Sulfur Isotope Research Articles

Continuous-Flow Stable Sulfur Isotope Analysis of Organic and Inorganic Compounds by EA-MC-ICPMS.

Elemental analysis (EA) coupled to isotope ratio mass spectrometry (IRMS) is a well-established method to derive stable isotope ratios of sulfur (34S/32S). Conversion of sulfur to SO2 by EA and measurement of SO2 isotopologues by IRMS represents the simplest and most versatile method to accomplish isotope measurement of sulfur even in bulk samples. Yet, interferences by oxygen isotopes in SO2 often impair the precision and trueness of measured results. In the current study, we coupled EA to multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) to establish a method that avoids such interferences due to direct measurement of S+ ions. In addition, measurement of the 33S/32S isotope ratios is possible, thus representing the first bulk method that is suitable to study mass-independent isotope fractionation (MIF). Analytical precision (σ) of available Ag2S and BaSO4 reference materials (RMs) was, on average, 0.2 mUr for δ33S and δ34S, never exceeding 0.3 mUr within this study (1 mUr = 1‰ = 0.001). Measured δ34S values of reference materials agreed within ±0.2 mUr of officially reported values. Measurement of wood samples yielded good precision (0.2 mUr) for sulfur amounts as low as 3.5 μg, but precision deteriorated for samples at lower sulfur contents due to poor peak shape. Finally, we explored cross-calibration of organic liquids separated via gas chromatography (GC) against solid RMs combusted via EA that avoids challenging offline conversion of RMs. Results indicate good precision (≤0.08 mUr) and acceptable trueness (≤0.34 mUr) for determination of δ34S, demonstrating the future potential of such an approach.

Extreme shifts in pyrite sulfur isotope compositions reveal the path to bonanza gold

Pyrite is the most common sulfide mineral in hydrothermal ore-forming systems. The ubiquity and abundance of pyrite, combined with its ability to record and preserve a history of fluid evolution in crustal environments, make it an ideal mineral for studying the genesis of hydrothermal ore deposits, including those that host critical metals. However, with the exception of boiling, few studies have been able to directly link changes in pyrite chemistry to the processes responsible for bonanza-style gold mineralization. Here, we report the results of high-resolution secondary-ion mass spectrometry and electron microprobe analyses conducted on pyrite from the Brucejack epithermal gold deposit, British Columbia. Our δ34S and trace element results reveal that the Brucejack hydrothermal system experienced abrupt fluctuations in fluid chemistry, which preceded and ultimately coincided with the onset of ultra-high-grade mineralization. We argue that these fluctuations, which include the occurrence of extraordinarily negative δ34S values (e.g., -36.1‰) in zones of auriferous, arsenian pyrite, followed by sharp increases of δ34S values in syn-electrum zones of nonarsenian pyrite, were caused by vigorous, fault valve-induced episodic boiling (flashing) and subsequent inundation of the hydrothermal system by seawater. We conclude that the influx of seawater was the essential step to forming bonanza-grade electrum mineralization by triggering, through the addition of cationic flocculants and cooling, the aggregation of colloidal gold suspensions. Moreover, our study demonstrates the efficacy of employing high-resolution, in situ analytical techniques to map out individual ore-forming events in a hydrothermal system.

Graphitisation of Neoproterozoic sedimentary marbles in The Aird, Scottish Highlands

Graphite occurs in Neoproterozoic (probable Loch Ness Supergroup) marbles of The Aird, in the Northern Highland Terrane, Scotland. The graphite occurs particularly in association with phlogopite mica, and also with other micas and Mg-chlorite. Although the graphite-phlogopite association is recorded widely elsewhere in mantle-derived rocks, our data suggests graphite at The Aird does not have a mantle origin. The carbon isotopic composition of the graphite ( δ 13 C, 0.4 to -1.6 ‰) indicates graphitisation occurred from a CO 2 -rich fluid associated with decarbonation or devolatilisation reactions of a carbonate-silicate protolith. Graphite-phlogopite bearing marbles in the Aird underwent extensive brecciation and haematite deposition that preceded carbon-rich, mantle-derived (carbonatite) fluids. Pyrite in veins within The Aird marble has a sulphur isotope composition depleted in 34 S (-15.5 to -16.6 ‰), suggesting a biogenic origin. Elsewhere in The Aird and in surrounding fenitised rocks 34 S -enriched pyrite has sulphur isotope compositions between 7.7 to 6.1 ‰, outside the sulphur isotopic composition range of most carbonatite-hosted pyrite, suggesting pyrite veining was likely influenced by crustal fluid-rock interactions. The observations show that if the protolith has a carbonate-silicate composition, a graphite-phlogopite association can form without the need for mantle-derived fluids. Thematic collection: This article is part of the Early Career Research collection available at: https://www.lyellcollection.org/topic/collections/early-career-research

Isotopic evidence of long-lived volcanism on Io.

Jupiter's moon Io hosts extensive volcanism, driven by tidal heating. The isotopic composition of Io's inventory of volatile chemical elements, including sulfur and chlorine, reflects its outgassing and mass loss history, and thus records information about its evolution. We used millimeter observations of Io's atmosphere to measure sulfur isotopes in gaseous SO2 and SO, and chlorine isotopes in gaseous NaCl and KCl. We find 34S/32S = 0.0595 ± 0.0038 (equivalent to δ34S = +347 ± 86‰), which is highly enriched compared to average Solar System values and indicates that Io has lost 94 to 99% of its available sulfur. Our measurement of 37Cl/35Cl = 0.403 ± 0.028 (δ37Cl = +263 ± 88‰) shows that chlorine is similarly enriched. These results indicate that Io has been volcanically active for most (or all) of its history, with potentially higher outgassing and mass-loss rates at earlier times.

Geology and Geochronology of Magmatic–Hydrothermal Breccia Pipes in the Yixingzhai Gold Deposit: Implications for Ore Genesis and Regional Exploration

Magmatic–hydrothermal breccia pipes are widespread in numerous major porphyry and epithermal gold deposits globally, representing significant repositories of metal resources and serving as potential indicators for exploration targeting. More than ten breccia pipes occur in the Central Taihangshan District (CTD) of the North China Craton. Some of these breccia pipes host gold mineralization and are proposed to be related to the adjacent lode gold mineralization. However, the lack of detailed geological constraints make this hypothesis ambiguous. To address this, the present study conducted comprehensive field observations, drill core logging, an in situ sulfur isotope analysis of pyrite, and the 40Ar/39Ar dating of adularia along a 1400 m section of the Tietangdong breccia pipe at Yixingzhai. Three distinct breccia facies were identified at Tietangdong, exhibiting variable proportions across the entire section, including a massive skarn breccia; polymictic, skarn matrix-supported breccia; and polymictic, intrusive rock cement chaotic breccia. Furthermore, adularia 40Ar/39Ar dating indicates a syn-/post-gold mineralization age of 136 ± 1.5 Ma, coinciding with the age of post-breccia felsite dike. The deepest sampled pyrite displays δ34S values of ~2.7‰, strongly indicating a magmatic–hydrothermal signature. These results, when combined with the geological, geochronological, and isotopic studies on the adjacent lode gold mineralization, further suggest a close genetic relationship between the breccia pipes and the lode Au mineralization, paving the way for their utilization as effective indicators for gold targeting within the CTD.

Proof of concept evidence that stable isotopes of carbon, nitrogen and sulphur may identify individual kittiwakes breeding in different colonies.

Carbon, nitrogen and sulphur stable isotopes in feathers grown by seabirds while breeding reflect the local isoscape and diet in the vicinity of the colony, so may make it possible to discriminate individual birds from different colonies. Black-legged kittiwake Rissa tridactyla inner primary feathers from two colonies about 350 km apart in the North Sea were used to test whether δ13C, δ15N and δ34S differed between individuals from the two colonies. Feather tips cut from breeding birds caught at nests were compared with tips of moulted feathers (grown 1year earlier) found on the ground. Isotopic compositions showed no overlap between the two colonies in δ13C, δ15N or δ34S in tips of newly-grown feathers sampled from breeding adult kittiwakes. There was some overlap in δ13C, δ15N and δ34S from moulted feathers, but discriminant analysis allowed >90% of individuals to be assigned to their colony. In five of six comparisons, mean isotopic compositions were the same in new and moulted feathers but not for δ34S at one of the two colonies. This study has demonstrated for the first time that stable isotopes in inner primary feathers of kittiwakes can allow accurate identification of the breeding colony of individual birds from two different colonies within the North Sea. Further research is required to determine if this method can be applied with greater spatial resolution and to a larger number of colonies.

Authigenic carbonate and native sulfur formation in Messinian (upper Miocene) marine sediments: Sedimentological, petrographical and geochemical constraints

Carbonate concretions accompanied by elemental sulfur were found in an early Messinian (Late Miocene) marine succession of NW Italy. The rocks were studied with an integrated approach including sedimentological, petrographical, stable isotope (carbon, oxygen, and multiple sulfur isotopes), and lipid biomarker analyses. Unlike other examples from Messinian strata of the Mediterranean area, the studied carbonate and sulfur concretions did not derive from the diagenetic replacement of sulfate minerals. Three lithofacies were distinguished: a) laminated lithofacies representing aphotic carbonate stromatolites enclosing fossils of filamentous sulfide-oxidizing bacteria; b) brecciated lithofacies deriving from the brecciation of carbonate stromatolites by mud injections; c) sulfur-bearing lithofacies deriving from the precipitation of thin laminae of elemental sulfur at or close to the sediment-water interface. The carbon and oxygen stable isotope composition of authigenic carbonate minerals and lipid biomarkers indicate that the initial formation of the laminated lithofacies was favored by organoclastic sulfate reduction in the shallow subsurface close to the sediment-water interface, producing sulfide that sustained dense microbial mats of sulfide-oxidizing bacteria at the seafloor. Calcification of the mats and consequent formation of stromatolites were possibly favored by nitrate-driven sulfide oxidation at the seafloor. The subsequent brecciation of the stromatolites was apparently the consequence of sulfate-driven anaerobic oxidation of methane (SD-AOM) in an underlying sulfate-methane transition zone (SMTZ). Focused fluid flow from below, possibly resulting from destabilization of gas hydrates, was not only responsible for the brecciation of the stromatolites, but also for the delivery of bicarbonate ions and the consequent precipitation of additional, 13C-depleted calcite (δ13C values as low as −52‰). Along with bicarbonate, also hydrogen sulfide was produced by SD-AOM at the SMTZ and was transported upwards. The oxidation of hydrogen sulfide at or close to the seafloor promoted the formation of elemental sulfur characterized by δ34S values and Δ33S values close to coeval seawater sulfate.

Energy flux couples sulfur isotope fractionation to proteomic and metabolite profiles in Desulfovibrio vulgaris.

Microbial sulfate reduction is central to the global carbon cycle and the redox evolution of Earth's surface. Tracking the activity of sulfate reducing microorganisms over space and time relies on a nuanced understanding of stable sulfur isotope fractionation in the context of the biochemical machinery of the metabolism. Here, we link the magnitude of stable sulfur isotopic fractionation to proteomic and metabolite profiles under different cellular energetic regimes. When energy availability is limited, cell-specific sulfate respiration rates and net sulfur isotope fractionation inversely covary. Beyond net S isotope fractionation values, we also quantified shifts in protein expression, abundances and isotopic composition of intracellular S metabolites, and lipid structures and lipid/water H isotope fractionation values. These coupled approaches reveal which protein abundances shift directly as a function of energy flux, those that vary minimally, and those that may vary independent of energy flux and likely do not contribute to shifts in S-isotope fractionation. By coupling the bulk S-isotope observations with quantitative proteomics, we provide novel constraints for metabolic isotope models. Together, these results lay the foundation for more predictive metabolic fractionation models, alongside interpretations of environmental sulfur and sulfate reducer lipid-H isotope data.

Isotopic evidence of high reliance on plant food among Later Stone Age hunter-gatherers at Taforalt, Morocco

The transition from hunting-gathering to agriculture stands as one of the most important dietary revolutions in human history. Yet, due to a scarcity of well-preserved human remains from Pleistocene sites, little is known about the dietary practices of pre-agricultural human groups. Here we present the isotopic evidence of pronounced plant reliance among Late Stone Age hunter-gatherers from North Africa (15,000–13,000 cal BP), predating the advent of agriculture by several millennia. Employing a comprehensive multi-isotopic approach, we conducted zinc (δ66Zn) and strontium (87Sr/86Sr) analysis on dental enamel, bulk carbon (δ13C) and nitrogen (δ15N) and sulfur (δ34S) isotope analysis on dentin and bone collagen, and single amino acid analysis on human and faunal remains from Taforalt (Morocco). Our results unequivocally demonstrate a substantial plant-based component in the diets of these hunter-gatherers. This distinct dietary pattern challenges the prevailing notion of high reliance on animal proteins among pre-agricultural human groups. It also raises intriguing questions surrounding the absence of agricultural development in North Africa during the early Holocene. This study underscores the importance of investigating dietary practices during the transition to agriculture and provides insights into the complexities of human subsistence strategies across different regions.

Local depositional and diagenetic conditions control the positive δ34S excursion during the Ordovician-Silurian transition: Evidence from the Wufeng-Longmaxi formations in Sichuan Basin

The Ordovician-Silurian (OS) transition was characterized by significant changes in global climate, marine redox conditions, and biological evolution, which include global seawater euxinia, the onset of the Hirnantian glaciation, and large-scale extinctions. During this time, the marine sulfur cycle was disrupted, and the pyrite sulfur isotope (δ34Spy) showed a large positive excursion. This excursion is closely tied to the Hirnantian glaciation, with δ34Spy increasing at the start of and decreasing at the end of the glaciation. Although it is thought that variations in marine sulfate concentration and primary productivity are responsible for the positive excursion in δ34Spy, contemporary marine sediment δ34Spy data suggest that sedimentary processes can also lead to significant fluctuations in δ34Spy. To assess the impact of local changes in sedimentary conditions on this positive δ34Spy excursion event, we conducted detailed depositional and geochemical analyses of sedimentary pyrite found in black shales from the Wufeng-Longmaxi formations in the Weiyuan area of the Sichuan Basin, China. These sedimentary pyrites include three types: framboidal, euhedral, and laminated pyrite. Bulk sample sulfur isotope analyses revealed that δ34Spy values vary from −16.2‰ to 15.8‰ (mean = −3.8‰, n = 22). In situ analyses of δ34Spy show that different pyrite crystals exhibit a range of intragranular δ34Spy values that are likely indicators of diagenesis. Variations in bulk sample δ34Spy are strongly and negatively correlated with the proportion of framboidal pyrite, i.e., lower levels of framboidal pyrite content resulted in a higher bulk sample δ34Spy value, suggesting diagenetic alteration controls on δ34Spy. In addition, the δ34Spy excursion in the Wufeng-Longmaxi formations also appears to be compatible with lithological changes related to sedimentation rate. The δ34Spy values from the Guanyinqiao Bed, which consists of calcareous shales, are higher than those from black shales with a relatively low sedimentation rate. Our results suggest that the positive δ34Spy excursion during the OS transition during the Hirnantian glaciation is controlled not only by diagenetic alterations but also by local sedimentation rate.

In-Situ Geochemical and Rb–Sr Dating Analysis of Sulfides from a Gold Deposit Offshore of Northern Sanshandao, Jiaodong Peninsula, North China: Implications for Gold Mineralization

The gold deposit offshore of Northern Sanshandao is an ultra-large-scale gold deposit discovered in the Jiaodong ore area in recent years. This deposit is a fractured-zone altered-rock-type gold deposit; however, its ore genesis and precise mineralization processes are still highly controversial. Based on petrographical observation, the trace elements, sulfur isotopes, and rubidium–strontium isotopes of the gold-bearing pyrite were analyzed using LA-MC-ICP-MS to obtain the source of the ore-forming fluids and ore genesis. The results show that Au has a good positive correlation with Ag, As, and Cu. It is speculated that the As in the pyrite of the gold deposit offshore of Northern Sanshandao is in the form of As−, replacing S− and entering the pyrite, causing its lattice defects, and thus promoting the entry of Au+ into the gold-bearing pyrite. The Co/Ni ratios mainly range between 0.1 and 10, indicating that the mineralization process has experienced different forms of hydrothermal evolution and the mixing of different fluids. The results of the in-situ sulfur isotope analysis show that pyrite δ34S in the mineralization period is characterized by a high sulfur value. The authors of this study believe that the initial sulfur isotope composition has mantle-derived components. The large-scale, deep cutting, and high degree of fragmentation in the Sanshandao fault zone are conducive to the interaction between fluids and rocks, as well as the mixing and addition of seawater, resulting in the characteristic high δ34S value. The Sr isotopic compositions indicate a crust–mantle mixing attribute of the mineralized material source. The Rb–Sr isochron age of the pyrite is 118.5 ± 0.65 Ma, which represents the age of gold mineralization. According to the characteristics of the trace elements and sulfur isotopes, it is inferred that the gold deposit minerals offshore of Northern Sanshandao originated from deep magmatic-hydrothermal reservoirs, and the mixing of seawater and Au–As-rich hydrothermal fluids was the formation mechanism of huge amounts of gold precipitation.

Biological and paleoceanographic controls on the postglacial sulfur isotope records in Arctic shelf sediments

The Arctic Ocean has experienced environmental fluctuations during the Pleistocene glacial-interglacial cycles. Since the last deglaciation, the reinundation of the Bering Strait and regional transgression have led to dramatic changes in the western Arctic Ocean, affecting coastal landscapes, depositional processes, marine ecosystem, and, inherently, biogeochemical element cycles. Here, we investigate the records of sulfur, carbon, and iron cycles in the Chukchi Sea of the western Arctic, with a primary focus on microbial sulfate reduction and subsequent pyrite formation. Variations in the pyrite abundance and sulfur isotopic composition, derived from a 10-m sediment core, demonstrate that dynamic changes in the factors governing pyrite formation – organic electron donor, reactive iron, and sulfate – are closely linked to the regional environmental conditions. In the early Holocene sediment, pyrite precipitation was impeded by the lack of organic matter, even in the presence of abundant sulfate and reactive iron. In the overlying sediment, pyrite contents increased due to vigorous microbial sulfate reduction fueled by enhanced availability of organic substrate and additional methane from the sulfate-methane transition zone. In general, the increased supply of organic matter to the Chukchi Shelf sediments can be attributed to the resumed inflow of nutrient-rich Pacific Water through the flooded Bering Strait. The increase in pyrite content, however, does not correlate exactly with either the increase in TOC or the opening of the Bering Strait, both of which precede the increased pyrite formation. These lags reflect the balance between marine primary production and terrestrial carbon sources, as well as the balance between the Pacific Inflow and the Beaufort Gyre. While a comparable increase in pyrite and TOC contents during the Holocene deglaciation has also been reported in the Black and Baltic Sea sediments, their distinct sulfur isotope records, contingent upon the availability of sulfate and reactive iron, highlight that pyrite can serve as a valuable proxy for tracking past climate and environmental change, especially in barren sedimentary records such as those found in the Arctic Ocean.

A guide to precise measurements of isotope abundance by ESI-Orbitrap MS.

Stable isotopes of carbon, hydrogen, nitrogen, oxygen and sulfur are widespread in nature. Nevertheless, their relative abundance is not the same everywhere. This is due to kinetic isotope effects in enzymes and other physical principles such as equilibrium thermodynamics. Variations in isotope ratios offer unique insights into environmental pollution, trophic relationships in ecology, metabolic disorders and Earth history including climate history. Although classical isotope ratio mass spectrometry (IRMS) techniques still struggle to access intramolecular information like site-specific isotope abundance, electrospray ionization-Orbitrap mass spectrometry can be used to achieve precise and accurate intramolecular quantification of isotopically substituted molecules ('isotopocules'). This protocol describes two procedures. In the first one, we provide a step-by-step beginner's guide for performing multi-elemental, intramolecular and site-specific stable isotope analysis in unlabeled polar solutes by direct infusion. Using a widely available calibration solution, isotopocules of trifluoroacetic acid and immonium ions from the model peptide MRFA are quantified. In the second approach, nitrate is used as a simple model for a flow injection routine that enables access to a diverse range of naturally occurring isotopic signatures in inorganic oxyanions. Each procedure takes 2-3 h to complete and requires expertise only in general mass spectrometry. The workflows use optimized Orbitrap IRMS data-extraction and -processing software and are transferable to various analytes amenable to soft ionization, including metabolites, peptides, drugs and environmental pollutants. Optimized mass spectrometry systems will enable intramolecular isotope research in many areas of biology.

Genesis of the Mahour Base Metal Deposit, Iran: Constraints from Fluid Inclusions and Sulfur Isotopes

The Mahour base metal deposit is located northeast of Badroud in the middle of the Urumieh–Dokhtar magmatic arc in the Isfahan province of Iran. The main host rocks to the ores are Eocene volcanic and volcaniclastic rocks. Hypogene ore minerals constituting the main ore body are galena, sphalerite, pyrite, and chalcopyrite. In addition to gangue quartz, a variety of supergene minerals comprising gypsum, goethite, hematite, “limonite”, malachite, azurite, covellite, and chalcocite are also present; gangue minerals are quartz, barite, calcite, sericite, and chlorite. Silicification, intermediate argillic, and propylitic are the main wall-rock alteration types. The presence of fluid inclusions with different vapor/liquid ratios in quartz and sphalerite could indicate a boiling process. The primary liquid-rich fluid inclusions suggest that the homogenization temperature was between 107 and 298 °C from fluids with salinities from 1.5 to 13.7 wt.% NaCl equiv. These data suggest that the ore-forming fluids were magmatic with a contribution from meteoric waters. The δ34S values of sulfides range from 1.9 to 3.4‰, those of barite range from 12.1 to 13.2‰, and those of gypsum range from 4.3 to 5.6‰. These data suggest that sulfur was mostly of magmatic origin with a minor contribution from sedimentary rocks. Our data suggest that the boiling of fluids formed an intermediate-sulfidation style of epithermal mineralization for the Mahour deposit.

Carbon-Sulfur isotope and major and trace element variations across the Permian–Triassic boundary on a shallow platform setting (Xiejiacao, South China)

We examined microbialites deposited near the Permian–Triassic boundary (PTB) at the Xiejiacao section of South China, including the size and morphology of pyrite framboids, carbonate carbon isotopes (δ13Ccarb), carbonate associated sulfur isotope (δ34SCAS), major and trace elements, and total organic carbon (TOC) concentrations. The microbialite unit is much thicker than the PTB beds in deeper water sections, providing more detailed geochemical records from that time. A prominent negative δ13Ccarb excursion was recognized in association with the second phase of the Permian–Triassic mass extinction (PTME), comparable with that of several other shallow platform facies sections worldwide. δ34SCAS stratigraphic profiles also show a negative excursion, with minimum values occurring slightly later than those of δ13Ccarb. The minimum peak can be calibrated to the middle part of the conodont Isarcicella staeschei Zone, corresponding to the second phase of PTME. Over all, the carbon and sulfur isotopes demonstrate a coupled long-term relationship with large negative excursions during the Permian–Triassic transition followed by gradual recovery in the lowest Triassic, represented an extremely low concentration of sulfate in the ocean during this period. In contrast, the CS isotopes are strongly decoupled within the microbialite unit, which could be linked with the oxygen-poor conditions and microbial sulfate reduction (MSR: Sulfate reducing microorganisms facilitated the precipitation of sulfide and carbonate, such as SO42− + 2CH2O → H2S + 2HCO3−). The second phase of PTME was calibrated to the top of the microbialite unit, which was marked by the second δ13Ccarb-δ34SCAS negative excursions. The distinct marine oxygen deficiency was indicated by the small pyrite framboids, relatively high values of UEF (>1) and Ce/Ce* (>0.8). Combined with the previous biostratigraphic work, we propose that continuous volcanic activity induced intensified marine anoxia, leading to biotic mortality in the second phase of the PTME. Overall, our isotopic and geochemical data, integrated with results of previous studies, provided a new explanation for the carbon and sulfur isotope variations and additional evidences into the concurrent environmental changes during the Permian–Triassic transition.

Origin and evolution of a porphyry-skarn-stratabound system: constraints from geology, magmatic-hydrothermal zircon U–Pb and molybdenite Re–Os geochronology, and in situ S isotopes of the Dongguashan Cu(–Au) deposit, eastern China

Intrusion-related stratabound deposits within Late Carboniferous carbonate units are an abundant and highly economically significant ore type in eastern China. In such deposits, stratabound mineralization commonly coexists with porphyry and/or skarn mineralization, and the vast majority of reserves (>90 %) are derived from extensive stratabound orebodies, which are easy to exploit and of great interest to geologists. However, it is unclear whether these deposits were formed via the Late Carboniferous seafloor sedimentary exhalation formation or the Early Cretaceous magmatic-hydrothermal processes. Moreover, the fluid and sulfur isotope variations within porphyry-skarn-stratabound systems have not been adequately constrained. We investigated the Dongguashan deposit, one of the largest and most representative stratabound Cu(–Au) deposits in eastern China. Three mineralization types were recognized based on field and petrologic studies: porphyry, skarn, and stratabound. In the stratabound mineralization zone, magmatic and hydrothermal zircons from laminated ores yielded concordant U–Pb ages of 137.3 ± 1.1 and 135.7 ± 1.4 Ma, respectively, while molybdenite samples from vein-like ores yielded Re–Os model ages of 137.8–133.1 Ma (isochron age, 135.9 ± 1.4 Ma). These ages were consistent with the zircon U–Pb age of quartz monzodiorite (137.8 ± 1.7 Ma). A total of 146 in situ S isotope analyses yielded δ34S values (1.9–7.4 ‰) indicating that the sulfur was derived from a magmatic source. Therefore, the Dongguashan deposit resulted from Early Cretaceous magmatism rather than submarine exhalative sedimentary processes. The fluctuations in S isotopes of sulfides across the three mineralization types are attributable to different factors (pH, temperature, and oxygen fugacity) during the evolution of hydrothermal ore-forming fluids. This study demonstrates the importance of geochronology of mineralization and in situ sulfur isotope analysis under robust geological and petrographic frameworks, which can yield information about the ore-forming processes and ore genesis.

Rb–Sr Pyrite Dating and S–Pb Isotopes in the Fang’an Gold Deposit, Wuhe Area, Eastern Anhui Province

The Fang’an gold deposit in the Wuhe area, Anhui Province, is located in the area adjacent to the Bengbu Uplift and Wuhe Platform Depression in the southeastern part of North China. This study aimed to determine the deposit’s mineralization age and the source of its metallogenic materials and mineralization processes through investigations into its geological characteristics, Rb–Sr isotopes, and S–Pb isotopes. The orebodies of the Fang’an gold deposit in the Neoarchean Xigudui Formation primarily exhibit a vein-type structure. The ore-forming process can be divided into four stages: (i) the quartz stage (Py1); (ii) the quartz–pyrite stage (Py2); (iii) the polymetallic sulfide stage (Py3); and (iv) the carbonate stage. Of these, the main mineralization stage is also the main period in which gold mineralization occurs. In situ sulfur isotope results of pyrite (Py1 to Py3) in the first three mineralization stages, suggesting a contribution of sulfur from crust–mantle magmatic fluids. The δ34S values for Py2 (average 5.51‰) are higher than Py1 (average 4.45‰) and showed that the magmatic fluids mixed with meteoric waters. The δ34S values for Py3 (average 5.18‰) are lower than Py2 (average 5.51‰), revealing that it related fluid immiscibility. The lead isotopic compositions of sulfides within the ores possessed 206Pb/204Pb ratios ranging from 16.759 to 16.93, 207Pb/204Pb ratios ranging from 15.311 to 15.402, and 208Pb/204Pb ratios ranging from 37.158 to 37.548. These lead data were plotted close to the Xigudui Formation, relatively distant from the Mesozoic granites, indicating that the Xigudui Formation was the source of lead for the Late Mesozoic ores of the deposit. Taken together, due to the degassing of mantle-derived magma in the shallow parts of the crust, it can be determined that the sources of ore-forming sulfur and lead were crust–mantle magmatic activities in the Wuhe area. Rb–Sr dating of pyrite from Fang’an gold deposit reveals that the mineralization occurred at 126.89 ± 0.58 Ma. Considering the previous research into the dating of magmatic rocks in the Wuhe area, we propose that the genesis of the Fang’an gold deposit is closely associated with magmatic activities in the area at around 130 Ma.

Robust sulfur and oxygen isotope evidence for a highly anoxic paleoenvironment in Late Devonian seawater: Insights from marine anhydrites in the Zaige Formation, South China

A global-scale mass extinction event occurred in the Late Devonian, and its triggering mechanisms have remained a subject of controversy. The key to resolving this controversy lies in elucidating paleoenvironmental characteristics and their coupling relationship with the mass extinction. Marine evaporites serve as sensitive indicators that can be used for reconstructing the geochemical history of ancient oceans. In this study, we present a dual sulfur and oxygen isotopic dataset of marine anhydrites in the Lunatian gypsum deposit (Yunnan, China), and investigate its paleoenvironmental significance within the framework of the Late Devonian mass extinction. These anhydrites originate in arid and hot continental margin seas near convergent plate boundaries, forming as a result of the dehydration of marine gypsums during burial processes. Anhydrites exhibit a conspicuous positive anomaly in δ34S values (23.6–25.1‰, averaging 24.3‰), primarily attributed to bacteria-mediated sulfate reduction. The δ18O values of the Lunatian anhydrites (12.2–15.2‰, averaging 14.0‰) indicate a slightly higher oxygen isotope composition for Late Devonian seawater (8.7–11.7‰, averaging 10.5‰) compared to those of contemporary seawater (9.5–10.1‰). Such an oxygen isotopic characteristic for the Lunatian anhydrites is intricately associated with the chemical processes that occur during the diffusion of sulfides into the upper seawater. The anhydrite-forming evaporating system has a noticeable brine layering where the surface seawater is less dense than the deeper brine, and bacterial processes gradually increase δ34S in the deep brine. When the deep brine and surface seawater rapidly mix, it leads to a significant positive shift in the sulfur isotope composition of the resulting evaporites. Our sulfur and oxygen isotope data from Lunatian anhydrites validate the existence of an exceedingly anoxic marine environment during the Late Devonian, potentially serving as a pivotal factor in the mass extinction event.

Decadal-to-centennial increases of volcanic aerosols from Iceland challenge the concept of a Medieval Quiet Period

AbstractExisting global volcanic radiative aerosol forcing estimates portray the period 700 to 1000 as volcanically quiescent, void of major volcanic eruptions. However, this disagrees with proximal Icelandic geological records and regional Greenland ice-core records of sulfate. Here, we use cryptotephra analyses, high-resolution sulfur isotope analyses, and glaciochemical volcanic tracers on an array of Greenland ice cores to characterise volcanic activity and climatically important sulfuric aerosols across the period 700 to 1000. We identify a prolonged episode of volcanic sulfur dioxide emissions (751–940) dominated by Icelandic volcanism, that we term the Icelandic Active Period. This period commences with the Hrafnkatla episode (751–763), which coincided with strong winter cooling anomalies across Europe. This study reveals an important contribution of prolonged volcanic sulfate emissions to the pre-industrial atmospheric aerosol burden, currently not considered in existing forcing estimates, and highlights the need for further research to disentangle their associated climate feedbacks.

Procedures from samples to sulfur isotopic data: A review.

Sulfur isotopes have been widely used to solve some key scientific questions, especially in the last two decades with advanced instruments and analytical schemes. Different sulfur speciation and multiple isotopes analyzed in laboratories worldwide and in situ microanalysis have also been reported in many articles. However, methods of sampling to measurements are multifarious, and occasionally some inaccuracies are present in published papers. Vague methods may mislead newcomers to the field, puzzle readers, or lead to incorrect data-based correlations. We have reviewed multiple methods on sulfur isotopic analyses from the perspectives of sampling, laboratory work, and instrumental analysis in order to help reduce operational inhomogeneity and ensure the fidelity of sulfur isotopic data. We do not deem our proposed solutions as the ultimate standard methods but as a lead-in to the overall introduction and summary of the current methods used. It has been shown that external contamination and transformation of different sulfur species should be avoided during the sampling, pretreatment, storage, and chemical treatment processes. Conversion rates and sulfur isotopic fractionations during sulfur extraction, purification, and conversion processes must be verified by researchers using standard or known samples. The unification of absence of isotopic fractionation is needed during all steps, and long-term monitoring of standard samples is recommended. This review compiles more details on different methods in sampling, laboratory operation, and measurement of sulfur isotopes, which is beneficial for researchers' better practice in laboratories. Microanalyses and molecular studies are the frontier techniques that compare the bulk sample with the elemental analysis/continuous flow-gas source stable isotope ratio mass spectrometry method, but the latter is widely used. The development of sulfur isotopic measurements will lead to the innovation in scientific issues with sulfur proxies.