Tangyin hydrothermal field.

Trace element contents and in situ sulfur isotope analyses of pyrite in the Baiyun gold deposit, NE China: Implication for the genesis of intrusion-related gold deposits

Trace elements distribution in minerals and formation mechanism of visible gold are poorly understood in intrusion-related gold systems. Here, we choose the Baiyun gold deposit, which is hosted within the Paleoproterozoic metamorphic rocks in the Liaodong Peninsula, NE North China Craton (NCC), as a case study, to address these issues. The ore deposit geology characteristics and paragenesis are described in details; In situ geochemical and sulfur isotopic compositions of pyrite and bulk Pb isotopic ratios of pyrite were presented to define the genesis of pyrite that is closely associated with gold mineralization. Three generations of pyrite were recognized based on petrographic studies: metamorphic pyrite (Py0), hydrothermal pyrite (Py1) coexisting with milky quartz, and hydrothermal pyrite (Py2) coexisting with smoky quartz. In situ laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) spot analysis suggests that both Py0 and Py1 contain low contents of invisible gold (mean 0.19 ppm and 0.17 ppm, respectively). However, Py1 is low in most other trace element contents and contains Au-Ag-Cu-Pb-Bi micro-inclusions. In contrast, Py2 contains both invisible gold (mean 0.50 ppm) and Au-Ag-Cu-Pb-Bi micro-inclusions. Furthermore, LA-ICP-MS mapping reveals the distributions of Ag, Cu, Pb, Bi and Te closely mimic that of Au, indicating an episode of ore-forming fluid rich in Au, Ag, Cu, Pb, Bi and Te. In situ sulfur isotope analysis of pyrite shows that Py0 has significantly positive δ34S values (+11.74–17.33‰), suggesting that sulfur was derived from sedimentary sources. Py1 and Py2 have negative δ34S values (–8.53––6.19‰, –10.44––6.86‰, respectively), indicating that sulfur was derived from oxidized magmatic fluids. The magmatic fluids are concluded to be released from the early Cretaceous microdiorite magmas, providing most of the sulfur and ore-forming metals. Proofs include the close spatial association of the ore bodies and the dykes, as well the uniform Pb isotopic ratios of Py1 and the early Cretaceous microdiorite. Lines of geological, mineralogical, geochemical and isotopic evidence consistently suggest that the gold mineralization in the Baiyun deposit is intrusion-related, and was resulted from the ~126 Ma magmatic-hydrothermal activities in the region. Visible gold precipitating in pyrite and fractures was from metal-rich magmatic fluids rather than being remobilized from the metamorphic pyrite.