Sulfur Isotope Values Research Articles

Recycled mantle source for porphyry mineralization: U[sbnd]Pb and Re[sbnd]Os geochronology, and S–Pb–Cu isotopic constraints from the Urumieh-Dokhtar magmatic arc, central Iran

The Urumieh−Dokhtar magmatic arc (UDMA) hosts some of the world-class porphyry copper deposits in Iran. Here, we present high-resolution geochronological and stable isotope data to gain insights into the timing and source of the metallogeny of Kahang porphyry Cu deposit. Zircon UPb data show crystallization age of ca. 15 Ma age for the host porphyry intrusion and ReOs geochronology yields 14.5 Ma from the molybdenite associated with the ores. Sulfur isotope values on the sulphide minerals range from −1.6 ‰ to + 2.1 ‰, indicating a magmatic source for sulfur. Lead isotopic compositions of the S-bearing minerals are akin to those of the intrusive rocks, suggesting that the metal was likely sourced from mantle reservoirs. We propose a model for the UDMA involving slab break-off during the maturity of arc magmatism from the syn- to post-collisional stages of orogenesis. The δ65Cu data trace a systematic change from the barren to the fertile magmas. We suggest that partial melting of the sub-continental lithospheric mantle that has previously been refertilized of Cu through time as the potential source for the formation of ore-bearing magmas.

Genesis of the Qingchayuan Flake Graphite Deposit in the Huangling Dome of Yangtze Block, South China

The Qingchayuan flake graphite deposit is located in the Huangling Dome, which represents a part of the Yangtze Block in South China. This deposit is a major and highly typical flake graphite deposit within this metallogenic region. The graphite ores are found within graphite-bearing mica schist and graphite-bearing biotite–plagioclase gneiss. The fixed carbon content varies from 3.52 to 13.78% with an average of 7.83%. The major element analysis shows that the main chemical components of the Qingchayuan flake graphite ore are SiO2, Al2O3, TFe2O3, and K2O. The carbon isotope study of the graphite ore indicates light carbon values ranging from −22.80 to −26.72‰, suggesting that it has a biogenic origin. In addition, the sulfur isotope values of the graphite samples range from −10.67 to −14.58‰, indicating the formation of the graphite deposit is related to biological processes. The presence of traces of migmatization around the graphite deposit indicates that the graphite has undergone ultra-high temperatures during the formation process. The origin of the Qingchayuan flake graphite deposit is explained by a two-stage genetic model, which involves material deposition and regional metamorphism (including migmatization). Firstly, after the deposition of carbonaceous material and its conversion into graphite by regional metamorphism, the graphite might have undergone recrystallization, resulting in the development of big flakes due to migmatization. This model is supported by previous studies and newly collected information.

Sulfur isotopic fractionation during hydrolysis of carbonyl sulfide

Carbonyl Sulfide (OCS) is the most abundant sulfur-containing gas in the atmosphere, and it is used as a proxy for terrestrial gross primary productivity (GPP). Oceans are the major source of OCS to the atmosphere, produced by photochemical and “dark” reactions. Hydrolysis to H2S and CO2 is the major removal process of OCS from the ocean's surface. Measuring the sulfur isotope values (δ34S) and the isotopic fractionation (ε) associated with these major OCS sources and sinks could decrease the uncertainties in its fluxes. In the current study, we aim to determine the ε during the hydrolysis process of OCS (εh). We used a purge and trap system coupled to a GC/MC-ICPMS to measure δ34S values during hydrolysis under different temperatures (4–40 °C), salinities (0.2–40 g/L), and pH (4–9), representing various natural environmental conditions. In addition, we use the quantum chemical method to calculate the equilibrium εh and compare it to the empirical results. Our results for the low salinity (S =0.2 g/L; pH 8.0) water show a temperature dependency of the εh from −3.9 ‰ ± 0.2 ‰ (4 °C,) to −2.2 ± 0.6 ‰ (40 °C). The higher fractionation at low temperatures has implication for ice-core data interpretation. However, in natural seawater at 4°C and 22 °C (S = 40 g/L, pH 8.2) there was no such temperature dependency and the εh averaged −2.6 ± 0.3 ‰. Thus, it seems that salinity cancels the temperature effect close to the freezing temperature of water. Varying the pH between 4 and 9 (at 22 °C) did not result in any εh trend. Ab-initio calculations suggest that OCS hydrolysis is not controlled by equilibrium. The εh values we report will aid in quantifying the impact of OCS's hydrolysis on the observable sulfur isotopic signature of OCS in oceanic and in freshwater environments. This in turn will facilitate more accurate mass-balance calculations for the OCS budget from the ocean to the atmosphere.

The Xilaokou carbonate-sulfide vein type gold deposit: A distinct mineralization in the giant Jiaodong gold province, North China

The Xilaokou gold deposit with ca. 50 t of gold reserve @ 2.7 g/t represents a novel type (carbonate-sulfide vein type) of gold mineralization within the Jiaodong gold province. However, its mineralization age and metallogenic mechanism remain poorly constrained, hindering a comprehensive understanding of the ore-forming processes in the Jiaodong gold province. In this study, we employ syn-ore stage hydrothermal monazite in situ U-Pb geochronology to determine the ore-forming age of the Xilaokou gold deposit. Additionally, we conduct in situ LA-(MC)-ICP-MS elemental mapping and sulfur isotope analysis in ore-related pyrite to unravel the sulfur source(s) and provide new insights into the ore-forming processes of the Xilaokou gold deposit. Our findings reveal the following key points: (1) U-Pb dating of hydrothermal monazite in Au-bearing pyrite yields an ore-forming age of119.9 ± 3.0 Ma. This age is consistent with the mineralization ages (around 120 ± 5 Ma) of other gold deposits in the region, including Liaoshang-, Jiaojia-, and Linglong-type deposits. (2) Gold in pyrite primarily occurs as micro-grains (5–20 μm) within pyrite fissures associated with sphalerite and galena. (3) Elemental mapping and sulfur isotope analysis indicate that major Au mineralization is linked to elevated concentrations of As, Sb, and Tl, along with heavy sulfur isotope values (δ34S∼24.7 ‰). (4) Early-stage Au mineralization is characterized by enrichment of As, Cu, and Bi, with normal sulfur isotopic composition (δ34S∼8 ‰). We propose that the carbonate-sulfide vein type gold deposits represented by the Liaoshang and Xilaokou gold deposits in the Jiaodong gold province are genetically linked to quartz-sulfide vein and disseminated type deposits. The major ore-forming stage involved the addition of S and Au from a metamorphic massif at slightly lower temperatures. These findings highlight a new exploration direction within the North China Craton. In summary, the Xilaokou gold deposit provides valuable insights into gold mineralization processes in Jiaodong, emphasizing the importance of considering diverse deposit types and their genetic relationships in the region.

Modern plants and sulfur isoscapes - A review, discussion, and construction of a pilot δ34S isoscape for mobility and provenance studies.

Sulfur isotopes are increasingly used as mobility indicators in humans and animals in biology, archaeology, and forensics. However, there has been a lack of modern sulfur isotope baseline "isoscape" studies using modern plants and animals, largely due to the possibility of contamination of the S isotope values by modern pollution. We collected plants from across a 900-km east-west transect of British Columbia Canada and measured their sulfur isotope values. We then used a random forest model to determine which variables best explained the isotope data patterning and produced a sulfur isoscape for the southern region of British Columbia. We see clear patterning in the plant sulfur isotope values that relate to geographical location and rainfall. Our model also shows that for this study area, it is unlikely that there is a significant influence of anthropogenic pollution on plant δ34S values. We also discuss the use of plants as a substrate for sulfur isoscapes and possible explanations for the often-observed difference between plant and animal δ34S values from the same region, related to differing sources of sulfur in plants compared to amino acids in human and animal tissues. We found that for areas of the world where sulfur pollution is likely less widespread, it is possible to produce a modern plant S isoscape that should be an accurate baseline for mobility studies. Using random forest modelling, we have produced a baseline sulfur isoscape map of southern British Columbia that can be used for ecology, forensic and archaeological studies.

Barite Replacement as a Key Factor in the Genesis of Sediment-Hosted Zn-Pb±Ba and Barite-Sulfide Deposits: Ore Fluids and Isotope (S and Sr) Signatures from Sediment-Hosted Zn-Pb±Ba Deposits of Iran

Iran hosts more than 350 Precambrian to Cenozoic sediment-hosted Zn-Pb±Ba and barite-sulfide deposits, including shale-hosted massive sulfide (SHMS, also called SEDEX) and Irish-type and Mississippi Valley-type (MVT) mineralization, and barite is a common mineral in these deposits. In the SHMS deposits, barite is typically found as fine-grained disseminations in thin laminae. In these deposits, the sulfide laminae often occur as diagenetic replacements and as bands containing authigenic and diagenetic barite and pyrite framboids. In the Irish-type Zn-Pb-Ba and stratabound barite-sulfide deposits, barite exhibits various textures, including fine-grained disseminated barite, banded zebra textures, veins, and massive barite lenses. In some of the giant Irish-type deposits, as well as in the stratabound barite-sulfide mineralization, the main stratabound sulfide ore is developed within a barite envelope and is characterized by the replacement of barite and pyrite by chalcopyrite, galena, and sphalerite. In the MVT deposits, the formation of barite is often related to dolomitization, and sulfide mineralization involves the replacement of the dolomitized carbonate rocks, as well as associated barite. Fluid inclusion studies on the Irish-type deposits indicate that the temperatures and salinities of the sulfide-forming fluids are higher compared to those of the barite-forming fluids. Fluid inclusion analyses of coarse-grained barites from Irish and MVT deposits reveal their hydrothermal origin. The δ3⁴S values of sulfide minerals (pyrite, sphalerite, and galena) in Irish-type deposits exhibit a broad range of low values (mostly −28 to +5‰), primarily revealing a process of bacterial sulfate reduction (BSR). However, the textures (replacement, colloform, and banded) and more positive sulfur isotope values (+1 to +36‰) in the SHMS Zn-Pb deposits suggest that bacterial sulfate reduction (BSR) plays a less significant role. We suggest that thermochemical sulfate reduction (TSR) connected to the direct replacement of barite plays a more relevant role in providing sulfur for the sulfide mineralization in the SHMS, barite-sulfide, and MVT deposits. Based on the textual evidence, sulfur isotopic data, and fluid inclusion studies, barite has been identified as a key controller for the subsequent Zn-Pb mineralization by providing a suitable host and significant sulfur contribution in the sediment-hosted Zn-Pb and stratabound barite-sulfide deposits. This implies that diagenetic barite might be a precursor to all types of sediment-hosted Zn-Pb mineralization.

Genesis of the Hajibolagh-Zalibolagh Cu-(Ag) intermediate-sulfidation epithermal deposit, Urumieh-Dokhtar magmatic arc, Iran: Evidence from ore geology, fluid inclusions, and stable isotopes

The Hajibolagh-Zalibolagh deposit located northeast of the city of Saveh in the central part of the Urumieh-Dokhtar magmatic arc of Iran, demonstrates vein and breccia vein style copper-(silver) mineralization hosted by Eocene volcano-sedimentary rocks. The main mineralization stage can be divided into four phases, respectively (1) jasperoid + quartz veins, chalcopyrite, and pyrite; (2) quartz veins along with chalcopyrite, bornite, chalcocite, arsenopyrite, and pyrite; (3) quartz-barite veins along with chalcopyrite, bornite, chalcocite and pyrite; and (4) veins of quartz, calcite, hematite, and oligist along with a small number of copper sulfides. The main stages of mineralization are cut by barren post-ore quartz and calcite veinlets. As a result of supergene processes, minerals are oxidized, and malachite, azurite, chrysocolla, chalcocite, covellite, goethite, and hematite are formed, presenting an important exploration guide. The hydrothermal alteration from the center of the vein-veinlets to the outside includes, respectively, silicification, sericitization, intermediate argillic, and propylitic. The average salinity and homogenization temperature (Th) of fluid inclusions is 14.2 wt% NaCl equiv. and 288 °C, respectively. The coexistence of the vapor phase, liquid-rich phase, and halite-bearing fluid inclusions is a sign of boiling in this hydrothermal system, which has contributed to copper saturation. Sulfur isotope values for pyrite, chalcopyrite, chalcocite, and bornite are mainly from –0.16 to 2.98 ‰, indicating a probable magmatic source for sulfur. Boiling, dilution, and mixing are the mechanisms for the ore deposition and facilitated the mineralization. The Hajibolagh-Zalibolagh deposit shows the highest similarity to intermediate-sulfidation epithermal deposits. The best environment for the mineralization and fluid circulation in these epithermal deposits is the intersection of faults with the Eocene volcanic and volcano-sedimentary rocks.

Amino acid-specific isotopes reveal changing five-dimensional niche segregation in Pacific seabirds over 50 years

Hutchison’s niche theory suggests that coexisting competing species occupy non-overlapping hypervolumes, which are theoretical spaces encompassing more than three dimensions, within an n-dimensional space. The analysis of multiple stable isotopes can be used to test these ideas where each isotope can be considered a dimension of niche space. These hypervolumes may change over time in response to variation in behaviour or habitat, within or among species, consequently changing the niche space itself. Here, we use isotopic values of carbon and nitrogen of ten amino acids, as well as sulphur isotopic values, to produce multi-isotope models to examine niche segregation among an assemblage of five coexisting seabird species (ancient murrelet Synthliboramphus antiquus, double-crested cormorant Phalacrocorax auritus, Leach’s storm-petrel Oceanodrama leucorhoa, rhinoceros auklet Cerorhinca monocerata, pelagic cormorant Phalacrocorax pelagicus) that inhabit coastal British Columbia. When only one or two isotope dimensions were considered, the five species overlapped considerably, but segregation increased in more dimensions, but often in complex ways. Thus, each of the five species occupied their own isotopic hypervolume (niche), but that became apparent only when factoring the increased information from sulphur and amino acid specific isotope values, rather than just relying on proxies of δ15N and δ13C alone. For cormorants, there was reduction of niche size for both species consistent with a decline in their dominant prey, Pacific herring Clupea pallasii, from 1970 to 2006. Consistent with niche theory, cormorant species showed segregation across time, with the double-crested demonstrating a marked change in diet in response to prey shifts in a higher dimensional space. In brief, incorporating multiple isotopes (sulfur, PC1 of δ15N [baselines], PC2 of δ15N [trophic position], PC1 and PC2 of δ13C) metrics allowed us to infer changes and differences in food web topology that were not apparent from classic carbon–nitrogen biplots.

Contrasting trophic transfer patterns of cadmium and mercury in the Arctic marine food web of east Hudson Bay, Canada

We investigated trophic transfer of cadmium (Cd) through an Arctic marine food web in Hudson Bay and compared it with mercury (Hg), a metal known to strongly biomagnify. We evaluated blue mussel, sea urchin, common eider, sculpin, Arctic cod, and ringed seal for the influence of dietary and biological variables on variation in Cd and Hg concentrations. Age and size influenced metal concentrations among individuals within a vertebrate species. Consumer carbon and sulfur isotope values were correlated with their Cd and Hg concentrations, indicating habitat-specific feeding influenced metal bioaccumulation. Trophic transfer patterns for Cd depended on the vertebrate tissue, with food web biodilution observed for the muscle but not the liver. Liver Cd concentrations were higher in ringed seal and some common eider relative to prey. In contrast, we observed mercury biomagnification for both tissues. Tissue- and species-specific physiology can explain discrepancies of Cd trophic transfer in this Arctic marine food web.

Sediment‐hosted disseminated gold mineralization at the Gegalaw deposit in Central Myanmar

AbstractGegalaw is one of the gold deposits situated in the Sagaing Fault zone, which marks the boundary between the Central Myanmar Basin to the west and the Mogok metamorphic belt to the east. The gold mineralization is mainly confined along northeast striking faults between carbonaceous silty limestone of the Kywethe Chaung Formation and carbonaceous and calcareous shale of the Eocene Male Formation. Hydrothermally induced dissolution breccia associated with progressive silica replacement increase near the northeast trending faults. The hydrothermal alteration associated with the mineralization is silicification in addition to illite‐kaolinite argillic alteration, of which illite is dated by the K‐Ar method as 40.26 ± 0.91 Ma. Sulfide minerals contained in the ores are mainly pyrite and arsenopyrite, with minor to trace amounts of marcasite, chalcopyrite, and sphalerite, among which pyrite and arsenopyrite are the hosts of gold. Pyrite and arsenopyrite are divided into diagenetic and hydrothermal stages, based on their mineral textures. Diagenetic stage pyrites are framboidal (Py1A) and coalescent framboidal (Py1B). Those of the hydrothermal stage are zoned pyrite with porous cores (Py2) and compact rims (Py4). In addition, euhedral homogeneous pyrites with or without compact rim are present (Py3). Some pyrites show pseudomorphs of ilmenite (Py3i) and carbonate minerals, possibly ankerite (Py3c). Arsenopyrites are also divided into porous, sooty arsenopyrite (Apy1), and compact arsenopyrite (Apy2) that co‐exists with Py3 and Py4 pyrites. Electron probe microanalysis for sulfides indicates that Py1A and Py1B are deficient in Fe while Py2, Py3 and Py4 are deficient in S compared to stoichiometry of pyrite. Such deficiencies are compensated by metal ions such as Co2+ and Ni2+ for Py1A, As2+ for Py1B, and As1− for Py2, Py3, and Py4. Arsenic equilibrium temperature of Apy2‐Py3 pairs shows a mode range of 250–270°C. Detected gold concentrations (~650 ppm) in arsenian pyrite (Py2, Py3, and Py4) indicate that gold in pyrite are below the solubility, suggesting that gold is present as solid‐solution in pyrite. Sulfur isotopic values of the pyrites in the unaltered host rocks are −18.9‰ and −8.9‰, and those of the pyrites from the hydrothermal altered rocks range from −17.3‰ to −0.5‰. These similar negative δ34S ranges of the pyrites suggest that the source of sulfur is dominated in biogenic reduction origin. Nevertheless, the two relatively heavier sulfur isotopic values (−4.9‰ and −0.5‰) suggest a contribution of an external hydrothermal fluid source. The research results indicate that gold mineralization occurred by infiltration of auriferous reduced hydrothermal fluids into the carbonaceous silty limestone and carbonaceous and calcareous shale through northeast trending secondary faults of the dextrally moving Sagaing Fault system and the fluids reacted with framboidal pyrite as well as iron‐bearing minerals in the host rocks to precipitate gold‐bearing arsenian pyrite. The age of hydrothermal illite suggests a link to the right‐lateral strike‐slip movement of the Sagaing Fault that is related to the collision of the Indian and Asian plates.

Similarities in Storage and Transport of Sulfate in Forested and Suburban Watersheds, Despite Anthropogenically Elevated Suburban Sulfate

AbstractSulfate is a potential pollutant and important nutrient linked with the nitrogen, carbon, and phosphorus cycles. The importance of different anthropogenic sulfate sources in suburban streams (septic systems, fertilizer, road salt, and infrastructure) is uncertain, and the temporal dynamics of stream export sparsely documented. We study sources and export dynamics of sulfate in suburban and forested headwater catchments. Stream baseflow discharge and sulfate concentrations were strongly positively correlated in both watersheds with the highest values in spring. Suburban concentrations and fluxes (2.48–7.5 mg/L or 25.8–78.1 μM, 16.6 kg/ha/yr) were consistently higher than forested (0.56–2.78 mg/L or 5.8–28.9 μM, 5 kg/ha/yr). Following precipitation, sulfate concentrations in both forested and suburban streams increased to concentrations above pre‐storm values and remained high after peak discharge. These dynamics suggest that both catchments have a large pool of sulfate that can be mobilized under wet conditions. Ridge‐top forest soil samples contained 210 kg/ha stored, extractable sulfate. Current atmospheric sulfate deposition rates (5–7 kg/ha/yr) are approximately in balance with sulfate export in the forested stream. In the suburban watershed, we estimated septic fields contribute up to 11 kg/ha/yr (about half from surfactants) and lawn care up to 4.3 kg/ha/yr and are the most likely sources of elevated stream sulfate. Sulfate sulfur (4.9–5.8‰ forested; 6.1–7.0‰ suburban) and oxygen isotope values (0.7–2.0‰ forested; −0.1–4.1‰ suburban) are consistent with this interpretation, but do not provide strong corroboration due to large variation and overlap in estimated source values.

In situ trace elements and sulfur isotope analyses of layered sphalerite as a record of ore-forming processes in the world-class Jinding sediment-hosted Zn-Pb Ore Deposit, China

The Jinding deposit is well-known to contain high concentrations of metals Zn, Pb, Cd, Tl, Ag, etc. in the world. The associated critical metals and their substitution mechanisms were wildly concerned. This study investigated and compared sphalerites using a combination of textural, trace element, and sulfur isotopic analyses to give insights into element substitution mechanisms and possible sources of ore-forming fluids and to constrain processes involved in ore genesis of the world-class Jinding sediment-hosted Zn-Pb deposit. LA-ICP-MS analyses reveal chemical zoning in the sphalerites together with the coupling of two main groups of trace elements substitution mechanisms: one is Fe + Ge + Mn + Pb + As + Tl and vacancies to substitute Zn, and the other is Cd + Cu + Ag + Sb to substitute Zn. The incorporation of trace elements is facilitated by the replacement of Zn by Cd and Fe. These two group elements have distinct color oscillatory zonation and are intertwined in the trace element LA-ICP-MS element maps. The sulfur isotopic values show high isotope fractionation in the sphalerite from −28.4 to −0.5 ‰, suggesting a bacteriogenic sulfur origin at Jinding. Sphalerite sample has observed that sulfur isotope is correlated with Fe concentration and anti-correlated with Cd concentration. These variations in isotope fractionation and trace element disequilibrium partitioning were interpreted as the effects of temperature and pH with less influence from sulfur activity. These variability zones of sphalerite alternately enriched in Cd- and Fe-related elements suggested that ore fluids may flow from metal-fertile sedimentary/basement sequences during their ascent, and colloform sphalerite was likely formed by a high degree of supercooling, over-saturation, and rapid mixing between bacteriogenic sulfur and metal-rich in spaces of collapse dome. Based on our observations, we suggested that these variability zones of layered sphalerite alternately enriched in Cd and Fe would likely provide useful insight for a potential economic Zn-Pb and associated critical metals mineral exploration deposit.

Evidence for high-frequency oxygenation of Ediacaran shelf seafloor during early evolution of complex life

Increasing oxygenation of the early Ediacaran Ocean is thought to have been responsible for the emergence of early animals. Although geochemical studies have suggested periods of oceanic oxygenation in the Ediacaran, direct evidence for seafloor oxygenation has been lacking. Here, we report frequent occurrences of distinctive, sub-millimetric, and early diagenetic pyrite-marcasite rosettes in phosphorites from the lower Ediacaran Doushantuo Formation (Weng’an, South China). They typically consist of a nucleus of framboidal pyrite, a cortex of radiating marcasite blades intergrown with quartz, and a rim of second-generation pyrite, recording partial oxidative dissolution of pyrite and co-precipitation of marcasite and quartz. This inference is further supported by near-zero carbon isotope values of the host dolostone, similarly low sulfur isotope values for pyrite and marcasite, and evident Fe-isotope fractionation between marcasite and pyrite. Collectively, our findings reveal intermittent bottom-water and porewater oxygenation events, providing direct evidence of high-frequency oxygenation of Ediacaran continental shelves.

Variability of sulfur and oxygen isotope values within wet precipitation and its correlation with diminished anthropogenic sulfur dioxide (SO2) emission

Atmospheric sulfate (SO42−) aerosols have the capacity to scatter solar radiation, thus exerting a cooling effect on the climate. It is widely acknowledged that SO42− deposition significantly contributes to ecosystem effect in aquatic and terrestrial environments worldwide. Over the course of several decades, considerable efforts have been undertaken to mitigate anthropogenic sulfur dioxide (SO2) emissions in China, leading to remarkably low SO2 concentrations. Nevertheless, the implications of reduced anthropogenic SO2 emission on atmospheric sulfate transformation and compositions of isotope values (δ34S-SO42–, δ18O-SO42–) remain inadequately understood. To address this knowledge gap, we conducted multiple rainfall sampling instances between 2010 and 2022 (n = 191), encompassing the period of transitioning anthropogenic SO2 emission from high to low levels. Remarkably, we observed a significant reduction in the volume-weighted mean value (VWMV) of SO42− concentrations, declining from 20.86 mg L−1 in 2010 to 2.41 mg L−1 in 2022, and the VWMV of SO42−/NO3− molar ratios also decreased from 12.90 in 2010 to 0.55 in 2022, reflecting the synchronously decreasing annual SO2 emissions and annual SO2 concentrations from 2010 to 2022. In contrast to the declining trends in VWMV of SO42− concentrations, the VWMV of δ34S-SO42– values exhibited a different pattern from 6.6‰ in 2010 to −0.1‰ in 2017 and slightly increased to 2.5‰ in 2022. Furthermore, the VWMV of δ18O-SO42– values demonstrated an increase from 8.8‰ in 2010 to 14.5‰ in 2018, but subsequently decreased to 5.4‰ in 2022. We attributed the sharply dropping VWMV of δ34S-SO42– values to the reduction in the input of primary sulfate with enriched δ34S-SO42– values. The strict desulfurization reduced SO2 emissions, leading to oxidation of these trace SO2 with negative δ34S values, resulting in low sulfate concentrations and negative δ34S-SO42– values. In addition, the monthly average δ18O-SO42– values exhibited a positive correlation with monthly mean δ18O-H2O values (p < 0.05), strongly indicating the water incorporation during SO2 heterogeneous oxidation. More importantly, during spring rainfall, positive δ18O-SO42– values but relatively negative δ34S-SO42– values were influenced by SO2 heterogeneous oxidation facilitated by air oxygen catalyzed under metal ions in dry weather condition, attributed to the low relative humidity (RH) coupled with high deuterium excess (dexcess) values. Conversely, in summer, negative δ18O-SO42– values but relatively positive δ34S-SO42– values resulted from the SO2 heterogeneous oxidation with H2O2 due to high RH and low dexcess values. Moreover, the VWMV of δ18O-H2O exhibited variations from −3.7‰ in 2019 to −9.7‰ in 2021, and displayed a positive correlation with annual temperature (p < 0.01) and a negative correlation with annual precipitation (p < 0.05), making it a valuable indicator of climate change alongside δ18O-SO42– values. Our findings underscore the importance of continued monitoring of atmospheric wet depositions in response to changes in anthropogenic SO2 emission activities. Furthermore, they highlight the substantial impact of variations in δ34S values of SO2 and primary sulfate on rainwater sulfate concentrations and isotope values.

Isotopic niche overlap among foraging marine turtle species in the Gulf of Mexico.

Sympatric species may overlap in their use of habitat and dietary resources, which can increase competition. Comparing the ecological niches and quantifying the degree of niche overlap among these species can provide insights into the extent of resource overlap. This information can be used to guide multispecies management approaches tailored to protect priority habitats that offer the most resources for multiple species. Stable isotope analysis is a valuable tool used to investigate spatial and trophic niches, though few studies have employed this method for comparisons among sympatric marine turtle species. For this study, stable carbon, nitrogen, and sulfur isotope values from epidermis tissue were used to quantify isotopic overlap and compare isotopic niche size in loggerhead (Caretta caretta), green (Chelonia mydas), and Kemp's ridley (Lepidochelys kempii) turtles sampled from a shared foraging area located offshore of Crystal River, Florida, USA. Overall, the results revealed high degrees of isotopic overlap (>68%) among species, particularly between loggerhead and Kemp's ridley turtles (85 to 91%), which indicates there may be interspecific competition for resources. Samples from green turtles had the widest range of isotopic values, indicating they exhibit higher variability in diet and habitat type. Samples from loggerhead turtles had the most enriched mean δ34S, suggesting they may forage in slightly different micro-environments compared with the other species. Finally, samples from Kemp's ridley turtles exhibited the smallest niche size, which is indicative of a narrower use of resources. This is one of the first studies to investigate resource use in a multispecies foraging aggregation of marine turtles using three isotopic tracers. These findings provide a foundation for future research into the foraging ecology of sympatric marine turtle species and can be used to inform effective multispecies management efforts.

Wet feet: developing sulfur isotope provenance methods to identify wetland inhabitants.

The stable isotopes of sulfur provide a distinctive signature for marine proximity and interaction. Exploring coastal proximity has been the principal application of sulfur isotopes in archaeology and palaeoecology, but this deals only with high (greater than 14‰) isotope values, meaning little interpretation has been gained from lower values. Progress has been hindered by issues with biosphere mapping. Air pollution can impact modern landscapes, significantly lowering sulfur isotope baselines, leading to the assumption that modern vegetation-based sulfur maps are not reliable. This research explores the potential of previously undiagnostic low, and often, negative sulfur isotope values for identifying wetland dwellers. Impervious clays that support wetlands are distinctive ecosystems and this study tests the hypothesis that they will produce low isotope values owing to both the underlying substrate and to redox conditions. Primary mapping of targeted areas using modern plants highlights zones with natural negative sulfur values and demonstrates that this constitutes a distinctive wetland signature. Analysis of modern and archaeological fauna demonstrates that these distinctive isotope compositions are transferred into the food chain. These findings propel the interpretative potential of sulfur isotopes forward and add to the growing knowledge to provide means for identifying archaeological humans and animals raised in wetlands.

In Situ Rb‐Sr Dates of Muscovite and Sulfur Isotope of Pyrite from the Yangshan Gold Deposit in Western Qinling, China

AbstractLocated along the southern part of the West Qinling orogenic belt, the Yangshan gold deposit is one of the largest in China. The major gold ores of Yangshan are disseminated in metasedimentary host rocks with minor native gold amounts in stibnite‐gold quartz veins. Pyrite and arsenopyrite are the major Au‐bearing minerals. Hydrothermal muscovite from gold‐bearing quartz veins was dated using the in situ Rb‐Sr method to determine the formation age of the Yangshan gold deposit. The Rb‐Sr isochron date of the muscovite yielded 210.1 ± 5.6 Ma (MSWD = 1.2). This date is near the lower end of the period of the mineralized granitic dykes (210.49–213.10 Ma). Two stages of gold enriching process are recognized in the gold‐bearing pyrite: the first is incorporated with the Co, Cu, As, Ni enrichment; and the second is accompanied by Bi, Co, Ni, Pb, Cu, Sb concentration. The in‐situ sulfur isotopic values of pyrites show a restricted Δ34s range of –1.43 ‰ to 2.86 ‰ with a mean value of 0.43 ‰. Trace‐element mapping and in‐situ sulfur isotopic analysis of pyrite suggest that the sulfur deposits are likely derived from a magmatic source and likely assimilated by sulfur from the sedimentary bedrock. Thus, magmatism plays a critical role in the formation of the Yangshan gold deposit.

Geology, Pb and S Isotope Geochemistry, and Genesis of the Na Bop-Pu Sap Lead-Zinc Deposit in the Cho Don area, Northeastern Vietnam

The Na Bop-Pu Sap Pb-Zn ore bodies represent a typical vein-type lead-zinc deposit situated in the Cho Don area and are currently being extracted for their lead and zinc resources. This deposit is characterized by its significant scale and quality and is considered one of the prominent lead-zinc deposits in the Cho Don area. Despite its significance, this deposit has not received adequate attention, resulting in limited knowledge of its geology, mineralization, and deposit genesis model. To address this knowledge gap, our study utilized several methodologies, including field surveying, ore mineral analysis under a microscope, and S and Pb isotopic geochemistry. By employing these approaches, we were able to obtain specific insights into the origin of mineralization and the deposit model. Our field survey suggests that the ore deposits are formed as Pb-Zn-bearing veins along Devonian shale, claystone, and limestone faults. Microscopic analyses of the veins reveal the presence of galena, sphalerite, chalcopyrite, pyrite, arsenopyrite, and pyrrhotite as ore minerals, and quartz, calcite, dolomite, and chalcedony as gangue minerals. Sulfur-isotope values (δ34SCDT) of galena 5.3 to 0.1‰ (average 2.8‰), sphalerite 6.8 to 2.5‰ (average 5.3‰), and pyrite 5.8 to 4.1‰ (average 4.9‰) indicate that the sulfide mineralization may be related to a deep source, possibly originating from magmatic activity in the region and contaminated by carbonate-bearing marine sedimentary rocks. Lead-isotope studies indicate a model age of 598-424 Ma for the lead reservoir, consistent with the possible presence of local source rocks containing sulfur. The lead and sulfur in the ore veins were probably contaminated by Devonian carbonate-bearing marine sedimentary rocks and leached from Neoproterozoic to Cambrian magmatic activity. The lead-zinc deposits in Na Bop-Pu Sap do not display any Mississippi valley-type (MVT) or Sedimentary exhalative (SEDEX) lead-zinc deposit characteristics, as they appear to be related to shear zone-hosted lead-zinc deposits.

New insights on the formation of the Jingchong Cu-Co-Pb-Zn deposit, South China: Evidence from sphalerite mineralogy and muscovite 40Ar-39Ar dating

The northeastern Hunan Province hosts numerous hydrothermal Pb-Zn(-Cu-Co) polymetallic deposits. As a representative example, the Jingchong Cu-Co-Pb-Zn deposit is characterized by the lower Cu-Co and upper Pb-Zn mineralization, whereas little is known about Pb-Zn mineralization. In this study, three generations of sphalerite were identified based on their textural and geochemical differences. The Sph-I exhibits the oscillatory zoning that consists of reddish-brown Sph-Ia (poor in chalcopyrite inclusion) alternating with dark Sph-Ib with zoned chalcopyrite inclusion. Sph-II is composed of honey-brown Sph-IIa (abundant chalcopyrite droplets) and white clean Sph-IIb (rare chalcopyrite inclusion). The black Sph-III is characterized by nano- to submicron-sized chalcopyrite inclusions with typical “dusting” or “watermelon” texture and crosscuts all other sphalerite generations in veinlets. The electron microprobe and laser ablation inductively coupled plasma mass spectrometry show that Sph-I has higher Fe and Mn contents, but lower Cd, Cu and Ag contents than Sph-II and Sph-III. Sphalerite geothermometry yields temperatures of 334–346 (±58)°C for Sph-I, 254–289 (±60)°C for Sph-II and 286 (±55) °C for Sph-III. The sulfur fugacity ranges from logfS2 values of −9.03 to −8.26 for Sph-I to −11.77 to −10.63 for Sph-II and −10.82 for Sph-III. The combined textural features and chemical compositions indicate that the self-organized mechanism forms Sph-I, and that the coupled dissolution and precipitation reactions triggered by the influx of Cu-elevated fluids are responsible for the formation of Sph-II and Sph-III. The associated pyrite and pyrrhotite inclusions in sphalerite are produced by the exsolution mechanism, while chalcopyrite inclusions are formed by co-precipitation due to local supersaturation at the interface of sphalerite with fluid. The 40Ar-39Ar dating of muscovite in the Jingchong deposit yields a mineralizing age of ca. 121.1 ± 2 Ma, consistent with the ca. 130–120 Ma Pb-Zn mineralizing events in the northeastern Hunan Province. The sulfur isotopic values (−3.0 to +3.5‰) of the Pb-Zn ores are similar to that of Cu-Co ores, indicating a magmatic sulfur origin. Together with the trace element affinity of sphalerite with magmatic-hydrothermal origin, it was proposed that the Jingchong Pb-Zn and Cu-Co mineralization were formed in the same magmatic-hydrothermal system. The placement of Pb-Zn orebodies at the upward zoning of Cu-Co orebodies could be attributed to the higher solubilities of Pb and Zn chloride complexes in hydrothermal fluids, relative to Cu chloride complex.

Rapid evaluation of organic and pyritic δ34S values in immature sedimentary rocks using a Rock-Eval 7S® coupled to MC-ICPMS

Sulfur isotopic values (δ34S) in sedimentary organic matter and pyrite provide essential information about the global S cycle. The measurement of δ34S values is commonly used to reconstruct paleo-environmental conditions of sediment deposition. In petroleum geochemistry, δ34S values are used to trace relationships between disparate elements of petroleum systems. However, the determination of organic and pyrite δ34S values requires a tedious and time-consuming (weeks) stepwise procedure. Here we used the latest version of the Rock-Eval® 7S analyzer, which can quantify different S-fractions in sedimentary rocks. We have coupled the Rock-Eval® pyrolysis cycle with a multi-collector inductively coupled plasma mass spectrometer (RE/MC-ICPMS). The analysis requires a small sample size (5 to 90 mg), and minimum sample preparation of acid treatment to avoid the carbonate effect on the pyrolyzed pyrite-S. The RE/MC-ICPMS system allows for measuring the pyrolysable organic-S and pyrite-S and directly determining δ34S values from a decarbonated rock. The new method was applied to a set of immature sedimentary rocks of various paleoenvironmental origins and geographic locations. The rapid analysis by the RE/MC-ICPMS, which takes only 20 min per sample, achieved an average precision of 0.5‰, for peaks above 5 nanomole of S. Accuracy was determined relative to a common wet chemistry method followed by an offline EA-IRMS analysis and reached an agreement of <1‰.