Stable Sulfur Isotope Research Articles

Trait based niche differentiation in tetrakas (Bernieridae) endemic to Madagascar: A multi-isotope approach

Introduction Tropical rainforest species interact with each other and their environment over a wide range of spatiotemporal scales. However, our understanding of resource partitioning and the mechanisms of avian species coexistence is largely restricted to subjective visual observations or acoustic monitoring. Therefore, the relative magnitudes of interspecific and intraspecific differences in resource use have remained difficult to quantify, particularly regarding different diets and habitat use. The eastern rainforest belt of Madagascar is inhabited by several species of insectivorous tetrakas belonging to an endemic bird family of Madagascar (Bernieridae). These species occupy similar habitats in the forest understory and are morphologically similar but because of likely differences (e.g., in foraging behaviors) we expect their foraging niches to be segregated allowing coexistence. Methods We examined the niche differentiation of four of these species: the Grey-crowned Tetraka ( Xanthomixis cinereiceps ), Long-billed Tetraka ( Bernieria madagascariensis ), Spectacled Tetraka ( Xanthomixis zosterops ), and White-throated Oxylabes ( Oxylabes madagascariensis ) in the Maromizaha rainforest in eastern Madagascar combining morphometry with stable carbon, nitrogen, and sulfur isotope ratios (δ 13 C, δ 15 N, and δ 34 S) from feathers. Results We show considerable variation in isotopic niche positions, niche breadth and interspecific niche overlap. In two species, the Long-billed Tetraka and Spectacled Tetraka, we found an indication of sex-specific niche space, with males exhibiting a larger isotopic niche-area relative to females. Morphological traits of five species (including the Wedge-tailed Tetraka, Hartertula flavoviridis ) coupled with stable isotope data provided explanations of patterns of niche overlap and isotopic position. Discussion The observed isotopic niche differences may be explained by differences in resource acquisition strategies that might be associated with specific morphological traits and spatial distribution. This may play an important role in niche differentiation among coexisting and phylogenetically closely related species.

Sulfur isotopic discrimination factors differ among avian tissues and diets: Insights from a case study in Gentoo Penguins

Abstract The use of stable isotopes of sulfur (δ34S) to infer avian diets, foraging habitats, and movements is relatively uncommon, resulting in a lack of information on patterns of δ34S incorporation in avian tissue. In a controlled study of Gentoo Penguins (Pygoscelis papua), we found that diet-tissue isotopic discrimination factors (Δ34Sdiet-tissue) differed among egg components and feathers synthesized from a common diet, ranging from –0.4 to –1.7‰. We also found that methodical choices such as lipid extraction and prey tissue selection influenced calculated Δ34Sdiet-tissue values. Specifically, Δ34Sdiet-tissue values were lower (i.e., more negative) when calculated using whole fish relative to fish muscle and lipid-extraction biased egg yolk, but not fish tissue, δ34S values. The Δ34Sdiet-tissue values obtained for Gentoo Penguins fed a marine fish diet were generally lower than those reported for freshwater fish consumption by Double-crested Cormorants (Phalacrocorax auritus), the only other bird species in which Δ34Sdiet-tissue has been quantified. We found support for the hypothesis that tissue Δ34Sdiet-tissue values are inversely related to dietary δ34S values in birds, similar to what has been observed in mammals. Given this relationship, the discrimination factors reported here for Gentoo Penguins may be broadly applicable to other avian species with a similar marine diet. Finally, we provide recommendations for future studies seeking to quantify Δ34Sdiet-tissue in avian tissues and guidance to allow for greater application of sulfur stable isotope analysis in ornithological research.

Origin of Disseminated Gold-Sulfide Mineralization from Proximal Alteration in Orogenic Gold Deposits in the Central Sector of the Yana–Kolyma Metallogenic Belt, NE Russia

The Yana–Kolyma metallogenic belt, NE Russia, is a world-class gold belt with resources numbering ~8300 tons of gold. The belt is localized in the central part of the Verkhoyansk–Kolyma orogen, formed by a collage of diverse terranes. The Tithonian-to-Early-Cretaceous orogenic gold deposits are hosted in a sequence of Permian–Triassic and Jurassic clastic rocks and altered Late Jurassic andesite, dacite, granodiorite, trachyandesite, and trachybasalt dykes. High-fineness gold (800–900‰) in quartz veins and invisible gold in disseminated arsenian pyrite-3 (Py3) and arsenopyrite-1 (Apy1) are present in ores. Here, we present new data about microtextures; the chemical composition and stable sulfur isotopes of auriferous pyrite-3 and arsenopyrite-1 from proximal alterations in sediment-hosted (Malo–Taryn, Badran, Khangalas); and intrusion-hosted (V’yun, Shumniy) orogenic Au deposits in the central sector of the Yana–Kolyma metallogenic belt to better constrain the ore-forming process and tracking their evolution. Detailed petrography defined the following generations of pyrite: syn-sedimentary/diagenetic Py1, metamorphic Py2 and hydrothermal Py3, and Apy1. Hydrothermal Py3 and Apy1 are localized in the proximal pyrite–arsenopyrite–sericite–carbonate–quartz alteration in ore zones and make a major contribution to the economic value of the veinlet-disseminated mineralization with “invisible” gold in the orogenic deposits of the Yana–Kolyma metallogenic belt. Electron microprobe analysis (EMPA) of Py3 in both types of deposits shows concentrations of As (up to 3.16 wt%), Co, Ni, Cu, Sb, and Pb. Py3 in intrusion-hosted orogenic gold deposits reveals elevated concentrations of Co (up to 0.87 wt%), Ni (up to 3.52 wt%), and Cu (up to 2.31 wt%). The identified negative correlation between S and As indicates an isomorphic substitution of sulfur by As1−. Py3 from igneous rocks is characterized by a high degree of correlation for the pairs Fe2+→ Co2+ and Fe2+→ Ni2+. For hydrothermal Apy1, Co (up to 0.27 wt%), Ni (up to 0.30 wt%), Cu (up to 0.04 wt%), and Sb (up to 0.76 wt%) are typomorphic. According to atomic absorption spectrometry, the concentration of Au in Py3 reaches 159.5 ppm; in Apy1, it reaches 168.5 ppm. The determination of the precise site of the invisible gold within Py3 and Apy1 showed the predominance of solid-solution Au+ in the crystal lattice. The values of δ34S in Py3 and Apy1 (from −6.4 to +5.6‰, mean value of about +0.6‰), both from sediment-hosted and from intrusion-hosted deposits, display a relatively narrow range and are characteristic of the hydrothermal ore stage. Our analytical results showed no systematic differences between the chemical and stable sulfur isotope compositions of both auriferous pyrite-3 and arsenopyrite-1 from the proximal alteration in sediment-hosted (Malo–Taryn, Badran, Khangalas) and intrusion-hosted (V’yun, Shumniy) orogenic Au deposits, indicating that the primary source of sulfur, gold, and mineralizing fluids was likely from subcrustal and metamorphic systems in the Late-Jurassic-to-Early-Cretaceous Verkhoyansk–Kolyma orogen.

Study of the possibility of using data on the content of stable isotopes of magnesium to predict the region of apple production

Relevance. Reliable criteria for determining the region of origin of fruit products attract the constant attention of researchers in various countries. A number of approaches aimed at solving this problem are already known, and some progress has been made in interpreting experimental data for fruits on the content of stable isotopes of hydrogen, carbon, oxygen, nitrogen, and sulfur. It is possible that information about the fractionation of stable isotopes of magnesium will allow us to obtain equally important and reliable information to achieve the same goals.Methods. A mass spectrometer with inductively coupled plasma, standard samples of stable isotopes of magnesium produced in Russia were used to perform the work. The total concentration of magnesium cations was determined by atomic absorption in the flame and on the capillary electrophoresis system.Results. During the research, the mass and percentage ratio of three stable isotopes (24Mg, 25Mg, 26Mg) in the studied samples of apples grown in different soil and climatic zones was established. The data obtained reflect the relative prevalence of isotopes of this element, expressed in the ratio of the least common isotope to the most common. The deviation of the isotopic composition of Mg prototypes from the conventional standard was determined, significant deviations were obtained for the magnetic isotope 25Mg and non-magnetic 26Mg. The initial data on the fractionation of stable isotopes of magnesium in raw materials growing in different regions were obtained, with the aim of possible subsequent use as indicators in biochemical and physiological studies. A combination of the obtained information on Mg isotopes is assumed, taking into account the content of isotopes of other metals, which will make it possible to specify the region of growth of raw materials with greater reliability.

Controls on sulfide accumulation in coastal soils during simulated sea level rise

A likely consequence of sea level rise during the next century will be progressive inundation of seawater through the current unsaturated zone in coastal-margin soils. It is unclear how this will change the biogeochemical cycling of iron, sulfur and carbon over different time scales and soil types. A long-term (540 day) laboratory experiment, slowly inundating intact coastal soil cores with seawater from the ‘bottom up’, was conducted to observe how coupled iron and sulfur dynamics change in different soil types. Pore water was extracted from the 60 cm cores at 10 cm depth intervals every 90 days and analysed for pH, electrical conductivity (EC), Fe2+, HS− and dissolved metals (Fe, Mn, As, Cd, Cu, Ni, Pb, Co, Zn) as well as stable sulfur (34S/32S) and radiogenic strontium (87Sr/86Sr) isotopes. Destructive solid phase analyses (for reactive Fe, acid volatile and chromium reducible sulfur (AVS and CRS) and total organic carbon (TOC)) were made at the start and end of the experiment. Iron and sulfate reduction was induced in soils with readily available TOC as anoxic conditions established, evidenced by statistically significant increases (P < 0.001) in dissolved Fe2+ and sulfide concentrations in porewaters, as well as simultaneous and progressive increase in the sulfur isotope (34S/32S) ratios. An increase in AVS indicated formation of metastable iron sulfide (FeS) minerals resulting from Fe2+ and sulfide in porewaters post inundation. This was supported by PHREEQC modelling of local mineral saturation states/indices in the system. Overall, the Fe2+ concentration increased to a peak at between 270 and 360 days, and then began decreasing at some depths, indicating slowing iron reduction, presumably because reactive iron (oxyhydro)oxides became progressively consumed by microbially driven reductive processes. However, microbially mediated sulfate reduction continued as abundant sulfate was still available from seawater. In the absence of free Fe2+, sulfide accumulated in the porewater, but only in those soils inundated the longest (>360 days), and with greater than 5% TOC. The combined use of sulfur (34S/32S) and strontium (87Sr/86Sr) isotopes supported the observed results, and represents a new and robust technique to quantify progressive sulfate reduction and seawater mixing phenomena in coastal soils. This study gives new insights into the biogeochemical cycling of sulfur and iron in soils experiencing seawater inundation from sea level rise over longer timescales. It is likely that sulfidisation (due to in-situ sulfate reduction) will begin to affect coastal wetland soils, especially in areas where TOC is high and where reactive iron depletes over time. This has potential consequences for sulfide toxicity in coastal soils and environments globally.

Insights into the metamorphic history and origin of flake graphite mineralization at the Graphite Creek graphite deposit, Seward Peninsula, Alaska, USA

Graphite Creek is an unusual flake graphite deposit located on the Seward Peninsula, Alaska, USA. We present field observations, uranium-lead (U–Pb) monazite and titanite geochronology, carbon (C) and sulfur (S) stable isotope geochemistry, and graphite Raman spectroscopy data from this deposit that support a new model of flake graphite ore genesis in high-grade metamorphic environments. The Graphite Creek deposit is within the second sillimanite metamorphic zone of the Kigluaik Mountains gneiss dome. Flake graphite, hosted in sillimanite-gneiss and quartz-biotite paragneiss, occurs as disseminations and in sets of very high grade (up to 50 wt.% graphite), semi-massive to massive graphite lenses 0.2 to 1 m wide containing quartz, sillimanite, inclusions of garnet porphyroblasts, K-feldspar, and tourmaline. Restitic garnet, sillimanite, graphite, and biotite accumulations indicate a high degree of anatexis and melt loss. Strong yttrium depletion in monazite, high europium ratios (Eu/Eu*), and excursions of high strontium and thorium concentrations are consistent with biotite dehydration melting. Monazite and titanite U–Pb ages record peak metamorphism from ~ 97 to 92 million years ago (Ma) and a retrograde event at ~ 85 Ma. Raman spectroscopy confirms the presence of carbonaceous material and highly ordered, crystalline graphite. Graphite δ13CVPDB values of − 30 to − 12‰ and pyrrhotite δ34SVCDT values of − 14 to 10‰ are consistent with derivation from organic carbon and sulfur in sedimentary rocks, respectively. These data collectively suggest that formation of massive graphite lenses occurred approximately synchronously with high-temperature metamorphism and anatexis of a highly carbonaceous pelitic protolith. Melt extraction and fluid release associated with anatexis were likely crucial for concentrating graphite. High-temperature, graphitic migmatite sequences within high-strain shear zones may be favorable for the occurrence of high-grade flake graphite deposits.

Chemical and Isotopic Features of a High pCO2 Natural Mineral Water from Essentuki Field (Caucasian Mineral Water Region, Russia)

This article presents the new data on the chemical and gas composition, the content of stable isotopes of oxygen, hydrogen, carbon, and sulfur in natural mineral waters of the Essentuki field. A detailed study of the geological and hydrogeological features of the water circulation area, its major chemical composition, the content of organic matter in water, temperature conditions and δ18OSMOW, δDSMOW, δ13CDIC, δ18ODIC, δ34SVCDT, δ13CCO2, δ13CCH4, δ15N values made it possible to specify the genesis of water, gas, and solute components of the Essentuki CO2-rich mineral water field. The stable isotopes values (δ18OSMOW and δDSMOW) in the water phase ranges from −13.75 to −9.69‰ and from −101.08 to −74.34‰, respectively. They correspond to GMWL, which indicates their predominantly infiltration genesis. The values of δ13CDIC in mineral waters of the Essentuki field vary widely from −14.43 to +8.59‰ and indicate their mixed genesis. δ15N gas values in mineral waters of the Essentuki field vary quite widely from −2.31 to 2.50‰ indicating a different source of this gas. Obtained data prove that all mineral waters in the Essentuki field are infiltration waters, and the heterogeneous component composition of waters circulating in different aquifers reflects the lithological composition of water-bearing strata, the rate of openness/closure of faults and the intensity of reactions in the «water-rock-gas-organic matter» system.

Tracing carbon flow and trophic structure of a coastal Arctic marine food web using highly branched isoprenoids and carbon, nitrogen and sulfur stable isotopes

Climate-driven alterations of the marine environment are most rapid in Arctic and subarctic regions, including Hudson Bay in northern Canada, where declining sea ice, warming surface waters and ocean acidification are occurring at alarming rates. These changes are altering primary production patterns that will ultimately cascade up through the food web. Here, we investigated (i) the vertical trophic structure of the Southampton Island marine ecosystem in northern Hudson Bay, (ii) the contribution of benthic and pelagic-derived prey to the higher trophic level species, and (iii) the relative contribution of ice algae and phytoplankton derived carbon in sustaining this ecosystem. For this purpose, we measured bulk stable carbon, nitrogen and sulfur isotope ratios as well as highly branched isoprenoids in samples belonging to 149 taxa, including invertebrates, fishes, seabirds and marine mammals. We found that the benthic invertebrates occupied 4 trophic levels and that the overall trophic system went up to an average trophic position of 4.8. The average δ34S signature of pelagic organisms indicated that they exploit both benthic and pelagic food sources, suggesting there are many interconnections between these compartments in this coastal area. The relatively high sympagic carbon dependence of Arctic marine mammals (53.3 ± 22.2 %) through their consumption of benthic invertebrate prey, confirms the important role of the benthic subweb for sustaining higher trophic level consumers in the coastal pelagic environment. Therefore, a potential decrease in the productivity of ice algae could lead to a profound alteration of the benthic food web and a cascading effect on this Arctic ecosystem.

What Controls the Sulfur Isotope Fractionation during Dissimilatory Sulfate Reduction?

Sulfate often behaves conservatively in the oxygenated environments but serves as an electron acceptor for microbial respiration in a wide range of natural and engineered systems where oxygen is depleted. As a ubiquitous anaerobic dissimilatory pathway, therefore, microbial reduction of sulfate to sulfide has been of continuing interest in the field of microbiology, ecology, biochemistry, and geochemistry. Stable isotopes of sulfur are an effective tool for tracking this catabolic process as microorganisms discriminate strongly against heavy isotopes when cleaving the sulfur-oxygen bond. Along with its high preservation potential in environmental archives, a wide variation in the sulfur isotope effects can provide insights into the physiology of sulfate reducing microorganisms across temporal and spatial barriers. A vast array of parameters, including phylogeny, temperature, respiration rate, and availability of sulfate, electron donor, and other essential nutrients, has been explored as a possible determinant of the magnitude of isotope fractionation, and there is now a broad consensus that the relative availability of sulfate and electron donors primarily controls the magnitude of fractionation. As the ratio shifts toward sulfate, the sulfur isotope fractionation increases. The results of conceptual models, centered on the reversibility of each enzymatic step in the dissimilatory sulfate reduction pathway, are in qualitative agreement with the observations, although the underlying intracellular mechanisms that translate the external stimuli into the isotopic phenotype remain largely unexplored experimentally. This minireview offers a snapshot of our current understanding of the sulfur isotope effects during dissimilatory sulfate reduction as well as their potential quantitative applications. It emphasizes the importance of sulfate respiration as a model system for the isotopic investigation of other respiratory pathways that utilize oxyanions as terminal electron acceptors.

Multi-isotopic analysis of zooarchaeological material from Estonia (ca. 200-1800 CE): Variation among food webs and geographical regions.

To better comprehend the dietary practices of past populations in the Eastern Baltic region we have created temporally and geographically restricted baselines for the time period of 200-1800 CE. In this multi-isotopic analysis, we report new δ13C, δ15N and δ34S values for 251 faunal bone collagen samples from various archaeological contexts in Estonia representing the most comprehensive set of Iron Age, Medieval and Early Modern Period faunal stable isotope values to date. The results map out the local carbon and nitrogen baselines and define isotopic ranges of local terrestrial, avian and aquatic fauna. We also demonstrate the potential application of sulfur stable isotope analysis in archaeological research. The results demonstrate a clear distinction between δ13C and δ34S values of marine and terrestrial species, however, freshwater fish display notable overlaps with both marine and terrestrial ranges for both δ13C and δ34S values. Herbivores show variation in δ34S values when grouped by region, explained by differences in the local biotopes. This study is the first attempt to connect the Eastern Baltic isotopic baselines and provides more detailed temporal and geographical references to study the local ecologies and interpret the human data.

New data on the chemical and isotopic (H, O, C, S, N) composition of mineral waters of the Essentuki deposit

The article presents modern data on the chemical, gas composition, the content of the stable isotopes of oxygen, hydrogen, carbon and sulfur in the natural mineral waters of the Essentuki field. A detailed study of the geological and hydrogeological features of the water circulation territory, their macro components composition, the content of organic matter in the water, temperature conditions and values of δ18ОSMOW, δDSMOW, δ13СDIC, δ18ОDIC, δ34SVCDT, δ13CCO2, δ13CCH4, δ15N revealed the genesis of the aqueous, gas and salt components of the natural mineral waters of the Essentuki field. Established that all natural mineral waters of the Essentuki field are meteoric infiltration waters. The heterogeneous component composition of the natural mineral waters, that circulate in various aquifers, represents the features of the lithological composition of the water-bearing rocks, the degree of openness or closeness of faults and the intensity of reactions in the water-rock-gas-organic matter system.

Investigating Past Livestock Mobility Using δ34S Stable Isotopes: Three Preliminary Case Studies From Prehistoric Croatia

The benefit of including sulfur (δ³⁴S) stable isotopes in studies of past human diet and migration is increasingly clear, but δ³⁴S analyses remain underutilized in addressing other patterns of mobility, animal management, and environmental change in the archaeological record. Here we evaluate the ability of δ³⁴S isotope values to act as proxies for prehistoric environments in three distinct regions of Croatia: northern Dalmatia, Lika, and central Croatia. We then assess if δ³⁴S isotope values can highlight differences in herding and management practices of livestock in these areas, specifically those that encourage the movement of herds into various parts of the landscape (e.g., transhumance vs. localized grazing). Analysis of faunal stable isotope values from these geographically diverse sites constitute the first step in building an environmental database for Croatia and addressing questions of how δ³⁴S can be applied to questions about animal husbandry in the archaeological record.

Effect of faulting on diagenetic processes in the silicate-sulfate-carbonate system: A case study from the Bonan Sag of Jiyang Depression, Bohai Bay Basin

Many extraordinary cements, including mosaic dolomite, poikilitic celestine–barite, anhydrite and chemically zoned saddle-formed dolomite–ankerite, were observed in a reservoir sandstone unit underlying an evaporite sequence in the northern Bonan Sag, which is a saline lacustrine rift basin in the Jiyang Depression of Bohai Bay Basin, China. A suite of petrologic and chemical methods, including optical observation with cathode luminescence, fluid inclusion with laser Raman spectroscopy, X-ray fluorescence, and stable isotopes of carbon, oxygen and sulfur, were carried out. The results suggest that these extraordinary cements are mainly distributed near a fault zone and related to episodes of faulting events. Fault rupturing at shallow burial depths resulted in the dislocation of the evaporites and sandstones and made it possible for an influx of alkaline fluid from evaporites into the fault zone, where mosaic dolomite precipitated, and near fault reservoir units, such as where celestine–barite precipitated. Within the ‘oil window’, the reactivated normal faults, which induced a pressure drop in the reservoir unit, may have resulted in gas influx (e.g., CO2 and H2S) and hydrocarbon charging, enhancing K-feldspar dissolution and cementation of assemblages of quartz, albite and illite. The cyclic fault rupturing and sealing in this setting probably resulted in repeated ‘openness’ of the diagenetic system, chemical perturbation of the pore fluids (e.g., pH dropping and returning), and cyclic dissolution–regrowth within the silicate–sulfate–carbonate diagenetic system. This study may highlight the awareness of diagenetic complexity in fault zones and shed light on reservoir evaluation in rift settings.

Anoxia-Related Biogeochemistry of North Indian Ocean

Complex interactions between microbial communities and geochemical processes drive the major element cycles and control the function of marine sediments as a dynamic reservoir of organic matter. Sulfate reduction is globally the dominant pathway of anaerobic mineralisation and is the main source of sulfide. The effective re-oxidation of this sulfide at the direct or indirect expense of oxygen is a prerequisite for aerobic life on our planet. Although largely hidden beneath the oxic sediment surface, the sulfur cycle is therefore critical for Earth’s redox state. This Geochemical Perspectives begins with a brief primer on the sulfur cycle of marine sediments and a description of my own scientific journey through nearly fifty years of studies of sulfur geochemistry and microbiology. Among the main objectives of these studies were to quantify the main processes of the sulfur cycle and to identify the microbial communities behind them. Radiotracers in combination with chemical analyses have thereby been used extensively for laboratory experiments, supported by diverse molecular microbiological methods. The following sections discuss the main processes of sulfate reduction, sulfide oxidation and disproportionation of the inorganic sulfur intermediates, especially of elemental sulfur and thiosulfate. The experimental approaches used enable the analysis of how environmental factors such as substrate concentration or temperature affect process rates and how concurrent processes of sulfate reduction and sulfide oxidation drive a cryptic sulfur cycle. The chemical energy of sulfide is used by chemolithotrophic bacteria, including fascinating communities of big sulfur bacteria and cable bacteria, and supports their dark CO2 fixation, which produces new microbial biomass. During the burial and aging of marine sediments, the predominant mineralisation processes change through a cascade of redox reactions, and the rate of organic matter degradation drops continuously over many orders of magnitude. The main pathways of anaerobic mineralisation and the age control of the organic matter turnover are discussed. In the deep methanic zone, only a few percent of the entire degradation process remains, which provides a small boost of substrate for sulfate reduction through the process of anaerobic methane oxidation. The stable isotopes of sulfur provide an additional tool to understand these diagenetic processes, whereby the combination of microbial isotope fractionation and open system diagenesis generate a differential diffusion flux of the isotopes. In relation to the organic carbon cycle of the seabed and the contribution of methane, the paper discusses the global sulfur budget and the role of sulfate reduction for organic matter mineralisation in different depth regions of the ocean - from coast to deep sea. The published estimates of these parameters are evaluated and compared. Finally, the paper looks at future perspectives with respect to gaps in our current understanding and the need for further studies.

Geology and geochemistry of the high-grade Zankan magnetite ore, Western Kunlun Mountains, NW China

Over the past decade, several magnetite-rich iron deposits have been discovered in the Taxkorgan region of the western Kunlun Mountains of northwestern China. These include the Zankan, Jiertieke, Laobing, Yelike, and Taaxi iron deposits. Prospective iron ore reserves are estimated at over 1 billion tons, with an average magnetite grade of 28% (Feng et al., 2018). The largest of the deposits, the Zankan Iron Deposit (ZID), is estimated to contain 628 million tons of iron ore, with at least 10% of the ores being high-grade (TFe > 50 wt%). However, the geological processes by which the high-grade ores in the ZID were formed remains poorly constrained. In this study, we combine whole rock and ore geochemistry data, oxygen and sulfur stable isotopes, and uranium-lead and hafnium isotopes from zircons to elucidate the plausible mechanisms underpinning the formation of the ZID ores. Based on mineralogy, we define two ore types. Type 1 is essentially comprised of quartz and magnetite, interlayered with schist, and it retains the sedimentary fabrics of the precursor iron-rich sediments which were an iron formation (IF). Type 2 formed by the intrusion of a dacite-porphyry into the IF which led to magnetite remobilization and recrystallization as manifest in magnetite-ferro actinolite veining. Rare earth element (REE) characteristics of the high-grade ores differs from those of the precursor IF, with chondrite normalized REE patterns showing enrichment of LREE and significant negative europium anomalies close to those of the dacite-porphyry. The oxygen and sulfur isotopic composition of magnetite and pyrite in the high-grade ores suggests a further meteoric influence on the ZID with silica enrichment driven by leaching of the precursor IF from elsewhere in the sequence. Circulation of the ore forming fluid is attributable to the development of faults and fracture zones that resulted from the intrusion of the dacite-porphyry. Laser ablation uranium-lead analyses of zircons from the dacite-porphyry yield two groups with ages of 551.25 ± 3.32 Ma and 497.82 ± 3.81 Ma, representing captured detrital zircons and the intrusive age of dacite porphyry, respectively. Given the intimate geological relationship between the dacite-porphyry and T2 ore, we suggest that the high-grade ores are formed after 497.82 Ma. Collectively our field observations and geochemical data reveal the detailed alteration processes that led to the development of the high-grade iron ores in the ZID, identifying distinctive features that may help to guide future exploration for additional high-grade ore deposits in the Taxkorgan region.

Using Stable Sulfur Isotope to Trace Sulfur Oxidation Pathways during the Winter of 2017-2019 in Tianjin, North China.

After the implementation of the Coal Replacing Project (CRP) in the northern parts of China in 2017, its effect on PM2.5 composition is still unclear. In the study, water-soluble ionic components (WSICs) and stable sulfur isotope ratios (δ34S) of SO42− in PM2.5 collected during the domestic heating period before and after the implementation of CRP in Tianjin were analyzed. Results showed that the average concentrations of both PM2.5 and WSICs have dropped dramatically after the CRP, especially for the SO42− (by approximately 57–60%). After the CRP, the range of δ34Ssulfate was significantly narrowed to 4.1–7.5‰ in January 2018 and 1.4–6.1‰ in January 2019, which suggested that the sulfur source was becoming simple. It was interesting that the δ34Ssulfate value in the pollution period before the CRP was higher than that in the clean period, whereas it showed the opposite tendency after the CRP, which implied that the contribution of sea salt was high during the pollution period before the CRP. The MIXSIAR model calculated that the contributions of the transition-metal ion (TMI) oxidation and NO2 oxidation pathways in the three sampling stages were higher than those of the OH radical oxidation and H2O2/O3 oxidation pathways, indicating that the formation pathway of sulfate was mainly dominated by heterogeneous oxidation. Before the CRP, the NO2 oxidation pathway was the dominant sulfate oxidation pathway during a haze episode, and the TMI oxidation pathway dominated the formation of sulfates after the CRP.

What is the menu today in a subantarctic kelp food web from the Kerguelen Islands? Phytodetritus, phytoplankton and phytobenthos; not living kelp

Kelp forests dominated by Macrocystis pyrifera are widely distributed in coastal waters from boreal, temperate and subantarctic regions. This widespread distribution may result in regional differences in food web structure and functioning. In temperate northern regions, where most studies on kelp forest benthic food webs have been conducted, kelp grazing is a well-documented phenomenon and can lead to the overgrazing of M. pyrifera by sea urchins when their predators (e.g., sea otters) are absent. In contrast, little is known about their counterparts in subantarctic areas. The present study aimed to reconstruct the benthic food web of a kelp forest dominated by M. pyrifera in a subantarctic environment using stable isotope analysis. Stable carbon (δ13C), nitrogen (δ15N) and sulfur (δ34S) isotope ratios were measured from food sources (macrophytobenthos, suspended particulate organic matter SPOM, and sediment) and consumers (sponges, bivalves, gastropods, sedentary and mobile polychaetes, arthropods and echinoderms) which were sampled in a kelp forest of the Kerguelen archipelago. Mixing models highlighted two interconnected trophic pathways which were either supported by SPOM and resuspended macrophytobenthos detritus (bentho-pelagic), or by live micro/macrophytobenthos (phytobenthos-based). No major prey were highlighted for several consumers, indicating the existence of potential supplementary trophic pathways. No consumer relying primarily on living M. pyrifera was highlighted by the mixing models. The investigated kelp forest is hence a complex ecosystem supporting multiple trophic pathways, and direct consumption of M. pyrifera is limited. Nonetheless, M. pyrifera and other macrophytobenthos species may constitute a pool of detritus supporting several trophic pathways.

Metal source and hydrothermal evolution of the Jiaoxi quartz vein-type tungsten deposit (Tibet): Insights from textural and compositional variations of wolframite and scheelite

Abstract We evaluate the controlling factors of hydrothermal wolframite and scheelite precipitation in the quartz vein-type Jiaoxi tungsten deposit situated in the western part of the Lhasa terrane (Tibet, China) using texture, major and trace element mineral geochemistry, and sulfur stable isotope geochemistry. Pyrite and chalcopyrite that are intergrown with Fe-enriched wolframite and siderite, have distinct in situ S isotope compositions (δ34SV-CDT) of −31.38 to +1.77‰, and +2.07 to +2.30‰, respectively. Major and trace element contents and in situ S isotope compositions of pyrite and chalcopyrite indicate that the hydrothermal evolution involved fluid-fluid mixing and greisenization. We report evidence for an early magmatic fluid, which is characterized by the enrichment of W, Mn, Zr, Ti, Sc, and Sn and depletion of Fe. This magmatic fluid was diluted by meteoric water and interacted with biotite monzogranite porphyry to leach Fe, Mg, and Zn into the system to form wolframites with variable Fe/(Fe+Mn) ratios ranging between 0.06–0.84. The late Fe-enriched magmatic fluid released from the muscovite granite mixed with meteoric water that leached minor Fe and S from shale to form late shale-hosted wolframite with a Fe/(Fe+Mn) mass ratio of &amp;gt;0.75 and coeval siderite and sulfides. This study highlights that multiple Fe sources were present in the system, including muscovite granite-released Fe through fluid exsolution, biotite monzogranite porphyry-released Fe during greisenization, and minor Fe released from the shale as a result of meteoric water leaching.

Stable sulphur isotope (δ 34S) ratios in bird feathers from India indicate strong segregation between the Himalaya and Gangetic plain, and the rest of India

ABSTRACT Although stable hydrogen (δ 2H) and carbon (δ 13C) isotopic compositions of bird feathers have been increasingly used to understand the migration of birds through assignment of individuals to established isoscapes, far less is known about the structure of feather isoscapes based on stable sulphur isotope (δ 34S) assays. While δ 2H isoscapes have been used to investigate the migratory origins of the Globe Skimmer (Pantala flavescens) dragonfly in India, no isotope studies have been applied to avian migration patterns in that region. Here, based on museum collections, we report the feather δ 34S values of 13 avian species that included marine birds with expected 34S enriched feathers, resident birds throughout India and a single migratory species, Bar-headed Goose (Anser indicus). Feathers from the marine birds were the most enriched (20.6 ± 1.2 ‰, n = 10; range = 4.4 ‰) in 34S but terrestrial resident species also showed unexpectedly high δ 34S values (11.7 ± 4.8 ‰, n = 74; range = 19.9 ‰) throughout most of India but the Himalayan region and Gangetic plain typically showed δ 34S values less than 6.4 ‰. Our results show the utility of feather δ 34S studies to decipher avian and other animal migration between these two regions.

Major sulfur cycle perturbations in the Panthalassic Ocean across the Pliensbachian-Toarcian boundary and the Toarcian Oceanic Anoxic Event

The early Toarcian Oceanic Anoxic Event (T-OAE, ~183 Ma) was characterized by marine deoxygenation and the burial of organic-rich sediments at numerous localities worldwide. However, the extent of marine anoxia and its impact on the sulfur cycle during the T-OAE is currently poorly understood. Here, stable sulfur isotopes of reduced metal-bound sulfur (δ 34 S pyrite ) and pyrite sulfur concentrations (S PY ) have been analyzed across the Pliensbachian-Toarcian boundary (Pl-To) and the T-OAE from the Sakahogi and Sakuraguchi-dani sections (Japan), which were deposited in the deep and shallow Panthalassic Ocean, respectively. Our data reveal marked positive δ 34 S pyrite excursions of >10‰ across both the Pl-To and the T-OAE at Sakahogi, coincident with increases in S PY , and a positive excursion of >20‰ at the onset of the T-OAE at Sakuraguchi-dani. Whilst the development of deep-water anoxic/euxinic conditions could have resulted in an enhanced burial of pyrite, and also partly contributed to the positive excursion of δ 34 S pyrite , variations in δ 34 S pyrite at Sakahogi were most likely controlled by elevated export production and/or preservation. On the shallow shelf generally low and highly variable S PY and the positive shift in δ 34 S pyrite were likely attributable mainly to elevated sedimentation rates, with redox playing only a minor role in controlling pyrite abundance. Our discovery of a positive δ 34 S pyrite excursion across the Pl-To at Sakahogi indicates a hitherto unrecognized perturbation to the deep-water sulfur cycle, potentially associated with increased seafloor organic matter flux and pyrite burial at this time, consistent with a transient interval of anoxia. • First pyrite S-isotope (δ 34 S pyrite ) data across the Toarcian OAE (T-OAE) • Positive pyrite S-isotope excursions across T-OAE from deep and shallow Panthalassa • Excursions mainly attributable to local depositional conditions. • Deep-water sulfur isotope excursion across Pliensbachian-Toarcian boundary