Pyrite Sulfur Isotope Research Articles

Sedimentary pyrite sulfur isotopes track the local dynamics of the Peruvian oxygen minimum zone

Sulfur cycling is ubiquitous in sedimentary environments, where it mediates organic carbon remineralization, impacting both local and global redox budgets, and leaving an imprint in pyrite sulfur isotope ratios (δ34Spyr). It is unclear to what extent stratigraphic δ34Spyr variations reflect local aspects of the depositional environment or microbial activity versus global sulfur-cycle variations. Here, we couple carbon-nitrogen-sulfur concentrations and stable isotopes to identify clear influences on δ34Spyr of local environmental changes along the Peru margin. Stratigraphically coherent glacial-interglacial δ34Spyr fluctuations (>30‰) were mediated by Oxygen Minimum Zone intensification/expansion and local enhancement of organic matter deposition. The higher resulting microbial sulfate reduction rates led to more effective drawdown and 34S-enrichment of residual porewater sulfate and sulfide produced from it, some of which is preserved in pyrite. We identify organic carbon loading as a major influence on δ34Spyr, adding to the growing body of evidence highlighting the local controls on these records.

The Paleoarchean Northern Mundo Novo Greenstone Belt, São Francisco Craton: Geochemistry, U–Pb–Hf–O in zircon and pyrite δ34S-Δ33S-Δ36S signatures

Greenstone belts contain several clues about the evolutionary history of primitive Earth. Here, we describe the volcano-sedimentary rock association exposed along the eastern margin of the Gavião Block, named the Northern Mundo Novo Greenstone Belt (N-MNGB), and present data collected with different techniques, including U–Pb–Hf–O isotopes of zircon and multiple sulfur isotopes (32S, 33S, 34S, and 36S) of pyrite from this supracrustal sequence. A pillowed metabasalt situated in the upper section of the N-MNGB is 3337 ± 25 Ma old and has zircon with εHf(t) = −2.47 to −1.40, Hf model ages between 3.75 Ga and 3.82 Ga, and δ18O = +3.6‰ to +7.3‰. These isotopic data, together with compiled whole-rock trace element data, suggest that the mafic metavolcanic rocks formed in a subduction-related setting, likely a back-arc basin juxtaposed to a continental arc. In this context, the magma interacted with older Eoarchean crustal components from the Gavião Block. Detrital zircons from the overlying quartzites of the Jacobina Group are sourced from Paleoarchean rocks, in accordance with previous studies, yielding a maximum depositional age of 3353 ± 22 Ma. These detrital zircons have εHf(t) = −5.40 to −0.84, Hf model ages between 3.66 Ga and 4.30 Ga, and δ18O = +4.8‰ to +6.4‰. The pyrite multiple sulfur isotope investigation of the 3.3 Ga supracrustal rocks from the N-MNGB enabled a further understanding of Paleoarchean sulfur cycling. The samples have diverse isotopic compositions that indicate sulfur sourced from distinct reservoirs. Significantly, they preserve the signal of the anoxic Archean atmosphere, expressed by MIF-S signatures (Δ33S between −1.3‰ to +1.4‰) and a Δ36S/Δ33S slope of −0.81 that is indistinguishable from the so-called Archean array. A BIF sample has a magmatic origin of sulfur, as indicated by the limited δ34S range (0 to +2‰), Δ33S ~ 0‰, and Δ36S ~ 0‰. A carbonaceous schist shows positive δ34S (2.1‰–3.5‰) and elevated Δ33S (1.2‰–1.4‰) values, with corresponding negative Δ36S between −1.2‰ to −0.2‰, which resemble the isotopic composition of Archean black shales and suggest a source from the photolytic reduction of elemental sulfur. The pillowed metabasalt displays heterogeneous δ34S, Δ33S, and Δ36S signatures that reflect assimilation of both magmatic sulfur and photolytic sulfate during hydrothermal seafloor alteration. Lastly, pyrite in a massive sulfide lens is isotopically similar to barite of several Paleoarchean deposits worldwide, which might indicate mass dependent sulfur processing from a global and well-mixed sulfate reservoir at this time.

Texture, trace elements, sulfur and He-Ar isotopes in pyrite: Implication for ore-forming processes and fluid source of the Guoluolongwa gold deposit, East Kunlun metallogenic belt

The Gouli goldfield is the most important gold producers of the East Kunlun metallogenic belt. Gold mineralization in this region is enigmatic, primarily because of uncertainties as to the mineralization processes, and the nature and sources of ore-forming fluids. Here, we investigate the ore-forming fluids and processes through a comprehensive study of the texture and geochemistry (LA-(MC)-ICPMS trace element analysis, mapping, S isotopes, and He-Ar isotopes) of pyrite from the Guoluolongwa gold deposit, the largest deposit in the Gouli goldfield. Four types of pyrite with distinct textures, trace element contents and sulfur isotopes were identified, and provide evidence for a multi-stage hydrothermal fluid evolution. The sedimentary-diagenetic Py0, representing the pre-ore stage, is characterized by high contents of Co and Ni, and negative δ34S values (−11.6‰ to −4.0‰), which are notably different from the subsequent hydrothermal Py1 to Py3. Hydrothermal Py1, comprising subtypes Py1a and Py1b, was deposited in pyrite-quartz veins during stage I. The Py1a subtype shows characteristic Co-Ni-As oscillatory zoning that replaced Py0 via dissolution-reprecipitation, and hence inherited high concentrations of Co and Ni from Py0. In contrast, the Py1b subtype was devoid of Py0 influence and represented the initial ore-forming fluid with low concentrations of Co and Ni, moderate Cu, Pb, Zn, Sb, and Bi, but high As, Au, and Ag. The next stage, Py2, formed in the quartz-pyrite veins during stage II and showed clear textural and compositional contrasts to Py1. Specifically, Py2 has elevated Cu, Pb, Zn, Ag, and Bi contents and somewhat lower δ34S values (+1.5‰ to +3.2‰) compared to Py1 (+1.6‰ to +5.6‰). In addition, Py2 shows irregular compositional zones, which we attribute to fluid phase separation caused by pressure fluctuation. Abundant Py2 precipitation triggered native gold deposition due to desulfidation of the ore-forming fluid. The next stage, Py3 in polymetallic sulfides-calcite-quartz veins at stage III, implies a new pulse of Cu-Pb-Zn-As-Au-Ag-rich and Bi-poor ore-forming fluid. This latter pyrite is characterized by inclusion-rich cores (Py3c), which contain abundant inclusions of chalcopyrite, galena, sphalerite, and native gold, and inclusion-free rims (Py3r). The cores, Py3c, likely represent abrupt destabilization of metal complexes and rapid precipitation during vigorous phase separation, whereas the euhedral Py3r rims formed under steadier physico-chemical conditions, contributing to lower δ34S values of Py3c (+0.5‰ to +3.0‰) than Py3r (+1.9‰ to +3.6‰). Noble gas isotopes of Py1-Py3 have crust-dominated 3He/4He (0.04–0.4 Ra) and 40Ar/36Ar (623–2081), mixed with minor mantle components. Sulfur isotopes and low Co and Ni contents of hydrothermal pyrite, and He-Ar isotopes of fluid inclusions in pyrite, are consistent with a model in which multiple pulses of ore-forming fluids were exsolved during sequential episodes of primarily crustal-derived felsic magmatism with lesser mantle influences. This model is also supported by previous H-O isotope analyses, as well as widespread granitoid magmatism in the eastern Central East Kunlun Belt.

Separation of Fe from Mn in the Cryogenian Sedimentary Mn Deposit, South China: Insights from Ore Mineral Chemistry and S Isotopes from the Dawu Deposit

Manganese and Fe have similar geochemical properties in the supergene environment. Separation of Mn and Fe is an important process for the formation of high-grade sedimentary manganese deposits. Large-scale manganese carbonate deposits (total reserves of approximately 700 Mt) were formed during the interglacial of the Sturtian and Marinoan in South China. The orebodies are hosted in the black rock series at the basal Datangpo Formation of the Cryogenian period. The Fe contents in ores range from 1.15 to 7.18 wt.%, with an average of 2.80 wt.%, and the average Mn/Fe ratio is 8.9, indicating a complete separation of Mn and Fe during the formation of manganese ores. Here, we present element data of manganese carbonates and sulfur isotopes of pyrite from the Dawu deposit, Guizhou, China, aiming to investigate the separation mechanism of Mn and Fe and the ore genesis. The Fe in ores mainly occurs as carbonate (FeCO3) and pyrite (FeS2). The Mn, Ca, Mg and Fe exist in the form of isomorphic substitutions in manganese carbonate. The contents of FeCO3 in manganese carbonates are similar in different deposits, with averages of 2.6–2.8 wt.%. The whole-rock Fe and S contents have an obvious positive correlation (R = 0.69), indicating that the difference of whole-rock Fe content mainly comes from the pyrite content. The δ34SV-CDT of pyrite varies from 40.0 to 48.3‰, indicating that the pyrite formed in a restricted basin where sulfate supply was insufficient and the sulfate concentrations were extremely low. Additionally, the whole-rock Fe content is negatively correlated with the δ34S values of the whole-rock and pyrite, with correlation coefficients of −0.78 and −0.83, respectively. Two stages of separations of Mn and Fe might have occurred during the mineralization processes. The reduced seawater became oxidized gradually after the Sturtian glaciation, and Fe2+ was oxidized and precipitated before Mn2+, which resulted in the first-stage separation of Mn and Fe. The residual Mn-rich and Fe-poor seawater flowed into the restricted rift basin. Mn and Fe were then precipitated in sediments as oxyhydroxide as the seawater was oxidized. At the early stage of diagenesis, organic matter was oxidized, and manganese oxyhydroxide was reduced, forming the manganese carbonate. H2S was insufficient in the restricted basin due to the extremely low sulfate concentration. The Fe2+ was re-released due to the lack of H2S, resulting in the second-stage separation of Mn and Fe. Finally, the manganese carbonate deposit with low Fe and very high δ34S was formed in the restricted basin after the Sturtian glaciation.

Response of a continental fault basin to the global OAE1a during the Aptian: Hongmiaozi Basin, Northeast China

This paper presents new research on a lacustrine anoxic event (LAE). These data include stable carbon isotope (δ13Corg), pyrite sulfur isotope (δ34Spy), trace element and biomarker ratios from the Hongmiaozi Basin (North China) and unravel the response of continental lakes under the influence of early Aptian extreme climate conditions. According to the stratigraphic chronology (122–118 Ma) and carbon isotope correlations, terrestrial sediment was influenced by the early Aptian Oceanic Anoxic Event (OAE1a). The results show that the Xiahuapidianzi Group experienced a significant warming process under negative excursions in carbon isotopes due to the influence of increased carbon dioxide partial pressure (pCO2). The climate varied from warm and humid to hot and arid (high Sr/Cu, low Rb/Sr, calcareous mudstone), the evaporation and salinity increased (high Sr/Ba and B/Ga), and land input sources decreased (low Zr, Ti and Th). Moreover, high total organic carbon (TOC) content was source from bacteria, algae (n-alkanes), and euxinic depositional environments (Pr/Ph, Cu/Zn and U V Mo). In the stage of continuous carbon isotopes positive excursion, organic matter accumulated rapidly. A paleolake environment model has provided a better understanding of current global climate issues under global warming caused by increased carbon dioxide concentrations.

Strong local, not global, controls on marine pyrite sulfur isotopes

Understanding variation in the sulfur isotopic composition of sedimentary pyrite (δ34Spyr) is motivated by the key role of sulfur biogeochemistry in regulating Earth's surface oxidation state. Until recently, the impact of local depositional conditions on δ34Spyr has remained underappreciated, and stratigraphic variations in δ34Spyr were interpreted mostly to reflect global changes in biogeochemical cycling. We present two coeval δ34Spyr records from shelf and basin settings in a single sedimentary system. Despite their proximity and contemporaneous deposition, these two records preserve radically different geochemical signals. Swings of ~65‰ in shelf δ34Spyr track short-term variations in local sedimentation and are completely absent from the abyssal record. In contrast, a long-term ~30‰ decrease in abyssal δ34Spyr reflects regional changes in ocean circulation and/or sustained pyrite formation. These results highlight strong local controls on δ34Spyr, calling for reevaluation of the current practice of using δ34Spyr stratigraphic variations to infer global changes in Earth's surface environment.

Carbon and sulfur isotope variations through the Upper Ordovician and Lower Silurian of South China linked to volcanism

Pronounced excursions of carbon and sulfur isotopes (δ13C and δ34S) spanning the Ordovician–Silurian (O–S) transition have been recognized globally, yet the causes of these isotope events and their causal relationships to environmental changes, especially during Early Silurian time, remain the topics of debate. In this study, we present organic carbon and pyrite sulfur isotope (δ13Corg and δ34Spyr) records and elemental concentrations from a drill core spanning from the Upper Ordovician (Katian) to Lower Silurian (Aeronian) succession of the Yangtze Platform, China. The newly presented δ13Corg profile records previously recognized positive excursions, including the Hirnantian isotopic carbon excursion (HICE), the middle Rhuddanian excursion, and the early Aeronian positive carbon isotope excursion (EACIE). In addition, two negative δ13Corg excursions are recognized during the Katian to early Hirnantian and late Hirnantian to middle Rhuddanian stages. The δ34Spyr profile exhibits a great amount of variation (−17.8‰ to +19.6‰) but mimics the δ13Corg record. Coupled positive δ13Corg and δ34Spyr excursions during the middle Hirnantian and late Rhuddanian to Aeronian are associated with decreased total organic carbon (TOC) content and less reducing water column conditions, whereas the negative δ13Corg and δ34Spyr excursions during the Katian to early Hirnantian and late Hirnantian to middle Rhuddanian are associated with enhanced TOC values and the establishment of more strongly anoxic to euxinic conditions. The δ13C and δ34S excursions during the O–S transition, then, cannot be explained by changes in redox conditions or the burial of organic carbon and pyrite. The heavier and less variable middle Hirnantian and late Rhuddanian to Aeronian δ34Spyr values probably reflect low marine sulfate concentration. In contrast, negative Katian to early Hirnantian and late Hirnantian to middle Rhuddanian δ34Spyr excursions may reflect increased sulfate concentration. The two negative δ13Corg and δ34Spyr excursions associated with the Katian to early Hirnantian and late Hirnantian to middle Rhuddanian correspond with episodes of volcanism. We therefore propose that volcanism was the main driver of coupled negative δ13Corg and δ34Spyr excursions. As volcanism diminished during the middle Hirnantian and late Rhuddanian to Aeronian, both δ13Corg and δ34Spyr returned to more positive values. Our results indicate that volcanism played a crucial role in triggering carbon and sulfur isotope perturbations and environmental changes during the Late Ordovician and Early Silurian.

Iron and sulfur isotopes of sulfides from the Wocan hydrothermal field on the Carlsberg Ridge, Indian Ocean

The basalt-hosted Wocan hydrothermal field (WHF) was identified in 2013 during Chinese Dayang 28th cruise, which is located on the slow-spreading Carlsberg Ridge, northwest Indian Ocean. Few investigation has been carried out on the hydrothermal activities and associated sulfide deposit in this area. Herein, we report Fe and S isotope compositions of sulfide minerals including chalcopyrite, bornite, pyrite and sphalerite collected from the WHF. The results showed that all sulfide minerals display small δ34S variations (2.44‰ to 5.37‰, with an average of 4.00‰), and a wide δ56Fe range (−2.05‰ to 0.10‰, with an average of −0.92‰). Sulfur and iron isotopes in paired pyrite and chalcopyrite minerals reveal that it did not reach the equilibrium fractionation during pyrite precipitation, and support that the FeS precipitates first during the pyrite formation. The δ56Fe values of chalcopyrite and concurrent bornite are characterized by a well-defined negative correlation, which may be related to the repeated dissolution-reprecipitation of these copper-bearing sulfides under Fe-limited conditions. Most pyrites from the WHF demonstrate a positive correlation between δ56Fe and δ34S values, in accord with those from other hydrothermal fields, which can be explained by the temperature gradient and similar degrees of isotope exchange in the stable hydrothermal system. Conversely, the δ56Fe and δ34S values of chalcopyrite exhibit a slightly negative correlation, in which the temperature gradient can explain the negative correlation, but cannot cover the wide ranges of δ56Fe and δ34S values. More work on fractionation parameters and chalcopyrite formation mechanisms is still needed. In summary, the coupling of Fe and S isotopes is a useful tool in helping to delineate processes of sulfide mineralization in hydrothermal systems

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 (<−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 <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.

In situ S isotope analysis and source tracing of pyrite from lacustrine hydrothermal sedimentary rocks: the Chang 7-3 sub-member, Triassic Yanchang Formation, Ordos Basin

The Ordos Basin developed a large depression-type lake basin in the Late Triassic. Here, we report on pyrites from lacustrine hydrothermal sedimentary rocks that were found at the bottom of a black shale layer from the Chang 7-3 sub-member of the Triassic Yanchang Formation in Tongchuan and Yaoqu and Well Z9 sections, on the southern margin of the Ordos Basin. Observations of field outcrops and underground cores were used to identify vein and brecciated pyrites that are distributed within water-explosive dolomite breccias or sandwiched in a textured layer of hydrothermal sedimentary rock. Based on previous work, scanning electron microscopy observations, electronic probe microanalysis, nano-SIMS trace-element mapping and in situ sulfur isotope analyses were completed. The crystal form of pyrites is mainly cubic with surfaces mostly smooth and clean. Pyrites contain trace elements, such as As, Au, Co, Cu, Cr and Zn. The pyrite sulfur isotope values are enriched in 34S (δ34SV-CDT = 7.31–10.05‰; average 8.49‰) and show that the pyrite is related to hydrothermal deposition. Late Triassic hydrothermal activity at the bottom of the lake provided sulfate for pyrite formation, and hydrothermal sulfide may have also been an important sulfur source. KEY POINTS Pyrites from lacustrine hydrothermal sediments were formed at the bottom of a black shale layer from the Chang 7-3 sub-member of the Triassic Yanchang Formation on the southern margin of the Ordos Basin. The pyrite contains trace elements such as As, Au, Co and Ni. In situ pyrite sulfur isotope values are enriched in 34S and show that the pyrite is related to hydrothermal deposition with sulfur derived from sulfate and hydrothermal sulfide

Integrated chemostratigraphy (δ13C-δ34S-δ15N) constrains Cretaceous lacustrine anoxic events triggered by marine sulfate input

During the Late Cretaceous period (~100.5–65 million years ago), two episodes of expansive lake anoxia occurred in the Songliao Basin (~3× the size of Lake Superior), NE China, either lasting less than one million years. These events, known as lacustrine anoxic events (LAEs), were the factors driving the development of the main source rocks for the most productive oilfields in China. The details underpinning the initiation of the LAEs, however, remain problematic. As a test of this scientific issue, we present time series of bulk organic carbon isotopes, pyrite sulfur isotopes, nitrogen isotopes and trace element concentrations from the Turonian–Coniacian Qingshankou Formation in the Songliao Basin. A notable δ34S excursion (~−10‰) and a spike in pyrite sulfur content are recorded in the basal Qingshankou Formation when the basin reached the maximum expansion. We attributed these changes to marine transgression, which would have brought high sulfate concentrations to the lake, thereby promoting microbial sulfate reduction (MSR). Subsequent sulfate limited by MSR and pyrite burial associated with isolation of the lake from the seawater drove a 20‰ positive δ34S shift. Note that the modes of the δ34S that fluctuations we describe from the LAEs have also been recognized in marine black shale during Oceanic Anoxic Event (OAE) 2, implying a common signature of anoxia. The carbon isotope data suggest that the maximal fractionation found in Qingshankou Member I was likely a consequence of the increased [CO2]aq in lake water and inputs from chemoautotrophs. Increased sedimentary δ15N during the interval of Qingshankou Member I implies intensified denitrification in the oxygen minimum zone, which lowered the water-column N/P ratios, thereby stimulating bacterial nitrogen fixation in Qingshankou Members II-III. By comparing and summarizing the sulfur, carbon and nitrogen cycles of the LAEs during deposition of the Qingshankou and Nenjiang formations, we argue that the forcing function underlying LAEs was enhanced sulfate levels from marine transgression, which might have intensified nutrient recycling and further regulated the lacustrine carbon and nitrogen cycles.

Microfabrics, in-situ trace element and sulfur isotope compositions of pyrite from the Jinjiwo copper deposit in Chengmenshan orefield, northern Yangtze Block: Syngenetic stratabound mineralization and hydrothermal remobilization

The Jinjiwo copper deposit is located in the Jiurui ore district of the Middle-Lower Yangtze Metallogenic Belt. The deposit has stratiform orebodies hosted by Late Carboniferous carbonate units. Pyrite is the dominant metallic mineral in the ores. Here we report on an integrated study on the microfabrics, Raman spectroscopy, in-situ LA-(MC-)ICP-MS trace element and sulfur isotope of pyrite, with a view to understand the geochemical variation, genesis of copper mineralization and ore-forming process. Textural observations suggested four types of pyrite corresponding to three metallogenic episodes: syngenetic sedimentation (PyI), metamorphism or deformation (PyII), and skarn-hydrothermal mineralization including the late skarn stage (PyIII) and hydrothermal stage (PyIV). Raman spectra of pyrite reveal subtle differences in band position and widths (FWHM) and display the increasing formation temperature of from PyI, through PyIV and PyIII, to PyII. Colloform and laminated pyrite (PyI) share similarities in behavior of pairs of elements and have low Co/Ni ratios, and the former contains the highest concentrations of Bi, Cu, Pb, Zn, Ag, Au, Mn that suggest rapid precipitation from highly saturated fluids. PyII shows high Co, Ni and As concentrations and Co/Ni ratios of 0.03 to 6.19. PyIII and PyIV have greatly varying Co/Ni ratios of 1.07 to 29 and typically low Au concentrations, suggesting a hydrothermal source. PyIII is rich in Co and Se, but is depleted in As, Cu, Pb, Zn, Ag, and Au in comparison with PyIV. There are two kinds of sulfur: one is that δ34S values are near zero, suggesting that the pyrite sulfur in the ores was derived from a mixed source in deep crust, and the other is that δ34S values are less than −39.1‰, indicating the sedimentary pyrite sulfur was originated from bacterial sulfate reduction. The combined textural and compositional data of pyrite suggest that the formation of the Jinjiwo copper deposit might have recorded the submarine exhalation sedimentation and the Mesozoic tectonic transition-deformation and hydrothermal overprint.

Origin and evolution of a porphyry-breccia system: Evidence from zircon U-Pb, molybdenite Re-Os geochronology, in situ sulfur isotope and trace elements of the Qiyugou deposit, China

The Qiyugou Au deposit, located in the Xiong'ershan ore cluster of central China, consists of breccia pipe hosted Au ore bodies (>60 t Au) and newly discovered porphyry ore body (8 t Au). The porphyry Au mineralization occurs in the silicified core of the apical part of porphyritic granite stock which shows close spatial relationship with the auriferous breccia pipes. Here we present an integrated study involving detailed field investigation, textural studies, in situ pyrite trace element and sulfur isotope analysis, and U-Pb and Re-Os geochronology to elucidate the genetic relationship and hydrothermal evolution of the porphyry and breccia pipe mineralization. The SIMS sulfur isotopic analyses for the five pyrite generations show consistent δ34S values between −3.6‰ and 0.6‰, indicating that the two styles of Au mineralization had a mixed source including crustal and mantle-derived components. Zircon LA-ICP-MS U-Pb geochronology of two porphyritic granites yield weighted mean ages of 133.0 ± 0.6 Ma and 130.3 ± 0.9 Ma, and six molybdenite samples display an isochron age of 131.3 ± 1.1 Ma, representing the timing of granitic magmatism and Au mineralization in the 189 porphyry ore body. Available geochronological data allow us to constrain the timing of granitic magmatism and gold mineralization to be 135.6–134.1 Ma in the breccia pipes and 133.0–128.6 Ma in the porphyry ore. Among the five pyrite generations, Py1b and Py2b from the J4 breccia pipe are characterized by higher Co, Ni, and comparable contents of other elements (e.g. Au, Ag, Te, Pb, Zn, Cu and Bi) than those in Py1p, Py2p and Py3p from the porphyry ore. The widely consistent metal concentrations and linear relationship of metals in pyrite between the breccia pipe and porphyry ore are most probably the result of fluid exsolution from the same magmatic-hydrothermal system, whereas the enriched Co and Ni values from the J4 breccia pipe can reflect the composition of pyrite precipitating fluid at the early stage of the prolonged magmatic-hydrothermal system. The Qiyugou porphyry and breccia pipe mineralization show close spatial-temporal association and consistent source materials, and thus we propose that they resulted from multiple pulses of fluid exsolution from a large, deep-seated magma chamber.

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.

Trace elements of pyrite and S, H, O isotopes from the Laowan gold deposit in Tongbai, Henan Province, China: implications for ore genesis

The Laowan deposit is a large gold deposit in the Qinling-Dabie orogenic belt where pyrite is the main Au-bearing mineral phase. We present results from the occurrences of gold, trace elements and sulfur isotopes of pyrite, and hydrogen and oxygen isotopes of quartz and calcite to elucidate the sources of ore-forming fluid; the genesis of pyrite and the ore-forming process. From field observations, five generations of pyrite are identified; one formed in a metamorphic-diagenetic epoch (PyI), and the others during four mineralization stages: 1) the coarse-grained pyrite-quartz stage (PyII), 2) the quartz and medium- to fine-grained pyrite stage (PyIII), 3) the polymetallic sulfide stage (PyIV), and 4) the carbonate-quartz stage (PyV). Gold mainly occurs in PyIII and PyIV. We find that Au, Ag, Pb, and Cu are incorporated into pyrite as micro-/nano-inclusions and that Co, Ni, As, and Se enter the pyrite lattice via isomorphous replacement. The Co/Ni values and Se concentrations indicate that PyI formed from metamorphic hydrothermal fluids and that pyrites (PyII, PyIII, and PyIV) from the ore-forming stages typically reflect a hydrothermal genesis involving magmatic fluid. The δ34S values of PyI (1.45 ‰–2.09‰) are similar to that of plagioclase amphibole schist, indicating that S was primarily derived from wall rock, while those of PyII, PyIII, and PyIV (3.10‰–5.55‰) suggest that S was derived from the Guishanyan Formation and the Laowan granite. The four mineralization stages show a systematic decrease in δD (from −77.1‰ to −82.8‰, −84.7‰, and −102.7‰), while the $${{\rm{\delta }}^{18}}{{\rm{O}}_{{{\rm{H}}_2}{\rm{O}}}}$$ values showed a gradual decrease from 5.7 to 2.7‰, 1.0‰, and −1.3‰. These data show that the ore-forming fluid was similar to a mixture of magmatic and meteoric waters. Thus, we conclude that the Laowan gold deposit is related to magmatic-hydrothermal fluid.

Environmental evolution of the East China Sea inner shelf and its constraints on pyrite sulfur contents and isotopes since the last deglaciation

To better understand the depositional constraints on the sulfate reduction process, we present a set of sulfur isotope data for hand-picked pyrites (δ34Spyr) from the coarse fraction (63–250 μm) of bulk sediments, coupled with the contents of carbonate, total organic carbon (TOC) and nitrogen (TN), as well as δ13C values of the TOC, from sediments of core EC2005 on the inner shelf of the East China Sea (ECS) since 16.4 ka. Our results show that core sediments were deposited in a terrestrial environment before 13.1 ka (stage I) when pyrite rarely occurred. During stages II (13.1–12.3 ka) and III (12.3–12.1 ka) seawater began to influence the core location, forming a tidal flat environment where abundant pyrites are well preserved. Then the inner shelf of the ECS was fully flooded, and two intervals with high (stage IV:12.1–6.0 ka; stage VI: 5.2–1.5 ka) and low sedimentation rate (stage V: 6.0–5.2; stage VII: 1.5 ka-present) are identified respectively. When compared with previous δ34S values of chromium-reducible sulfur (δ34SCRS) derived from the bulk sediments, δ34Spyr values are usually higher, indicating the macroscopic pyrites form in the later stages of sedimentary diagenesis when ongoing sulfate reduction has distilled porewater sulfate to a high degree. Considering the wide occurrence of biogenic shallow gas (dominated by CH4) in these sediments, sulfate-driven anaerobic oxidation of methane (SO4-AOM) and organoclastic sulfate reduction (OSR) are expected to be two competitive pathways for sulfate reduction. We propose that the changes in sedimentation rate controls the pace of migration of the sulfate methane transition zone (SMTZ). When sedimentation rate is low, the SMTZ may be fixed in a certain depth (e.g., sediments deposited in stage III and V), where H2S is produced by SO4-AOM. In contrast, when sedimentation rate is very high (> 1 cm/yr), the SMTZ would be deep, and H2S is mostly produced by OSR. Further, our results imply that sulfur diagenesis in recent (since 1.5 ka) ECS mud sediments might be influenced by physical reworking (e.g., typhoon) and/or biological activity (bioturbation), resulting in partial reoxidation of pyrite crystals in fluid mud. Our findings therefore demonstrate that pyrite sulfur isotope compositions (bulk δ34SCRS & hand-picked δ34Spyr) are sensitive to local environmental evolution and the combined use of these two indicators can provide new insights into pathway of sulfate reduction in unsteady environments.

Anomalous positive pyrite sulfur isotope in lacustrine black shale of the Yanchang Formation, Ordos Basin: Triggered by paleoredox chemistry changes

The pyrite sulfur isotope in the black shale of the Chang 7 unit are anomalous positive compared with those of the current paradigm, in which the value of pyrite sulfur isotopes should be negative due to sulfur isotopic fractionation through bacterial sulfate reduction (BSR). A series of geological and geochemical analysis (FeT/Al and δ34Spy, average of 0.51 and 6.5‰, respectively) are carried out to confirm that sulfur speciation is derived from sulfate in watermass rather than hydrothermal fluids, and the δ34Spy values are effective records of the original sedimentary environment. Integrated geochemical data including redox sensitive elements (RSE) ratios, ratio of organic carbon to phosphorus (Corg:P, molar, average of 85.4), organic sulfur to carbon (organic S:C, average of 10.47%) and pyrite framboid size distribution (range in 9.7–16.6 μm), are represented to reconstruct the paleoredox chemical conditions during the deposition of the Chang 7 unit black shale. The results suggest that the paleoredox chemical conditions of the middle and lower subunits (the Ch 72 and Ch 73 subunits) were dominated by suboxic environments with intermittent anoxic environments and that changed to oxic with intermittent suboxic environments in the upper subunit (the Ch 71 subunit). Based on the analysis of sulfur isotope fractionation during the sulfur cycle, the paleoredox chemical conditions are confirmed to be the trigger for the anomalous sulfur isotopic compositions. The limited sulfate in watermass and overlying fine-grained sediments resulted in a relatively closed system for BSR, where limited sulfur isotope fractionation lead to the formation of heavy pyrite. Subsequently, due to the dissolved oxygen penetrated into the sediment, the reactivation of anaerobic oxidants resulted in reoxidation of hydrogen sulfide derived from BSR, then to “heavier” pyrite via Rayleigh-type distillation in the Ch 71 subunit.

Source and distribution of pyrite and inorganic sulfur isotopes in the Saray and Pınarhisar Coalfields, North Thrace Basin, Turkey

This study is mainly concerned with sulfur isotope (δ34S) values of inorganic sulfur species associated with the North Thrace Basin's coals (Saray and Pınarhisar coalfields). Sulfur isotope analyses were performed on pyritic sulfur, native sulfur, sulfate sulfur (rozenite) and the precipitated sulfate (P-BaSO4) (leached sulfate from the coal). The δ34S values of pyritic sulfur, rozenite, native sulfur and P-BaSO4 samples in Saray coals ranging from −6.9‰ to −37.3‰ are comparable to the δ34S values of Pınarhisar coals which change from −1.1‰ to −59.3‰. A wide range of strong negative δ34S values in both coalfields, particularly in Pınarhisar site, indicate that bacterial sulfate reduction (BSR) and subsequent pyrite formation were the key processes in the peat depositional environments. As in the δ34S values of both coalfield sites, comparable Sr/Ba and Th/U ratios and pyrite forms (cleat filling and partly massive) of the coals imply that besides marine sulfate hydrothermal solutions, originated from volcanism being active during peat accumulation in the basin, also contributed to the sulfur pools in the coal depositional environments.Overall, the δ34S values of inorganic sulfur species, and the largest sulfur isotope fractionation between δ34S P-BaSO4 and the δ34Spyrite, obtained for the first time for the Thrace Coal Basin, suggest that bacterial reduction of sulfate, possibly marine and hydrothermally derived, and subsequent pyrite formation and its fast burial may have been contributed to sulfur budget in the basin.

Integrated sedimentary, biotic, and paleoredox dynamics from multiple localities in southern Laurentia during the late Silurian (Ludfordian) extinction event

The Silurian was a time of major climatic transition punctuated by multiple biotic crises and global carbon cycle perturbations. The most severe of these biotic events was the late Silurian (Ludfordian) Lau/Kozlowskii extinction event (LKE) and the associated Lau carbon isotope excursion (CIE). Although the extinction event and Lau CIE are globally documented, the only records thus far of local and global marine paleoredox conditions through this interval are from a single region in Scandinavia. Here we examine four sections along a bathymetric transect of mixed carbonate-siliciclastic sediments from western Tennessee, USA. A novel approach using a multi-proxy dataset combining high-resolution geochemical data and microfacies analyses from multiple localities explores the possibilities of local/regional-scale redox heterogeneities during a time of widespread environmental upheaval on a global scale. Paired positive excursions recorded in carbonate carbon isotopes and carbonate-associated sulfate sulfur isotopes support recent work from carbonate and siliciclastic successions from Scandinavia, suggesting a global enhancement of organic carbon and pyrite burial driven by an expansion of euxinic (anoxic and sulfidic water column) conditions in the oceans during the mid-Ludfordian. Furthermore, positive excursions in organic carbon isotopes and pyrite sulfur isotopes reflect the global changes in redox. Stratigraphic trends in I/Ca ratios imply a local expansion of low-oxygen conditions, with low, but non-zero values during the rising limb and peak of the CIE. The fossil assemblages vary across the shelf and through the CIE interval. Stratigraphic changes in fossil assemblages and I/Ca are closely associated with local and global changes in oxygenation and sea level during the mid-Ludfordian. The collective data indicate significant biotic reorganization in response to changes in marine redox conditions and in conjunction with sea-level variation during the LKE interval, but detailed macroscopic biodiversity is currently unconstrained for this region.

Marine redox variability from Baltica during extinction events in the latest Ordovician–early Silurian

It is well documented that Upper Ordovician and Silurian successions record multiple marine turnover events – including the second-largest mass extinction in the Phanerozoic – widespread glaciation, and multiple global carbon cycle perturbations. Whereas causal mechanisms for the Late Ordovician major mass extinction event involving climate, paleoceanographic variation, and δ13C records have been published, similar records remain poorly constrained for subsequent extinction events in the early Silurian. Here, we present new organic matter carbon isotope (δ13Corg) chemostratigraphy and corresponding paleoredox proxies (Fe speciation, [Mn, V, Mo], and pyrite sulfur isotopes) from two organic-rich drill core sections in Sweden and Latvia that span the upper Katian through lower Wenlock stages (446–431 Ma). Pyritized Fe and bulk sedimentary Mn concentrations from Upper Ordovician strata in southern Sweden suggest a local redox shift to more reducing conditions in the late Hirnantian, possibly including euxinic (anoxic and sulfidic water column) conditions that coincide with the second mass extinction pulse. The new high-resolution δ13Corg and δ34Spyr datasets from the late Aeronian (early Silurian) interval within both drill cores show positive excursions that are broadly coincident with the associated Sandvika and sedgwickii extinction events. Independently, Fe speciation and bulk sedimentary trace metal data from this late Aeronian interval record locally euxinic conditions in both the deep basinal (Sweden) and distal shelf (Latvia) settings before and during the late Aeronian positive δ13C excursion. This multiproxy paleoredox dataset provides the first direct evidence for local to regional expansion of reducing marine conditions coincident with this early Silurian (late Aeronian) biotic event and positive δ13C excursion. Additionally, new δ34Spyr values spanning the Llandovery/Wenlock boundary interval in the Latvia core show a positive excursion coincident with Fe speciation and trace metal enrichments that imply a local redox perturbation with intermittently euxinic bottom waters during the rising limb of the Ireviken positive δ13C excursion. The combination of these geochemical data for local- to regional-scale (more data required for global interpretations) changes in marine redox conditions with paleobiological records and evidence for eustatic sea-level rise indicate that environmental stresses related to an expansion of anoxic to euxinic conditions were a probable driver for several extinction events during the latest Ordovician–early Silurian.