Stable Sulfur Isotope Research Articles

Diet in high mediaeval Florence through stable isotope analysis of carbon, nitrogen and sulphur

In this paper, we aim to reconstruct the dietary habits of supposedly lower rank nobles or middle-class High Middle Ages individuals recovered from the cloister arcade of San Pier Scheraggio within the Uffizi Museum complex in Florence, Italy. Notably, the High Middle Ages was a period of cultural and social changes, which is partly reflected in the dietary habits, as suggested by historical sources. Here we apply stable carbon, nitrogen, and sulphur isotope analysis on humans (n = 34) and animals (n = 13) from San Pier Scheraggio to directly investigate food consumption in this peculiar assemblage. The diet of human individuals was based on terrestrial C3 sources without clear contribution of marine fish (δ13C mean and 1SD: −19.5 ± 0.7 ‰; δ15N mean and 1SD: 9.6 ± 0.4 ‰; δ34S values are mean and 1SD: 7.6 ± 1.2 ‰). The comparison with animal and human samples from other Italian Middle Ages contexts shows that the overall diet of the population buried at San Pier Scheraggio is in line with that of other mediaeval communities in Italy, although with a generally higher contribution of terrestrial animal products. Our data seem to suggest that at the site there was no dietary differentiation concerning age at death or biological sex of the individuals. Some differences, however, can be outlined, for example, in the contribution of C4 crops. In addition to this, we identify two individuals as possible non-locals.

Deformation and fluid flow history of a fractured basement hydrocarbon reservoir below the Sab'atayn Basin, Habban Field, Yemen

Fractured crystalline basement reservoirs are of increasing economic interest for oil and gas exploration and subsurface fluid storage. The successful characterization of these reservoirs is commonly challenged by their structural heterogeneity, complexity in fracture distribution and flow properties at multiple scales, and the difficulty of imaging fractures in exploration seismic. We analyzed the fracture geometry and fracture diagenetic attributes in two oriented cores from the Habban Field in the Late Jurassic Sab'atayn Basin (Yemen) to evaluate the multi-phase deformation history and fracture flow pathway evolution for (hydrothermal) fluids and hydrocarbons. Analyses included petrographic and fluid inclusion analysis of fracture-filling cements, and stable sulfur isotope analyses of fracture-filling pyrite.The Paleoproterozoic basement consists of amphibolite-facies metamorphic ortho- and paragneiss cut by several phases of Neoproterozoic granitoid intrusions. The investigated lithologies in the drill cores comprise (1) epidote quartzite, (2) amphibolite, (3) monzogranite, (4) meta-arkose, and (5) quartz-feldspar porphyry. These lithologies show an inhomogeneous fracture network that is partially cemented. Ediacaran brittle-ductile deformation (D1) recognized only within a Pan-African monzogranite lead to cataclasis and porosity generating alteration. Late Jurassic – Early Cretaceous extension (D2) related to the break-up of Gondwanaland and the formation of the Sab'atayn Basin is found in all lithologies and likely resulted in pervasive quartz cementation. Late Jurassic fractures parallel to the NW-SE trending long axis of the Sab'atayn Basin are best recognized in a strongly foliated amphibolites. Cenozoic extensional fracturing (D3) reactivated older structures, which probably formed during activity of the Neoproterozoic Najd Fault System and caused multi-phased (pyrite-(saddle) dolomite-calcite) fracture cementations. The sulfur isotope compositions of pyrite with δ34S values ranging between −17.4 and + 26.4‰ vs. V-CDT reflects the variability of the fluid source during sulphide mineral formation from hydrocarbon-rich hydrothermal solutions. Fluid inclusions indicate that cementation reactions occurred in a relatively narrow temperature field between 120 °C and 140 °C, ideal for hydrocarbon maturation. Our results demonstrate the potentially complex charge history of basement reservoirs, involving multiple phases of fracture formation and cementation, and fluid charge episodes.

Tracing sulfate sources in a tropical agricultural catchment with a stable isotope Bayesian mixing model

Sulfate (SO42−) is an essential anion in drinking water and a vital macronutrient for plant growth. However, elevated sulfate levels can impact ecosystem or human health and could be an important indicator of acid rock drainage or pollution. Therefore, monitoring SO42− sources and transport is important for water quality assessments. This study focused on exploring the sources and transformations of SO42− as well as estimating the proportional contribution of the potential SO42− pollutant sources to groundwater and surface water in a tropical river basin, the Densu River Basin. The study used major ions combined with stable sulfur and oxygen isotope compositions and a Bayesian isotope mixing model, MixSIAR. The major ion characteristics indicate that SO42− concentrations remain stable throughout the rainy and dry seasons but originate from diverse sources. The multi-isotope model (δ34SSO4, δ18OSO4) identified four potential SO42− sources: detergent, precipitation, sewage, and sulfate fertilizer. However, the δ34SSO4 and δ18OSO4 values of the fertilizer source signatures overlapped with those of precipitation and sewage. Nevertheless, the contributions from each source were disentangled using the MixSIAR model, which revealed sewage as the most dominant SO42− pollutant in the Densu Basin, accounting for ~47 % of sulfate in groundwater and ~ 56 % of sulfate in surface water. Sulfate fertilizer (~33 %) was the second most important source after sewage for groundwater, while detergent (~23 %) was the second most important source for surface water. The redox processes of bacterial sulfate reduction and sulfide oxidation were determined to have a minimal impact on the sulfur isotope fractionation within the basin. This study highlights the benefits of combining major ions, sulfur isotopes and the MixSIAR model for identifying sources of sulfate. This approach accounts for uncertainties in source contributions which allows for more robust and reliable apportionment of sulfate sources. The study emphasizes the need for effective waste management and pollution control measures to protect water quality and provides vital guidelines on how to partition sulfate sources on a large catchment scale and evidence for making pollution management decisions on water resources.

Tracing the orogenic sulfur cycle in the Andes using stable isotope composition of dissolved sulfate in thermal springs

The cycling of sulfur (S) to the upper crust and surface via thermal springs at convergent margins has not been explored outside areas with active arc volcanism, even though subduction plays a key role in the Earth's long-term S cycle. To address this knowledge gap, we analyzed stable sulfur and oxygen isotope compositions (δ34S and δ18O values) of dissolved sulfate (SO42−) in 55 thermal springs from five distinct settings in the Andean orogen. These regions are the Peruvian flat slab and backarc, transition between these two, Argentinian backarc, and Chilean forearc. Although the flat-slab settings had lower SO42− concentrations (<2000 mg/L) compared to the steep-slab settings (<12,700 mg/L), there was no significant relationship between isotope composition of SO42− and slab geometry. The δ34S and δ18O values of SO42− varied widely across the studied areas (+0.2 to +23.5 ‰ and − 3.3 to +16.0 ‰, respectively) and reflected the isotope compositions of local bedrock endmembers from dissolution of marine evaporites (+5 to +25 ‰ and + 10 to +20 ‰, respectively) and oxidation of magmatic and/or hydrothermal S and ore sulfide minerals with variable δ34S (0 to +16 ‰). The δ18O and δ2H values of thermal spring water (−18.5 to −3.3 ‰ and − 141.1 to −23.7 ‰, respectively) were consistent with meteoric precipitation, and in most cases decreased with increasing altitude following precipitation in the Andes. Generally, our isotope results do not support the direct transfer of slab-derived S/SO42− to thermal springs in the investigated settings. Rather, the δ34S and δ18O of SO42− in the thermal springs are a sensitive indicator of local water-rock interactions that remobilize bedrock S originating from a complex orogenic cycle reflecting tectonic uplift, erosion, weathering, and exhumation history across the duration of Andean Mountain building.

Evaluating The Impact of Increased Heavy Oil Consumption on Urban Pollution Levels through Isotope (δ13C, δ34S, 14C) Composition

The impact of heavy fuel oil (HFO) on the chemical and isotopic composition of submicron particulate matter (PM1) was investigated. For this purpose, we conducted an analysis of water-soluble inorganic ions (WSIIs) and multiple isotopes (δ34S, δ13C, 14C) of PM1 and SO2 collected during two heating periods: before (2021–2022) and during the use of HFO (2022–2023) in Vilnius, Lithuania. The results showed that the combustion of HFO increased the concentrations of SO₂ (by 94%) and PM1-related sulfate (by 30%). It also altered the chemical composition of PM1, with sulfate becoming the predominant component (~40%) of WSIIs. The stable sulfur isotope ratios of SO2 (δ34SSO2) and sulfate (δ34SPM1) shifted significantly to more negative values (δ34SSO2 = 0.4‰, δ34SPM1 = −0.3‰) compared to the previous heating period. Anticorrelation between δ¹³C and δ³⁴S values indicated increased contributions of ¹³C-enriched fossil fuel sources (coal and HFO) in EC, although the share of fossil fuels in elemental carbon (EC) slightly decreased during the HFO period. The combustion of HFO affected the concentrations of PM1 chemical components and substantially impacted the isotopic composition and source contributions of sulfate and EC.

Atmosphere and biological impact during sulfide formation in the Archean Central-Vozhma sulfide deposit (Karelia)

Relevance. The need of new knowledge about the early stages of the Earth. Sulfur isotope analysis of sulfide minerals is a powerful tool to understand the processes during the Archaean and Paleoproterozoic. Combined with other data, isotope geochemistry provides an insight into sulfur sources of sulfides from ancient sulfide volcanosedimentary deposits; geochemical factors affecting Archaean sulfide volcanosedimentary ore formation; adjust genetic models and determine the degree of influence of bacteria on the mineral formation. Aim. To identify the sources of sulfur during the formation of sulfide deposits via isotope analysis, and to evaluate bacteria affect mineral formation. Objects. They were obtained from the core of boreholes of Mesoarchaean volcanosedimentary sulfide Central-Vozhma deposit, being a part of the Sumozersko-Kenozersky greenstone belt of the Karelian craton. Methods. Mineralogical studies of rock and ore samples were carried out using optical microscopy; scanning electron microscopy and energy dispersive X-ray spectroscopy. The ratios of four stable sulfur isotopes were analyzed in sulfide minerals of the deposit (33S/32S, 34S/32S, 36S/32S). Results. The results obtained demonstrated the polygenic source of sulfur in sulfides. The sulfides have both positive and negative Δ33S values, indicating the presence of atmospheric sulfur formed under UV photolysis during mineral formation. Sulfide minerals include the following components: Seawater sulfate sulfur of photolytic genesis showed a negative anomaly Δ33S (∼ –0.4‰). It was the source of authigenic pyrite. Sulfides crystallized as a result of biological sulfate reduction demonstrated a narrow range of δ34S values (–2.64‰˂0˂+4.27‰). Elemental sulfur of photolytic genesis mobilized from the host sedimentary rocks by hydrothermal fluids. This sulfur, with a positive Δ33S anomaly (up to +1.6‰) took part in the massive sulfide ores formation.

Tracing the evolution of the world's first mined bauxite from palaeotopography to pyritization: Insights from Minjera deposits, Istria, Croatia

The Minjera bauxites are the first analysed and mined bauxites in the world. They are a group of pyritised bauxites situated in northern Istria, developed during the subaerial exposure phase which marked a major part of the Late Cretaceous and Palaeocene in northern Istria. In this study, the morphology, petrography, mineralogy, geochemistry as well as stable sulphur isotopes of the D-1 and D-15 deposits from Minjera were studied, as well as the evolution of their bedrock and cover. This study found that those two deposits differ in morphology, mineralogy and geochemistry as a consequence of their different palaeotopographical positions, with the D-1 deposit located at a higher position at the time of its formation compared to D-15, which led to the higher degree of leaching and desilicification in the D-1 deposit. The pyritisation in the studied deposits was a multi-phase process, which began with the deposition of framboidal pyrite and micrometre-sized anhedral pyrite, over which colloform pyrite was precipitated. This indicates that the solutions were initially supersaturated with iron sulphide, saturation of which subsequently changed, as finally euhedral, dendritic and acicular pyrite were deposited, indicating undersaturated conditions. The final stage was marked by deposition of pyrite veins. This formational sequence of pyrites is also supported by stable sulphur isotopes, as the δ34S values exhibit a wide range from -40.86 to 2.32 ‰, where lower values indicate an open system with an unrestricted sulphate supply in which supersaturated conditions could have been achieved, while the higher values indicate a change towards a closed system with limited sulphate supply. The organic matter necessary for microbial sulphate reduction was derived from the marshy environment established atop of the bauxite. The initial flooding started in the Palaeocene, with the first part of the sequence being deposited under lacustrine conditions, which changed towards fully marine with the deposition of Foraminiferal limestones.

Oxygen and sulfur stable isotope ratios of Late Devonian vertebrates trace the relative salinity of their aquatic environments

Late Devonian aquatic environments hosted the fin-to-limb transition in vertebrates. Upper Devonian (ca. 365−360 Ma) strata in Pennsylvania, USA, preserve a diversity of fishes and tetrapods in coastal marine to fluvial depositional environments, making this region ideal for investigating the ecology and evolution of Late Devonian vertebrates. A key unresolved issue has been reconstructing the specific aquatic habitats that hosted various vertebrates during this period. Specifically, the salinity of environments spanning fresh to shallow marine water is difficult to discern from sedimentological and paleontological analyses alone. Here, we analyze rare earth elements and yttrium (REY) as well as stable oxygen and sulfur isotope compositions (δ18O, δ34S) in fossil vertebrate bioapatite from late Famennian (ca. 362−360 Ma) strata of the Catskill and Lock Haven formations in the Appalachian Basin, USA, to determine the relative salinity of their aquatic environments. These results confirm the ecological euryhalinity of several taxa (Bothriolepis sp., tristichopterids, and Holoptychius sp.). Our results are the first demonstrating that some early tetrapod species occupied unequivocally freshwater habitats by late Famennian time (ca. 362−360 Ma). Our study shows that integrating sedimentological and paleontological data with combined oxygen and sulfur isotope analysis allows precise tracing of the relative salinity of vertebrate habitats deep in the past.

Sulfur stable isotopes in Paleogene coals of Northeast India

Sulfur stable isotope signatures are instrumental in tracing the sources and tracking the movement of sulfur in different environmental compartments, besides providing vital insights into the origin and transport dynamics. Sulfur stable isotope composition in coal can give valuable information regarding sulfur sources and the process of sulfur incorporation in coal. The present study was conducted to determine the total sulfur content and sulfur isotopic composition for bulk sulfur (bulk S δ34S) in Oligocene and Eocene coal samples from coal mines and a few coal stockings in northeast India. The results revealed that the total sulfur content in coal samples varied between 1.03 and 4.80 (wt%) with an average value of 2.64 wt%. The bulk S δ34S in coal samples exhibited a wide range between −4.66 ‰ to 14.78 ‰ (VCDT). Oligocene coal samples from mines in Arunachal Pradesh, Assam, and Nagaland were enriched with heavier sulfur isotopes relative to Eocene coal samples from the Jaintia Hills region of Meghalaya. A moderate positive correlation was observed in the Oligocene coal samples, in contrast to the moderate negative correlation found in the Eocene coal samples. The bulk S δ34S values and sulfur content in coal samples from coal stockings matched closely with Assam and Meghalaya mine samples. The findings of this study can be used to track the sources and movement of coal sulfur in various environmental compartments, besides providing valuable information about sulfur sources, the process of sulfur incorporation in coal, and the depositional environment.

The stable sulfur isotope and abundance fluxes of reduced inorganic sulfur and organic sulfur phases recorded in the Permian-Triassic transition of the Meishan type section

Sulfur cycle fluxes implicated in the Permian-Triassic mass extinction have traditionally been studied by the sulfur phase abundances in sedimentary rocks and the stable sulfur isotopic value (δ34S) of seawater sulfate inferred from mineral sulfate analyses. This information might be complemented by studies of the reduced inorganic sulfur and organic sulfur produced following bacterial sulfate reduction. To explore this potential the δ34S and concentration analyses of total reduced inorganic sulfur (TRIS) and organic sulfur – separately in the forms of kerogen (Ker) and individual organosulfur compounds, specifically dibenzothiophenes (DBTs) – has been conducted on sediments across the Late Permian to Early Triassic marine type section of Meishan-1 (South China). The relatively steady δ34S profiles (e.g., < 5 ‰ variation) of all sulfur phases measured through much of the late Permian were indicative of a primary seawater sulfate control, but other biogeochemical modulators caused prominent δ34S fluctuations of TRIS and DBT adjacent to the extinction event. The late Triassic δ34STRIS profile of Meishan-1 displayed a notable 34S enrichment (+15 ‰ increase) in bed 22–24 sediments concomitant with lower δ34SDBT values (−7 ‰ decrease), whereas co-eval δ34SKerS values remained relatively constant. The contrasting δ34SDBT and δ34SKerS data suggests the dynamic behavior of specific diagenetic sulfurisation processes may be resolved by the δ34S of discrete organic sulfur compounds (i.e., dibenzothiophenes, DBTs), but dissipated by the sulfurisation collective represented by the bulk kerogen fraction. The inverse isotopic trend observed between DBT and TRIS resulted in negative Δδ34SDBT-TRIS values identifying an organic sulfurisation pathway(s) with an unusual preference over pyrite (FeS2) for the lighter stable sulfur isotope. A redox control of the δ34SDBTs and δ34STRIS deviations in the bed 22–24 extinction interval was confirmed by coincident variation in TRIS/(TRIS + KerS) and pyrite (Py) and highly reactive (HR) iron ratios (FePy/FeHR). The iron (Fe) speciation data indicated a transition to ferruginous conditions, ruling out Fe2+ limitation as a factor in the bias against 34S evident in DBT formation. The 34S depletion of the DBTs promoted by the ferruginous setting may arise from the rapid and irreversible reaction of organic substrates with labile sulfur anions (e.g. HS-) or be supported by an especially localised sediment–water depositional microenvironment. Our study highlights the potential of incorporating stable sulfur isotope analytics of reduced and organic sulfur phases, particularly of specific organic compounds, into a holistic assessment of the dynamic sulfur biochemical periods of Earth’s past.

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

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

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

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

Multiple sulfur isotopes evidence deep intra-slab transport of sulfate-rich fluids

Sub-arc mantle oxidation is often attributed to sulfates from seawater transported in aqueous fluids derived from slab dehydration, but sulfur speciation and origin(s) in high-pressure fluids remain weakly constrained. Here, we use the four sulfur stable isotopes (32S, 33S, 34S, 36S) to decipher processes, e.g. mixing of two end-member reservoirs and open-system reaction occurring during sulfur devolatilization, and deduce the nature and origin of sulfur species in aqueous slab-derived fluids. We analyzed high pressure metamorphic rocks from the Monviso massif Lower Shear Zone (LSZ; Western Alps), recording evidence of an interface-parallel, channelized fluid flow near peak burial metamorphic conditions (∼550 °C and 2.7 GPa). We sampled variably metasomatized Fe-Ti metagabbros, hybrid (talc) schists and serpentinites containing sulfides supposed to preserve the aqueous fluid composition, as well as other alpine metagabbro, metabasalt and serpentinites from greenschist to eclogite-facies devoid of the studied metasomatic overprint.The millimeter to centimeter-sized sulfide crystals found in abundance within LSZ lithologies are mainly pyrites containing inclusions of the peak burial mineral assemblage (e.g. garnet, omphacite, rutile) indicating their crystallization at peak conditions or during incipient exhumation. The sulfides in the non-metasomatic metagabbros and metabasalts cover a narrow range in δ’34S of 0.89 ± 0.63 ‰ and Δ’33S of 0.017 ± 0.01 (n = 6) that could be inherited from hydrothermal sulfides formed on the seafloor. In contrast, the LSZ sulfides from the Fe-Ti metagabbros, serpentinites and hybrid schists (n = 24) are enriched in 34S and 33S (bulk δ’34S from 4.91 to 21.32 ‰ and Δ’33S from 0.02 to 0.06 ‰) compared to the sulfides from the non-metasomatic rocks. Mixing between reduced sulfur species cannot explain all the data without requiring an end-member composition as high as δ34S ∼ 22 ‰ and Δ33S ∼ 0.06 ‰, i.e. values rarely recorded by sulfides in the literature. Instead, we propose that this 33S-34S-enrichment results from open-system sulfate reduction to sulfides in aqueous fluids at 550°C, with an initial δ34S ∼ 12 ± 3 ‰ and Δ33S ∼ 0.025 ± 0.010 ‰. Because this signature is different from seawater sulfate, we suggest that sulfate was produced by hydrothermal sulfide oxidation during antigorite breakdown at 650°C, in agreement with Mg, Ni and Cr enrichments in the metasomatized HP mafic lithologies. This model is consistent with relatively oxidized 34S-enriched arc lavas and can potentially explain recycled sulfur with positive δ34S signature recorded by ocean island basalts.

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

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

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

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

Speciation and Possible Origins of Organosulfur Compounds in Rice Paddy Soils Affected by Acid Mine Drainage.

Although sulfur cycling in acid mine drainage (AMD)-contaminated rice paddy soils is critical to understanding and mitigating the environmental consequences of AMD, potential sources and transformations of organosulfur compounds in such soils are poorly understood. We used sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy to quantify organosulfur compounds in paddy soils from five AMD-contaminated sites and one AMD-uncontaminated reference site near the Dabaoshan sulfide mining area in South China. We also determined the sulfur stable isotope compositions of water-soluble sulfate (δ34SWS), adsorbed sulfate (δ34SAS), fulvic acid sulfur (δ34SFAS), and humic acid sulfur (δ34SHAS) in these samples. Organosulfate was the dominant functional group in humic acid sulfur (HAS) in both AMD-contaminated (46%) and AMD-uncontaminated paddy soils (42%). Thiol/organic monosulfide contributed a significantly lower proportion of HAS in AMD-contaminated paddy soils (8%) compared to that in AMD-uncontaminated paddy soils (21%). Within contaminated soils, the concentration of thiol/organic monosulfide was positively correlated with cation exchange capacity (CEC), moisture content (MC), and total Fe (TFe). δ34SFAS ranged from -6.3 to 2.7‰, similar to δ34SWS (-6.9 to 8.9‰), indicating that fulvic acid sulfur (FAS) was mainly derived from biogenic S-bearing organic compounds produced by assimilatory sulfate reduction. δ34SHAS (-11.0 to -1.6‰) were more negative compared to δ34SWS, indicating that dissimilatory sulfate reduction and abiotic sulfurization of organic matter were the main processes in the formation of HAS.

Shrouded in history: Unveiling the ways of life of an early Muslim population in Santarém, Portugal (8th- 10th century AD).

In around 716 AD, the city of Santarém, Portugal, was conquered by the Berber and Arab armies that swept the Iberian Peninsula and went on to rule the region until the 12th century. Archaeological excavations in 2007/08 discovered an Islamic necropolis (Avenida 5 de Outubro #2-8) that appears to contain the remains of an early Muslim population in Santarém (8th- 10th century). In this study, skeletal material from 58 adult individuals was analysed for stable carbon (δ13Ccol; δ13Cap), nitrogen (δ15N) and sulphur (δ34S) isotope ratios in bones, and stable oxygen (δ18O), carbon (δ13Cen) and radiogenic strontium (87Sr/86Sr) isotopes in tooth enamel. The results of this study revealed a dietary pattern of predominantly C3-plant and domestic C3-fed herbivore consumption during adulthood (δ13Ccol and δ15N, respectively) but a higher proportion of C4-plant input during childhood (δ13Cen) for some individuals-interpreted as possible childhood consumption of millet porridge, a common practice in North Africa-in those with unorthodox burial types (Groups 1 and 2) that was not practiced in the individuals with canonical burials (Group 3). In this first mobility study of a medieval Muslim population in Portugal, δ18ODW values revealed greater heterogeneity in Groups 1 and 2, consistent with diverse origins, some in more humid regions than Santarém when compared to regional precipitation δ18O data, contrasting the more homogenous Group 3, consistent with the local precipitation δ18O range. Ancient DNA analysis conducted on three individuals revealed maternal (mtDNA) and paternal (Y-chromosome) lineages compatible with a North African origin for (at least) some of the individuals. Additionally, mobility of females in this population was higher than males, potentially resulting from a patrilocal social system, practiced in Berber and Arab communities. These results serve to offer a more detailed insight into the ancestry and cultural practices of early Muslim populations in Iberia.

Allochthonous marsh subsidies enhances food web productivity in an estuary and its surrounding ecosystem mosaic.

Terrestrial organic matter is believed to play an important role in promoting resilient estuarine food webs, but the inherent interconnectivity of estuarine systems often obscures the origins and importance of these terrestrial inputs. To determine the relative contributions of terrestrial (allochthonous) and aquatic (autochthonous) organic matter to the estuarine food web, we analyzed carbon, nitrogen, and sulfur stable isotopes from multiple trophic levels, environmental strata, and habitats throughout the estuarine habitat mosaic. We used a Bayesian stable isotope mixing model (SIMM) to parse out relationships among primary producers, invertebrates, and a pelagic and demersal fish species (juvenile Chinook salmon and sculpin, respectively). The study was carried out in the Nisqually River Delta (NRD), Washington, USA, a recently-restored, macrotidal estuary with a diverse habitat mosaic. Plant groupings of macroalgae, eelgrass, and tidal marsh plants served as the primary base components of the NRD food web. About 90% of demersal sculpin diets were comprised of benthic and pelagic crustaceans that were fed by autochthonous organic matter contributions from aquatic vegetation. Juvenile salmon, on the other hand, derived their energy from a mix of terrestrial, pelagic, and benthic prey, including insects, dipterans, and crustaceans. Consequently, allochthonous terrestrial contributions of organic matter were much greater for salmon, ranging between 26 and 43%. These findings demonstrate how connectivity among estuarine habitat types and environmental strata facilitates organic matter subsidies. This suggests that management actions that improve or restore lateral habitat connectivity as well as terrestrial-aquatic linkages may enhance allochthonous subsidies, promoting increased prey resources and ecosystem benefits in estuaries.

Quantifying SO2 oxidation pathways to atmospheric sulfate using stable sulfur and oxygen isotopes: laboratory simulation and field observation

Abstract. The formation of secondary sulfate in the atmosphere remains controversial, and it is an urgent need to seek a new method to quantify different sulfate formation pathways. Thus, SO2 and PM2.5 samples were collected from 4 to 22 December 2019 in the Nanjing region. Sulfur and oxygen isotopic compositions were synchronously measured to study the contribution of SO2 homogeneous and heterogeneous oxidation to sulfate. Meanwhile, the correlation of δ18O values between H2O and sulfate from SO2 oxidation by H2O2 and Fe3+ / O2 was simulatively investigated in the laboratory. Based on isotope mass equilibrium equations, the ratios of different SO2 oxidation pathways were quantified. The results showed that secondary sulfate constituted higher than 80 % of total sulfate in PM2.5 during the sampling period. Laboratory simulation experiments indicated that the δ18O value of sulfate was linearly dependent on the δ18O value of water, and the slopes of linear curves for SO2 oxidation by H2O2 and Fe3+ / O2 were 0.43 and 0.65, respectively. The secondary sulfate in PM2.5 was mainly ascribed to SO2 homogeneous oxidation by OH radicals and heterogeneous oxidation by H2O2 and Fe3+ / O2. SO2 heterogeneous oxidation was generally dominant during sulfate formation, and SO2 oxidation by H2O2 predominated in SO2 heterogeneous oxidation reactions, with an average ratio around 54.6 %. This study provided an insight into precisely evaluating sulfate formation by combining stable sulfur and oxygen isotopes.

Geographic distribution of feather δ34S in Europe

AbstractGeographic distribution models of environmentally stable isotopes (the so‐called “isoscapes”) are widely employed in animal ecology, and wildlife forensics and conservation. However, the application of isoscapes is limited to elements and regions for which the spatial patterns have been estimated. Here, we focused on the ubiquitous yet less commonly used stable sulfur isotopes (δ34S). To predict the European δ34S isoscape, we used 242 feather samples from Eurasian Reed Warbler (Acrocephalus scirpaceus) formed at 69 European wetland sites. We quantified the relationships between sample δ34S and environmental covariates using a random forest regression model and applied the model to predict the geographic distribution of δ34S. We also quantified within‐site variation in δ34S and complementarity with other isotopes on both individual and isoscape levels. The predicted feather δ34S isoscape shows only slight differences between the central and southern parts of Europe while the coastal regions were most enriched in 34S. The most important covariates of δ34S were distance to coastline, surface elevation, and atmospheric concentrations of SO2 gases. The absence of a systematic spatial pattern impedes the application of the δ34S isoscape, but high complementarity with other isoscapes advocates the combination of multiple isoscapes to increase the precision of animal tracing. Feather δ34S compositions showed considerable within‐site variation with highest values in inland parts of Europe, likely attributed to wetland anaerobic conditions and redox sensitivity of sulfur. The complex European geography and topography as well as using δ34S samples from wetlands may contribute to the absence of a systematic spatial gradient of δ34S values in Europe. We thus encourage future studies to focus on the geographic distribution of δ34S using tissues from diverse taxa collected in various habitats over large land masses in the world (i.e., Africa, South America, or East Asia).