Sulfur Isotope Measurements Research Articles

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.

Genesis of copper mineralization in the polymetallic tin deposits from the Herberton Mineral Field, Queensland, Australia

The Herberton Mineral Field hosts multiple small-scale, polymetallic Sn-Cu and Sn-Zn deposits. The Baal Gammon and Isabel polymetallic deposits in the Herberton Mineral Field contain early Sn that is overprinted by sulfides. At Baal Gammon, the sulfide overprinting is Cu-In-rich, whereas Isabel is a Zn-Pb-In-rich system. These deposits are hosted in the meta-sedimentary rocks of the Hodgkinson Formation and the porphyry dikes and volcanic rocks of the Kennedy Igneous Association. Primary Sn in these deposits occurs as cassiterite, which was altered to stannite during sulfide mineralization. The sulfide ores from Baal Gammon consist of chalcopyrite, pyrrhotite, and minor sphalerite, and sphalerite, galena, and minor chalcopyrite are observed at Isabel. Chalcopyrite from Baal Gammon contains on average 609 ppm Ag, 1194 ppm In, and 1410 ppm Sn, whereas chalcopyrite from the Isabel deposit contains on average 2302 ppm Ag, 725 ppm In, and 1042 ppm Sn. Sulfur isotope (δ34S) measurements of in-situ chalcopyrite-pyrrhotite mineral pairs show limited variation and low values that are indicative of a magmatic sulfur source with limited interaction with sulfur from connate and meteoric fluids during mineralization. The chalcopyrite and pyrrhotite δ34S values at the Baal Gammon deposit vary between 0.99–1.91‰ and 1.35–2.48‰, respectively. The δ34S values at the Isabel deposit vary between 0.91–1.45‰ for chalcopyrite and 1.12–2.11‰ for pyrrhotite. The trace element composition of major sulfides and sulfur isotopes of chalcopyrite and pyrrhotite combined with thermodynamic modeling indicates that the mineralizing fluids at the Baal Gammon and Isabel deposits have an igneous source, where the metals were transported as metal-chloride complexes at low pH (< 5) and below ~ 300 °C. The source of these sulfide-rich mineralizing fluids is most likely derived from the magmatic activity associated with the emplacement of the Slaughter Yard Creek Volcanics during a period of crustal thinning between 300 and 280 Ma.

Sulfur isotopes quantify the impact of anthropogenic activities on industrial-era Arctic sulfate in a Greenland ice core

Anthropogenic sulfate aerosols are estimated to have offset 60% of greenhouse-gas-induced warming in the Arctic, a region warming four times faster than the rest of the world. However, sulfate radiative forcing estimates remain uncertain because the relative contributions from anthropogenic versus natural sources to total sulfate aerosols are unknown. Here we measure sulfur isotopes of sulfate in a Summit, Greenland ice core from 1850 to 2006 CE to quantify the contribution of anthropogenic sulfur emissions to ice core sulfate. We use a Keeling plot to determine the anthropogenic sulfur isotopic signature (δ34Santhro = +2.9 ± 0.3 ‰), and compare this result to a compilation of sulfur isotope measurements of oil and coal. Using δ34Santhro, we quantify anthropogenic sulfate concentration separated from natural sulfate. Anthropogenic sulfate concentration increases to 67 ± 7% of non-sea-salt sulfate (65.1 ± 20.2 µg kg−1) during peak anthropogenic emissions from 1960 to 1990 and decreases to 45 ± 11% of non-sea-salt sulfate (25.4 ± 12.8 µg kg−1) from 1996 to 2006. These observations provide the first long-term record of anthropogenic sulfate distinguished from natural sources (e.g. volcanoes, dimethyl sulfide), and can be used to evaluate model characterization of anthropogenic sulfate aerosol fraction and radiative forcing over the industrial era.

The Sulfur Isotopic Characteristics of Evaporites in the Yarkand Basin of Xinjiang Province in the Paleocene and Its Paleoenvironmental Evolution

The Yarkand Basin, located in the southwest of the Tarim Basin, is a northeastern part of the eastern Paratethys ocean in the Paleocene, and a significant amount of evaporites, with gypsum, anhydrite, and halite as the main types, were developed in this area. These evaporites record the sedimentary environment at that time. A study was conducted on the sulfur isotopic composition of gypsum in the Paleocene of the Yarkand Basin to explore the origin of the evaporites and interpret the sedimentary environment. The experimentally measured sulfur isotope δ34SCDT values of 187 gypsum samples ranged from 6.69‰ to 25.92‰ with an average value of 18.64‰. The overall trend of the Paleocene gypsum sulfur isotopic curve is consistent with the global seawater sulfur isotopic curve, which shows a decreasing trend. In the early and middle Paleocene, the curve shows four stages of sulfur isotope increase, indicating that the sedimentary environment during that time was mainly influenced by bacterial reduction and a relatively open sedimentary environment, while the late period shows a decreasing trend, suggesting that the late period may be primarily influenced by terrigenous freshwater. In addition, the sulfur isotope value has the characteristics of decreasing from northwest to southeast of the basin, which may indicate that the sedimentary environment of Paleocene evaporites in the Yarkand Basin may also be related to paleotopography and distance from the estuary, resulting in differences in sedimentary environments. The mainly original sulfur isotope values of the Paleocene evaporites in the Yarkand Basin should be in the range of 18‰–20‰, which is a supplement to the Paleocene global paleoseawater and is of great significance for the reconstruction of the marine transgressive–regressive cycle and sulfur isotopic composition of the eastern Paratethys ocean during this period.

Toward the Origins of Quadruple Sulfur Isotope Anomalies in Modern Sulfate: A Multitracer Approach and Implications for Paleo- and Planetary Atmospheres

Sulfur isotope mass-independent fractionation signatures (S-MIF) have been widely found in modern sulfate aerosols. Their mechanistic origins and potential implications for atmospheric sulfate formation chemistry are however poorly understood. Of particular importance is that the mystery of modern sulfate S-MIF hinders precise interpretations of S-MIF in geological sediment and meteorite samples. Here, we examine several proposed origins of modern sulfate S-MIF using a multiple-tracer approach. Quadruple sulfur isotopes of sulfate aerosols collected from Guangzhou, a megacity in South China, were measured along with various chemical and isotopic tracers for high-altitude air masses, biomass burning, and mineral dusts in the same samples. Similar to previous studies, we found that negative Δ36S values in modern sulfate aerosols are linked to combustions, and to a larger extent, to high-temperature processes that may involve symmetry-dependent recombination reactions of sulfur. The origins of Δ33S anomalies widely observed in modern sulfate aerosols remain elusive and require further investigation before we can unambiguously use this proxy to quantify sulfur emission and transformation pathways in the modern atmosphere. From a comparative planetology perspective, we highlight that a complete understanding of S-MIF in modern aerosols is crucial for tracking paleo- and planetary atmospheres by multiple sulfur isotope measurements in Phanerozoic sediments and Martian meteorites because their S-MIF magnitudes are similar.

Giant Mesozoic gold ores derived from subducted oceanic slab and overlying sediments

Orogenic gold deposits account for more than 30 % of the global gold resources. To understand the genesis of orogenic gold deposits and ultimately target new orogenic gold deposits, it is important to determine the origin of gold. However, there has been a continuing debate surrounding gold source reservoirs. The Jiaodong gold province, comprising ore hosted within Mesozoic granitoids that intruded Archean metamorphic rocks, together with other gold occurrences in the North China block, collectively constitute the only Mesozoic world-class gold resource in a Precambrian basement. This geological setting, with young deposits in ancient rocks, offers a great opportunity to better determine the gold source because it allows us to fingerprint the isotopically distinct reservoirs. Specifically, it is possible to determine whether the mass-independent isotopic fractionation sulfur (MIF-S)-bearing Archean supracrustal rocks that form the lower crust are a permissive source. We present multiple sulfur isotope (δ34S and Δ33S) measurements of pyrite grains (n = 161) from 18 gold deposits in the six main districts of the Mesozoic Jiaodong gold province. Gold-associated pyrite grains yield non-MIF-S signatures (Δ33S = 0 ‰), indicating that Archean metasedimentary rocks are not a source reservoir of sulfur and gold. The isotopically heavy S (average δ34S = +9.0 ± 3.7 ‰, 2SD) demonstrates a sulfur contribution from a subducted oceanic slab and, in particular, its overlying sediments while excluding mantle and magmatic sources. The subduction-related metamorphism released appreciable gold and sulfur from the top of the downgoing slab into aqueous-carbonic fluids that ascended into the upper plate along crustal structures traversing a tectonically thinned crust. Here, we demonstrate that these giant Mesozoic orogenic gold deposits sourced gold and sulfur during subduction-related devolatilization reactions.

Underestimated Passive Volcanic Sulfur Degassing Implies Overestimated Anthropogenic Aerosol Forcing

AbstractThe Arctic is warming at almost four times the global rate. An estimated sixty percent of greenhouse‐gas‐induced Arctic warming has been offset by anthropogenic aerosols, but the contribution of aerosols to radiative forcing (RF) represents the largest uncertainty in estimating total RF, largely due to unknown preindustrial aerosol abundance. Here, sulfur isotope measurements in a Greenland ice core show that passive volcanic degassing contributes up to 66 ± 10% of preindustrial ice core sulfate in years without major eruptions. A state‐of‐the‐art model indicates passive volcanic sulfur emissions influencing the Arctic are underestimated by up to a factor of three, possibly because many volcanic inventories do not include hydrogen sulfide emissions. Higher preindustrial volcanic sulfur emissions reduce modeled anthropogenic Arctic aerosol cooling by up to a factor of two (+0.11 to +0.29 W m−2), suggesting that underestimating passive volcanic sulfur emissions has significant implications for anthropogenic‐induced Arctic climate change.

Multiple Sulfur Isotope Evidence for Bacterial Sulfate Reduction and Sulfate Disproportionation Operated in Mesoarchaean Rocks of the Karelian Craton

Sulfur isotope in sulfides from the Paleoarchean and the Neoarchean sedimentary rocks evidence microbial sulfur metabolism in Archean sulfur cycle. However, sulfur metabolism for the Mesoarchean interval is less obvious since evidence for a large range in sulfur isotope values has not yet been observed in Mesoarchean samples. We report the results of multiple sulfur isotope measurements for sulfide minerals from ~2.8 Ga sedimentary rocks in the southeastern part of the Karelian Craton. In situ isotope analysis of sulfide grains have been performed using a femtosecond laser-ablation fluorination method. Sulfide samples studied here yielded Δ33S values between −0.3 and +2.7‰ and δ34S values between −10 and +33‰. The Δ33S dataset was interpreted to indicate the incorporation of sulfur from two coexisting sulfur pools, photolytic sulfate and photolytically derived elemental sulfur. We suggest that the relative contributions of these Δ33S different pools to the pyritic sulfur could be controlled by the metabolic activity of coexisting sulfate-reducing and sulfur-disproportionating bacteria during pyrite formation. We therefore suggest the operation of different metabolic pathways of sulfur in Mesoarchean sedimentary environments.

Mineral-scale variation in the trace metal and sulfur isotope composition of pyrite: implications for metal and sulfur sources in mafic VMS deposits

The link between metal enrichment and the addition of a magmatic volatile phase in volcanogenic massive sulfide deposits and actively forming seafloor massive sulfide deposits remains poorly characterized. This is especially true when considering how metal, sulfur and fluid flux change with time. In this study, we combine in situ sulfur isotope (δ34S; n = 31) measurements with trace metal chemistry of pyrite (n = 143) from the Mala VMS deposit, Troodos, Cyprus. The aim of our study is to assess the links between volatile influx and metal enrichment and establish how, or indeed if, this is preserved at the scale of individual mineral grains. We classify pyrite based on texture into colloform, granular, disseminated and massive varieties. The trace metal content of different pyrite textures is highly variable and relates to fluid temperature and secondary reworking that are influenced by the location of the sample within the mound. The sulfur isotope composition of pyrite at Mala ranges from − 17.1 to 7.5‰ (n = 31), with a range of − 10.9 to 2.5‰ within a single pyrite crystal. This variation is attributed to changes in the relative proportion of sulfur sourced from (i) SO2 disproportionation, (ii) thermochemical sulfate reduction, (iii) the leaching of igneous sulfur/sulfide and (iv) bacterial sulfate reduction. Our data shows that there is no correlation between δ34S values and the concentration of volatile elements (Te, Se) and Au in pyrite at Mala indicating that remobilization of trace metals occurred within the mound.

A simple and rapid ICP-MS/MS determination of sulfur isotope ratios (34S/32S) in complex natural waters: A new tool for tracing seawater intrusion in coastal systems

Conventional sulfur isotope measurements in complex natural liquid or solid samples via GS-IRMS are complicated, time consuming and relatively expensive. Here we assessed a novel ‘collision cell’ based ICP-MS/MS approach which can determine the sulfur isotope abundances (i.e., 34S/32S ratios, expressed as δ34S) in complex coastal waters rapidly, accurately and with minimal sample preparation. The approach was validated via repeated ICP-MS/MS measurement of S isotope certified reference materials (CRM) providing accurate and reproducible results, with a typical uncertainty on δ34S of around 1.1–1.5‰ (1SD). This novel approach is suitable for water samples with sulfur concentrations at or above 2 μg/mL (ppm). Matrix matching between samples and the CRM was necessary when seawater-like solutions were analysed addressing common matrix related errors. The ICP-MS/MS approach was used to investigate δ34S signature of porewaters from a variety of coastal systems in South Australia (including acid sulfate soils), and how they responded to progressive seawater inundation. Importantly, inundation induced a shift in S isotope ratio in affected porewaters in which δ34S approached that of seawater. The simple sample preparation, with rapid and accurate δ34S determination of complex natural waters using the ICP MS/MS approach, greatly increases the applicability of sulfur isotope tracing studies to identify and monitor sources and bio-geochemical pathways of S in coastal and near-surface environments.

Tropospheric carbonyl sulfide mass balance based on direct measurements of sulfur isotopes

Robust estimates for the rates and trends in terrestrial gross primary production (GPP; plant CO2 uptake) are needed. Carbonyl sulfide (COS) is the major long-lived sulfur-bearing gas in the atmosphere and a promising proxy for GPP. Large uncertainties in estimating the relative magnitude of the COS sources and sinks limit this approach. Sulfur isotope measurements (34S/32S; δ34S) have been suggested as a useful tool to constrain COS sources. Yet such measurements are currently scarce for the atmosphere and absent for the marine source and the plant sink, which are two main fluxes. Here we present sulfur isotopes measurements of marine and atmospheric COS, and of plant-uptake fractionation experiments. These measurements resulted in a complete data-based tropospheric COS isotopic mass balance, which allows improved partition of the sources. We found an isotopic (δ34S ± SE) value of 13.9 ± 0.1‰ for the troposphere, with an isotopic seasonal cycle driven by plant uptake. This seasonality agrees with a fractionation of -1.9 ± 0.3‰ which we measured in plant-chamber experiments. Air samples with strong anthropogenic influence indicated an anthropogenic COS isotopic value of 8 ± 1‰. Samples of seawater-equilibrated-air indicate that the marine COS source has an isotopic value of 14.7 ± 1‰. Using our data-based mass balance, we constrained the relative contribution of the two main tropospheric COS sources resulting in 40 ± 17% for the anthropogenic source and 60 ± 20% for the oceanic source. This constraint is important for a better understanding of the global COS budget and its improved use for GPP determination.

Revisiting Ediacaran sulfur isotope chemostratigraphy with in situ nanoSIMS analysis of sedimentary pyrite

Abstract Reconstructions of ancient sulfur cycling and redox conditions commonly rely on sulfur isotope measurements of sedimentary rocks and minerals. Ediacaran strata (635–541 Ma) record a large range of values in bulk sulfur isotope difference (Δ34S) between carbonate-associated sulfate (δ34SCAS) and sedimentary pyrite (δ34Spy), which has been interpreted as evidence of marine sulfate reservoir size change in space and time. However, bulk δ34Spy measurements could be misleading because pyrite forms under syngenetic, diagenetic, and metamorphic conditions, which differentially affect its isotope signature. Fortunately, these processes also impart recognizable changes in pyrite morphology. To tease apart the complexity of Ediacaran bulk δ34Spy measurements, we used scanning electron microscopy and nanoscale secondary ion mass spectrometry to probe the morphology and geochemistry of sedimentary pyrite in an Ediacaran drill core of the South China block. Pyrite occurs as both framboidal and euhedral to subhedral crystals, which show largely distinct negative and positive δ34Spy values, respectively. Bulk δ34Spy measurements, therefore, reflect mixed signals derived from a combination of syndepositional and diagenetic processes. Whereas euhedral to subhedral crystals originated during diagenesis, the framboids likely formed in a euxinic seawater column or in shallow marine sediment. Although none of the forms of pyrite precisely record seawater chemistry, in situ framboid measurements may provide a more faithful record of the maximum isotope fractionation from seawater sulfate. Based on data from in situ measurements, the early Ediacaran ocean likely contained a larger seawater sulfate reservoir than suggested by bulk analyses.

Microbial and thermogenic hydrogen sulfide in the Qianjiang Depression of Jianghan Basin: Insights from sulfur isotope and volatile organic sulfur compounds measurements

Improved understanding of the hydrogen sulfide (H2S) origins is of significant importance for petroleum exploration, exploitation and refinement due to it being highly toxic and corrosive. H2S was discovered from the Qianjiang Formation (Eq) in the northern area and Xinggouzui Formation (Ex) in the southern area of the Qianjiang Depression, Jianghan Basin, China. The sulfur isotopic compositions of H2S, water-dissolved sulfates and oils and chemical compositions of volatile organic sulfur compounds (VOSCs) in natural gas as well as molecular and stable carbon isotopic compositions of oil and gas samples were measured to decipher the specific generation pathways of H2S. The conventional wisdom relays on bacteria sulfate reduction (BSR) for producing H2S because of the current low thermal regime (<80 °C). Crude oils, H2S and water-dissolved sulfates are progressively enriched in 34S. The δ34S values of H2S are around 12.0–32.0‰ lower relative to that of the dissolved sulfates and 0.8–24.0‰ greater relative to that of crude oils. This indicates that the current major contribution of H2S is actually related to BSR according to the S isotopic fractionation levels in BSR. The secondary contribution of H2S is attributed to be thermogenic mainly by thermal cracking alteration of organic matters (TCA). This clue is provided by the distribution patterns of VOSCs in natural gas rather than S isotope of crude oils, H2S and water-dissolved sulfates due to the limited input of TCA-associated H2S. The Eq TCA-associated gases are significantly enriched in thiols, sulfides, and alklyated thiophenes, the Ex BSR-associated gases contain mainly thiols and a little bit sulfides and alkylated thiophenes. The relevant early-matured Eq oils are also rich in labile organosulfur compounds, favoring the generation of VOSCs by TCA. VOSCs detected on the artificially pyrolyzed gaseous products of Eq rock and oil both show the identical distribution patterns as those of Eq natural gas samples, supporting the occurrence of TCA-associated H2S in the Eq reservoirs. The positive correlation between i-C4/n-C4 and H2S concentration for Eq gases indicates the catalytic effects of clays, promoting the generation by non-biological processes within the low thermal regimes. This study presents a novel method to clarify the origins of H2S by VOSCs in natural gas and improves our understanding of H2S generation pathways within low-temperature regime in nature.

A comparison of sulfur isotope measurements of geologic materials by inductively coupled plasma and gas source mass spectrometry

Sulfur isotope measurements by multi collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) require up to one hundred times less sulfur than traditional measurements via elemental analyzer isotope ratio mass spectrometry (EA-IRMS). Here, we report an improved MC-ICP-MS protocol for measuring δ34S values in different natural samples, specifically, calcium-sulfate minerals, carbonate associated sulfate, and dissolved sulfate in water. Sample preparation and subsequent anion exchange chromatography quantitatively recovers sulfur as sulfate. However, for samples with high and complex anion budgets, such as meteoric water, a stronger retention of sulfate on the anion exchange resin is observed relative to samples that contain sulfur as pure sulfate such as calcium-sulfate minerals and carbonate associated sulfate. An extended elution scheme with HNO3 is therefore required to achieve full recovery of sulfur, and thus accurate and reproducible δ34S values for the different materials investigated. Sulfur isotope measurements were performed on a Neptune Plus MC-ICP-MS coupled to an Apex-Ω desolvator, resulting in a “dry” plasma, negligible level of isobaric interferences, a sensitivity of >40 V ppm−1 sulfur, and a precision of 0.2‰ (2 S.D.) for δ34S for as little as 70 ng sulfur of a pure sulfate solution. The accuracy of the procedure was tested against duplicate δ34S EA-IRMS measurements for eleven different geologic samples. The EA-IRMS and MC-ICPMS values generally agree well within analytical uncertainty. However, procedural blank levels are on the order of a few tens of nanogram sulfur, and are thus the main limiting factor for accurate low-level sulfur isotope measurements with MC-ICP-MS.

Constraining the atmospheric OCS budget from sulfur isotopes

Carbonyl sulfide (OCS), the most abundant sulfur-containing gas in the atmosphere, is used as a proxy for photosynthesis rate estimation. However, a large missing source of atmospheric OCS has been inferred. Sulfur isotope measurements (34S/32S ratio and δ34S) on OCS are a feasible tool to distinguish OCS sources from oceanic and anthropogenic emissions. Here we present the latitudinal (north-south) observations of OCS concentration and [Formula: see text]S within Japan. The observed [Formula: see text]S of OCS of 9.7 to 14.5‰ reflects source and sink effects. Particularly in winter, latitudinal decreases in [Formula: see text]S values of OCS were found to be correlated with increases in OCS concentrations, resulting an intercept of (4.7 ± 0.8)‰ in the Keeling plot approach. This result implies the transport of anthropogenic OCS emissions from the Asian continent to the western Pacific by the Asian monsoon outflow. The estimated background [Formula: see text]S of OCS in eastern Asia is consistent with the [Formula: see text]S of OCS previously reported in Israel and the Canary Islands, suggesting that the background [Formula: see text]S of OCS in the Northern Hemisphere ranges from 12.0 to 13.5‰. Our constructed sulfur isotopic mass balance of OCS revealed that anthropogenic sources, not merely oceanic sources, account for much of the missing source of atmospheric OCS.

A Potential New Chalcopyrite Reference Material for Secondary Ion Mass Spectrometry Sulfur Isotope Ratio Analysis

Chalcopyrite is an important sulfide mineral in many types of ore deposits, but matrix‐matched chalcopyrite reference materials for microanalysis are lacking. A new natural chalcopyrite‐bearing specimen (HTS4‐6) was analysed in this study to investigate its potential as a reference material for microbeam sulfur isotope ratio measurement. Detailed textural examination and major element determination showed that the HTS4‐6 chalcopyrite grains have no growth rim or zoning. A total of 607 sulfur isotope ratio spot measurements with secondary ion mass spectrometry (SIMS) conducted on the cruciform sections, and over 120 randomly selected grains yielded highly consistent sulfur isotope ratio. The intermediate measurement precision for four measurement sessions of the 34S/32S measurement results was better than 0.39‰ (2s). Randomly selected chalcopyrite grains of HTS4‐6 were further analysed by LA‐MC‐ICP‐MS, which gave a mean δ34S value of +0.58 ± 0.38‰ (2s, n = 95). The maximum variance (expressed as intermediate precision from SIMS and LA‐MC‐ICP‐MS measurements) is not worse than 0.39‰ (the SIMS value), indicating that HTS4‐6 chalcopyrite is a potential reference material for in situ microbeam sulfur isotope measurements. The mean δ34S value determined by gas source isotope ratio mass spectrometry (GS‐IRMS) is +0.63 ± 0.16‰ (2s, n = 23), consistent with that derived by LA‐MC‐ICP‐MS, and can represent the recommended value for this potential reference material.

The Great Oxidation Event preceded a Paleoproterozoic “snowball Earth”

The inability to resolve the exact temporal relationship between two pivotal events in Earth history, the Paleoproterozoic Great Oxidation Event (GOE) and the first "snowball Earth" global glaciation, has precluded assessing causality between changing atmospheric composition and ancient climate change. Here we present temporally resolved quadruple sulfur isotope measurements (δ34S, ∆33S, and ∆36S) from the Paleoproterozoic Seidorechka and Polisarka Sedimentary Formations on the Fennoscandian Shield, northwest Russia, that address this issue. Sulfides in the former preserve evidence of mass-independent fractionation of sulfur isotopes (S-MIF) falling within uncertainty of the Archean reference array with a ∆36S/∆33S slope of -1.8 and have small negative ∆33S values, whereas in the latter mass-dependent fractionation of sulfur isotopes (S-MDF) is evident, with a ∆36S/∆33S slope of -8.8. These trends, combined with geochronological constraints, place the S-MIF/S-MDF transition, the key indicator of the GOE, between 2,501.5 ± 1.7 Ma and 2,434 ± 6.6 Ma. These are the tightest temporal and stratigraphic constraints yet for the S-MIF/S-MDF transition and show that its timing in Fennoscandia is consistent with the S-MIF/S-MDF transition in North America and South Africa. Further, the glacigenic part of the Polisarka Formation occurs 60 m above the sedimentary succession containing S-MDF signals. Hence, our findings confirm unambiguously that the S-MIF/S-MDF transition preceded the Paleoproterozoic snowball Earth. Resolution of this temporal relationship constrains cause-and-effect drivers of Earth's oxygenation, specifically ruling out conceptual models in which global glaciation precedes or causes the evolution of oxygenic photosynthesis.

Preservation of 34S-enriched sulfides in fossil sulfate-methane transition zones: new evidence from Miocene outcrops of the northern Apennines (Italy)

We provide new evidence of the preservation of 34S-enriched signals in methane seep-impacted sediments from two onshore Miocene outcrops located in the northern Apennines (Italy). Selected outcrops include methane-derived authigenic carbonates (MDAC) with δ13C composition between − 42.3 and − 18.2‰. MDACs contain chemosynthetic clams and abundant pyrite indicative of formation close to or within a shallow sulfate-methane transition zone (SMTZ). This study aims to evaluate the relative contributions of background organic matter mineralization and anaerobic oxidation of methane (AOM) to sulfate consumption and to gain insight into the transport process (i.e., diffusion, advection) controlling the depth of the SMTZ. Host sediments were investigated by CHN elemental analysis coupled with total sulfur (TS) and sulfur isotopic measurements on bulk samples. Total organic carbon (TOC) measurements reveal a consistent and low amount of organic carbon (TOC 0‰ and up to + 17.1‰), which is characteristic of sulfides precipitated in association with AOM. We propose that advection of methane-rich fluids was responsible for maintaining the shallow depth of the studied paleo-SMTZs. AOM at paleo-SMTZ positions in the investigated seep-impacted sediments resulted in excess bicarbonate and sulfide production, favoring solid-phase MDAC and iron sulfide precipitation.

Radiocarbon measurements using new automated graphite preparation laboratory coupled with stable isotope mass-spectrometry at Birbal Sahni Institute of Palaeosciences, Lucknow (India)

Conventional beta counting technique based radiocarbon dating facility at Birbal Sahni Institute of Palaeosciences- Lucknow was established in 1974 (Rajagopalan,1978). In 2017–18, BSIP received an upgrade with installation of an Automated Graphitization Equipment (AGE) coupled with an Elemental Analyser, a Carbonate Handling System (CHS) along with an in-line stable isotope mass-spectrometer (IRMS). Using this combo, stable Carbon (C), Nitrogen (N) and Sulfur (S) isotopic measurements could be carried out in both organic and inorganic type samples followed by graphite preparation (~1 mg) for 14C measurement by Accelerator Mass Spectrometry (AMS). This communication addresses details of pre-processing, processing, and quality checks adopted for achieving acceptable and demonstrable accuracy and precision of measured Δ14C, δ13C, δ15N, and δ34S measurements. Information regarding chemical preparation of samples for aforesaid stable and radio isotopic analysis is provided in succinct manner. Overall, average coefficient of variation determining precision of our graphite powders for 14C measurements is ~2.4%. The mean age of blank (anthracite) processed using established EA-IRMS-AGE unit comes as 42,100 ± 300 years.

Mercury and in situ sulfur isotopes as constraints on the metal and sulfur sources for the world’s largest Sb deposit at Xikuangshan, southern China

It has been well established that metal and sulfur sources in mineral deposits can be very difficult to identify, especially for ore deposits hosted in sedimentary rocks. Using the world’s largest Sb deposit at Xikuangshan in southern China as a case study, this study combined Hg isotopes and in situ sulfur isotope measurements to constrain the sources of Sb and sulfur. A variation of 1.1‰ in δ202Hg (0.04 to 1.15‰) was observed in stibnite ore samples, suggesting that mass-dependent fractionation of Hg isotopes occurred during the formation of the deposit. Significant mass-independent fractionation of Hg isotopes, with △199Hg ranging from − 0.03 to − 0.17‰, was also observed in the ore samples, suggesting that Hg transported by the ore fluids was inherited from Proterozoic basement metamorphic rocks as these rocks show similar △199Hg signatures (− 0.03 to 0.07‰). In situ sulfur isotope measurements yielded δ34S values that cluster in the range of + 6.8 to + 10.2‰, providing evidence that sulfur contained in ore fluids may also have been dominantly derived from underlying Proterozoic basement metamorphic rocks (δ34S = +5.6 to + 11.5‰). Using the new results from Hg and S isotopes, we proposed that deep-circulated meteoric water mobilized Sb, Hg, and S from the Proterozoic metamorphic basement, ascended along deep faults, and subsequently deposited Sb at favorable structural zones as a result of boiling of the hydrothermal fluids, generating the world-class Xikuangshan Sb deposit. This study also highlights the combined use of Hg-S isotopes as a novel method to provide new and additional insights into the source regions of ore materials for sedimentary-hosted Sb deposits.