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.

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

RATIONALE: 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. METHODS: 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 1 year earlier) found on the ground. RESULTS: 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. CONCLUSIONS: 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.

Evaluating the multiple sulfur isotope signature of Eoarchean rocks from the Isua Supracrustal Belt (Southwest-Greenland) by MC-ICP-MS: Volcanic nutrient sources for early life.

On the anoxic Archean Earth, prior to the onset of oxidative weathering, electron acceptors were relatively scarce, perhaps limiting microbial productivity. An important metabolite may have been sulfate produced during the photolysis of volcanogenic SO2 gas. Multiple sulfur isotope data can be used to track this sulfur source, and indeed this record indicates SO2 photolysis dating back to at least 3.7 Ga, that is, as far back as proposed evidence of life on Earth. However, measurements of multiple sulfur isotopes in some key strata from that time can be challenging due to low sulfur concentrations. Some studies have overcome this challenge with NanoSIMS or optimized gas-source mass spectrometry techniques, but those instruments are not readily accessible. Here, we applied an aqua regia leaching protocol to extract small amounts of sulfur from whole rocks for analyses of multiple sulfur isotopes by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Measurements of standards and replicates demonstrate good precision and accuracy. We applied this technique to meta-sedimentary rocks with putative biosignatures from the Eoarchean Isua Supracrustal Belt (ISB, >3.7 Ga) and found positive ∆33S (1.40-1.80‰) in four meta-turbidites and negative ∆33S (-0.80‰ and -0.66‰) in two meta-carbonates. Two meta-basalts do not display significant mass-independent fractionation (MIF, -0.01‰ and 0.16‰). In situ Re-Os dating on a molybdenite vein hosted in the meta-turbidites identifies an early ca. 3.7 Ga hydrothermal phase, and in situ Rb-Sr dating of micas in the meta-carbonates suggests metamorphism affected the rocks at ca. 2.2 and 1.7 Ga. We discuss alteration mechanisms and conclude that there is most likely a primary MIF-bearing phase in these meta-sediments. Our new method is therefore a useful addition to the geochemical toolbox, and it confirms that organisms at that time, if present, may indeed have been fed by volcanic nutrients.

Using sulfur stable isotope ratios (δ34 S) for animal geolocation: Estimating the delay mechanisms between diet ingestion and isotope incorporation in tail hair.

RATIONALE: Metabolism and diet quality play an important role in determining delay mechanisms between an animal ingesting an element and depositing the associated isotope signal in tissue. While many isotope mixing models assume instantaneous reflection of diet in an animal- tissue, this is rarely the case. Here we use data from wildebeest to measure the lag time between ingestion of 34 S and its detection in tail hair. METHODS: We use time-lagged regression analysis of δ34 S data from GPS-collared blue wildebeest from the Serengeti ecosystem in combination with δ34 S isoscape data to estimate the lag time between an animal ingesting and depositing 34 S in tail hair. RESULTS: The best fitting regression model of δ34 S in tail hair and an individual- position on the δ34 S isoscape is generated assuming an average time delay of 78 days between ingestion and detection in tail hair. This suggests that sulfur may undergo multiple metabolic transitions before being deposited in tissue. CONCLUSION: Our findings help to unravel the underlying complexities associated with sulfur metabolism and are broadly consistent with results from other species. These findings will help to inform research aiming to apply the variation of δ34 S in inert biological material for geolocation or understanding dietary changes, especially for fast moving migratory ungulates such as wildebeest.

Multiple Sulfur Isotopic Evidence for Sulfate Formation in Haze Pollution.

The mechanism of sulfate formation during winter haze events in North China remains largely elusive. In this study, the multiple sulfur isotopic composition of sulfate in different grain-size aerosol fractions collected seasonally from sampling sites in rural, suburban, urban, industrial, and coastal areas of North China are used to constrain the mechanism of SO2 oxidation at different levels of air pollution. The Δ33S values of sulfate in aerosols show an obvious seasonal variation, except for those samples collected in the rural area. The positive Δ33S signatures (0‰ < Δ33S < 0.439‰) observed on clean days are mainly influenced by tropospheric SO2 oxidation and stratospheric SO2 photolysis. The negative Δ33S signatures (-0.236‰ < Δ33S < ∼0‰) observed during winter haze events (PM2.5 > 200 µg/m3) are mainly attributed to SO2 oxidation by H2O2 and transition metal ion catalysis (TMI) in the troposphere. These results reveal that both the H2O2 and TMI pathways play critical roles in sulfate formation during haze events in North China. Additionally, these new data provide evidence that the tropospheric oxidation of SO2 can produce significant negative Δ33S values in sulfate aerosols.

Multi-isotope identification of key hydrogeochemical processes and pollution pathways of groundwater in abandoned mining areas in Southwest China.

Acid mine drainage (AMD) is considered one of the serious environmental issues in the mining area. Understanding the key processes and pathways of hydrogeochemical evolution is critical for the effective control of AMD pollution. Hydrogeochemical analysis along with environmental isotope tracing was utilized to provide information regarding the hydrogeochemical process of groundwater pollution by using the multi-aquifer of abandoned Dashu pyrite in Southwest China as an example. Using the deuterium excess parameter d of groundwater and the results of 2H, 18O, and T analysis, the water-rock interaction intensity was determined. The distribution characteristics of d-T revealed that the groundwater primarily originated from the Quaternary reservoir platform groundwater and that there was a close hydraulic connection among the aquifers. The results of ion analysis and sulfur isotope tracing indicated that the sulfur in groundwater was primarily derived from gypsum dissolution, whereas the sulfur in mine water was primarily derived from pyrite oxidation. The results of the hydrogeochemical inversion indicated that mining activities altered the water level and flow conditions, promoted water-rock interactions, altered the hydrogeochemical process, and caused aquifer and mine water cross-contamination. The findings provide theoretical guidance for identifying the pollution sources and critical hydrogeochemical processes that affect groundwater in depleted mining areas of multi-aquifers and also provide technical support for developing water source control and prevention techniques.

Wide-spread microbial sulfate reduction (MSR) in northern European freshwater systems: Drivers, magnitudes and seasonality.

Microbial sulfate reduction (MSR), which transforms sulfate into sulfide through the consumption of organic matter, is an integral part of sulfur and carbon cycling. Yet, the knowledge on MSR magnitudes is limited and mostly restricted to snap-shot conditions in specific surface water bodies. Potential impacts of MSR have consequently been unaccounted for, e.g., in regional or global weathering budgets. Here, we synthesize results from previous studies on sulfur isotope dynamics in stream water samples and apply a sulfur isotopic fractionation and mixing scheme combined with Monte Carlo simulations to derive MSR in entire hydrological catchments. This allowed comparison of magnitudes both within and between five study areas located between southern Sweden and the Kola Peninsula, Russia. Our results showed that the freshwater MSR ranged from 0 to 79 % (interquartile range of 19 percentage units) locally within the catchments, with average values from 2 to 28 % between the catchments, displaying a non-negligible catchment-average value of 13 %. The combined abundance or deficiency of several landscape elements (e.g., the areal percentage of forest and lakes/wetlands) were found to indicate relatively well whether or not catchment-scale MSR would be high. A regression analysis showed specifically that average slope was the individual element that best reflected the MSR magnitude, both at sub-catchment scale and between the different study areas. However, the regression results of individual parameters were generally weak. The MSR-values additionally showed differences between seasons, in particular in wetland/lake dominated catchments. Here MSR was high during the spring flood, which is consistent with the mobilization of water that under low-flow winter periods have developed the needed anoxic conditions for sulfate-reducing microorganisms. This study presents for the first time compelling evidence from multiple catchments of wide-spread MSR at levels slightly above 10 %, implying that the terrestrial pyrite oxidation may be underestimated in global weathering budgets.

A comprehensive evaluation of sulfur isotopic analysis (δ34S and δ33S) using multi-collector ICP-MS with characterization of reference materials of geological and biological origin.

Sulfur isotope ratios are often used as biogeochemical tracers to gain understanding of abiotic and biological processes involved in the sulfur cycle in both modern and ancient environments. There is however a lack of matrix-matched well-characterized isotopic reference materials that are essential for controlling the accuracy and precision. This study therefore focused on expanding and complementing the currently available sulfur isotope ratio data by providing the bulk sulfur isotopic composition, as determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS), for a comprehensive set of commercially and/or readily available biological and geological reference materials. A total 7 isotopic reference materials and 41 elemental reference materials were studied. These reference materials include standards of terrestrial and marine animal origin, terrestrial plant origin, human origin, and geological origin. Different sample preparation protocols, including digestion and subsequent chromatographic isolation of S, were evaluated and the optimum approach selected for each matrix type. For achieving enhanced robustness, the sample preparation and sulfur isotope ratio measurements were done at two different laboratories for selected reference materials, while at one of the laboratories the measurements were additionally performed using two different MC-ICP-MS instruments. Determined δ34SVCDT and δ33SVCDT values compared well between the different laboratories, as well as between the different generation MC-ICP-MS instruments, and for standards that were previously characterized, our data are similar to literature values. The δ34SVCDT ranges determined for the different categories of the reference materials - terrestrial animal origin: +2 to +9‰, marine animal origin: +15 to +20‰, human origin: +6 to +10‰, terrestrial plant origin: -20 to +7‰, and geological origin: -12 to +21‰ - fit the expected values based on previous studies of similar types of matrices well. No significant mass-independent fractionation is observed when considering the expanded uncertainties for Δ33SV-CDT.

Stable Isotopic and Metagenomic Analyses Reveal Microbial-Mediated Effects of Microplastics on Sulfur Cycling in Coastal Sediments.

Microplastics are readily accumulated in coastal sediments, where active sulfur (S) cycling takes place. However, the effects of microplastics on S cycling in coastal sediments and their underlying mechanisms remain poorly understood. In this study, the transformation patterns of different S species in mangrove sediments amended with different microplastics and their associated microbial communities were investigated using stable isotopic analysis and metagenomic sequencing. Biodegradable poly(lactic acid) (PLA) microplastics treatment increased sulfate (SO42-) reduction to yield more acid-volatile S and elementary S, which were subsequently transformed to chromium-reducible S (CRS). The S isotope fractionation between SO42- and CRS in PLA treatment increased by 9.1‰ from days 0 to 20, which was greater than 6.8‰ in the control. In contrast, recalcitrant petroleum-based poly(ethylene terephthalate) (PET) and polyvinyl chloride (PVC) microplastics had less impact on the sulfate reduction, resulting in 7.6 and 7.7‰ of S isotope fractionation between SO42- and CRS from days 0 to 20, respectively. The pronounced S isotope fractionation in PLA treatment was associated with increased relative abundance of Desulfovibrio-related sulfate-reducing bacteria, which contributed a large proportion of the microbial genes responsible for dissimilatory sulfate reduction. Overall, these findings provide insights into the potential impacts of microplastics exposure on the biogeochemical S cycle in coastal sediments.

Multiple sulphur isotope record of Paleoarchean sedimentary rocks across the Onverwacht Group, Barberton Greenstone Belt, South Africa.

This study presents multiple sulphur isotope (32 S, 33 S, 34 S, 36 S) data on pyrites from silicified volcano-sedimentary rocks of the Paleoarchean Onverwacht Group of the Barberton greenstone belt, South Africa. These rocks include seafloor cherts and felsic conglomerates that were deposited in shallow marine environments preserving a record of atmospheric and biogeochemical conditions on the early Earth. A strong variation in mass independent sulphur isotope fractionation (MIF-S) anomalies is found in the cherts, with Δ33 S ranging between -0.26‰ and 3.42‰. We explore possible depositional and preservational factors that could explain some of this variation seen in MIF-S. Evidence for microbial activity is recorded by the c. 3.45 Ga Hooggenoeg Formation Chert (HC4) preserving a contribution of microbial sulphate reduction (-Δ33 S and -δ34 S), and a c. 3.33 Ga Kromberg Formation Chert (KC5) recording a possible contribution of microbial elemental sulphur disproportionation (+Δ33 S and -δ34 S). Pyrites from a rhyo-dacitic conglomerate of the Noisy Formation do not plot along a previously proposed global Felsic Volcanic Array, and this excludes short-lived pulses of intense felsic volcanic gas emissions as the dominant control on Archean MIF-S. Rather, we suggest that the MIF-S signals measured reflect dilution during marine deposition, early diagenetic modification, and mixing with volcanic/hydrothermal S sources. Given the expanded stratigraphic interval (3.47-3.22 Ga) now sampled from across the Barberton Supergroup, we conclude that large MIF-S exceeding >4‰ is atypical of Paleoarchean near-surface environments on the Kaapvaal Craton.

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.

Multi-isotopes in human hair: A tool to initiate cross-border collaboration in international cold-cases.

Unidentified human remains have historically been investigated nationally by law enforcement authorities. However, this approach is outdated in a globalized world with rapid transportation means, where humans easily move long distances across borders. Cross-border cooperation in solving cold-cases is rare due to political, administrative or technical challenges. It is fundamental to develop new tools to provide rapid and cost-effective leads for international cooperation. In this work, we demonstrate that isotopic measurements are effective screening tools to help identify cold-cases with potential international ramifications. We first complete existing databases of hydrogen and sulfur isotopes in human hair from residents across North America by compiling or analyzing hair from Canada, the United States (US) and Mexico. Using these databases, we develop maps predicting isotope variations in human hair across North America. We demonstrate that both δ2H and δ34S values of human hair are highly predictable and display strong spatial patterns. Multi-isotope analysis combined with dual δ2H and δ34S geographic probability maps provide evidence for international travel in two case studies. In the first, we demonstrate that multi-isotope analysis in bulk hair of deceased border crossers found in the US, close to the Mexico-US border, help trace their last place of residence or travel back to specific regions of Mexico. These findings were validated by the subsequent identification of these individuals through the Pima County Office of the Medical Examiner in Tucson, Arizona. In the second case study, we demonstrate that sequential multi-isotope analysis along the hair strands of an unidentified individual found in Canada provides detailed insights into the international mobility of this individual during the last year of life. In both cases, isotope data provide strong leads towards international travel.

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.

Isotope evidence for temporal and spatial variations of anthropogenic sulfate input in the Yihe River during the last decade.

Pyrite oxidation and sedimentary sulfate dissolution are the primary components of riverine sulfate (SO42-) and are predominant in global SO42- flux into the ocean. However, the proportions of anthropogenic SO42- inputs have been unclear, and their tempo-spatial variations due to human activities have been unknown. Thus, field work was conducted in a spatially heterogeneous human-affected area of the Yihe River Basin (YRB) during a wet year (2010) and drought years (2017/2018). Dual sulfate isotopes (δ34S-SO42- and δ18O-SO42-) and Bayesian isotope mixing models were used to calculate the variable anthropogenic SO42- inputs and elucidate their temporal impacts on riverine SO42- flux. The results of the mixing models indicated acid mine drainage (AMD) contributions increased from 56.1% to 83.1% of upstream sulfate and slightly decreased from 46.3% to 44.0% of midstream sulfate in 2010 and 2017/2018, respectively, in the Yihe River Basin. The higher upstream contribution was due to extensive metal-sulfide-bearing mine drainage. Sewage-derived SO42- and fertilizer-derived SO42- inputs in the lower reaches had dramatically altered SO42- concentrations and δ34S-SO42- and δ18O-SO42- values. Due to climate change, the water flow discharge decreased by about 70% between 2010 and 2017/2018, but the riverine sulfate flux was reduced by only about 58%. The non-proportional increases in anthropogenic sulfate inputs led to decreases in the flow-weighted average values of δ34S-SO42- and δ18O-SO42- from 10.3‰ to 9.9‰ and from 6.1‰ to 4.4‰, respectively. These outcomes confirm that anthropogenic SO42- inputs from acid mine drainage (AMD) have increased, but sewage effluents SO42- inputs have decreased.

Removal of contamination in helium for precise SF6 -based Δ36 S measurements.

RATIONALE: Quantifications of quadruple sulfur isotopic compositions (δ34 S, Δ33 S, and Δ36 S) of sulfur-bearing compounds in nature are valuable for providing new insights into the Earth's evolution such as the crust-mantle cycle, oxygenation of atmosphere and oceans, and the origin and evolution of early life. SF6 -based isotope ratio mass spectrometry is the most widely used method of quantification, but Δ36 S measurements at high precision and accuracy have always been technically difficult due to the low abundance of 36 S (~0.01%). In this paper, we identify a major source of isobaric interferences (i.e., contamination in helium carrier gas in the gas chromatography purification step) and propose a simple strategy to solve this problem. METHODS: An SF6 fluorination and purification system was built. Laboratory SF6 reference gas and international Ag2 S standard (IAEA-S1) were used as reference materials to test our method. Contamination from helium carrier gas (99.999%) was purified by a simple two-step cryogenic method to allow for accurate and precise measurements of Δ36 S using the SF6 -based isotope ratio mass spectrometry method. RESULTS: Without proper purification of helium carrier gas, large errors in Δ36 S measurements were found. Measured Δ36 S values of SF6 with trace contamination from helium were >10‰ higher than expected values. Using a newly developed purification strategy, the difference in Δ36 S values of SF6 before and after passing through the gas chromatography is less than instrumental errors (<0.2‰). Our improved method yielded an overall Δ36 S precision for IAEA-S1 of 0.12‰ (n = 6). This precision is comparable to that found by other laboratories around the world. CONCLUSION: Our simple two-step cryogenic method significantly improved the accuracy and precision of Δ36 S measurements and is therefore recommended for future determination of quadruple sulfur isotopic compositions in natural samples.

Sulfur isotopes of hydrothermal vent fossils and insights into microbial sulfur cycling within a lower Paleozoic (Ordovician-early Silurian) vent community.

Symbioses between metazoans and microbes involved in sulfur cycling are integral to the ability of animals to thrive within deep-sea hydrothermal vent environments; the development of such interactions is regarded as a key adaptation in enabling animals to successfully colonize vents. Microbes often colonize the surfaces of vent animals and, remarkably, these associations can also be observed intricately preserved by pyrite in the fossil record of vent environments, stretching back to the lower Paleozoic (Ordovician-early Silurian). In non-vent environments, sulfur isotopes are often employed to investigate the metabolic strategies of both modern and fossil organisms, as certain metabolic pathways of microbes, notably sulfate reduction, can produce large sulfur isotope fractionations. However, the sulfur isotopes of vent fossils, both ancient and recently mineralized, have seldom been explored, and it is not known if the pyrite-preserved vent organisms might also preserve potential signatures of their metabolisms. Here, we use high-resolution secondary ion mass spectrometry (SIMS) to investigate the sulfur isotopes of pyrites from recently mineralized and Ordovician-early Silurian tubeworm fossils with associated microbial fossils. Our results demonstrate that pyrites containing microbial fossils consistently have significantly more negative δ34 S values compared with nearby non-fossiliferous pyrites, and thus represent the first indication that the presence of microbial sulfur-cycling communities active at the time of pyrite formation influenced the sulfur isotope signatures of pyrite at hydrothermal vents. The observed depletions in δ34 S are generally small in magnitude and are perhaps best explained by sulfur isotope fractionation through a combination of sulfur-cycling processes carried out by vent microbes. These results highlight the potential for using sulfur isotopes to explore biological functional relationships within fossil vent communities, and to enhance understanding of how microbial and animal life has co-evolved to colonize vents throughout geological time.

Carbon­sulfur coupling in a seasonally hypoxic, high-sulfate reservoir in SW China: Evidence from stable CS isotopes and sulfate-reducing bacteria.

Anthropogenic input of sulfate (SO42-) in reservoirs may enhance bacterial sulfate reduction (BSR) under seasonally hypoxic conditions in the water column. However, factors that control BSR and its coupling to organic carbon (OC) mineralization in seasonally hypoxic reservoirs remain unclear. The present study elucidates the coupling processes by analyzing the concentrations and isotopic composition of dissolved inorganic carbon (DIC) and sulfur (SO42-, sulfide) species, and the microbial community in water of the Aha reservoir, SW China, which has high SO42- concentration due to the inputs from acid mine drainage about twenty years ago. The water column at two sites in July and October revealed significant thermal stratification. In the hypoxic bottom water, the δ13C-DIC decreased while the δ34S-SO42- increased, implying organic carbon mineralization due to BSR. The magnitude of S isotope fractionation (Δ34S, obtained from δ34Ssulfate-δ34Ssulfide) during the process of BSR fell in the range of 3.4‰ to 27.0‰ in July and 21.6‰ to 31.8‰ in October, suggesting a change in the community of sulfate-reducing bacteria (SRB). The relatively low water column stability in October compared to that in July weakened the difference of water chemistry and ultimately affected the SRB diversity. The production of DIC (ΔDIC) scaled a strong positive relationship with the Δ34S in July (p < 0.01), indicating that high OC availability favored the survival of incomplete oxidizers of SRB. However, in October, Δ13C-DIC was correlated with the Δ34S in the bottom hypoxic water (p < 0.01), implying that newly degraded OC depleted in 13C could favor the dominance of complete oxidizers of SRB which caused greater S isotope fractionation. Moreover, the sulfide supplied by BSR might stimulate the reductive dissolution of Fe and Mn oxides (Fe(O)OH and MnO2). The present study helps to understand the coupling of C and S in seasonally hypoxic reservoirs characterized by high SO42- concentration.

The Dziani Dzaha Lake: A long-awaited modern analogue for superheavy pyrites.

Sedimentary records of superheavy pyrites in Phanerozoic and Proterozoic successions (i.e., extremely positive δ34 Spyrite values together with higher δ34 Spyrite than coeval δ34 SCAS ) are mostly interpreted as resulting either from secondary postdepositional processes or from multiple redox reactions between sulfate and sulfide in stratified sulfate-poor environments. We report here the first observation of strongly positive δ34 S values for both dissolved sulfate and sulfide (average δ34 Sdiss.sulfate value of 34.6‰ and δ34 Sdiss.sulfide values of 36.7‰) compared to the present-day seawater δ34 Sdiss .sulfate (~21‰), with a negative apparent fractionation between sulfate and sulfide (∆34 Sdiss.sulfate-diss.sulfide ~ -2.1 ± 1.4‰), in the sulfate-poor (<3 mm) modern thalassohaline lacustrine system Dziani Dzaha (Mayotte, Indian Ocean). Overall, surface sediments faithfully record the water column isotopic signatures including a mainly negative ∆34 Ssed.sulfate-sed.sulfide (-4.98 ± 4.5‰), corresponding to the definition of superheavy pyrite documented in the rock record. We propose that in the Dziani Dzaha this superheavy pyrite signature results from a two-stage evolution of the sulfur biogeochemical cycle. In a first stage, the sulfur cycle would have been dominated by sulfate from initially sulfate-rich marine waters. Overtime, Raleigh distillation by microbial sulfate reduction coupled with sulfide burial in the sediment would have progressively enriched in 34 S the water column residual sulfate. In a second still active stage, quantitative sulfate reduction not only occurs below the halocline during stratified periods but also in the whole water column during fully anoxic episodes. Sulfates are then regenerated by partial oxidation of sulfides as the oxic-anoxic interface moves downward. These results demonstrate that the atypical superheavy pyrite isotope signature does not necessarily require postdepositional or secondary oxidative processes and can result from primary processes in restricted sulfate-poor and highly productive environments analogous to the Dziani Dzaha.

Sedimentary pyrite sulfur isotope compositions preserve signatures of the surface microbial mat environment in sediments underlying low-oxygen cyanobacterial mats.

The sedimentary pyrite sulfur isotope (δ34 S) record is an archive of ancient microbial sulfur cycling and environmental conditions. Interpretations of pyrite δ34 S signatures in sediments deposited in microbial mat ecosystems are based on studies of modern microbial mat porewater sulfide δ34 S geochemistry. Pyrite δ34 S values often capture δ34 S signatures of porewater sulfide at the location of pyrite formation. However, microbial mats are dynamic environments in which biogeochemical cycling shifts vertically on diurnal cycles. Therefore, there is a need to study how the location of pyrite formation impacts pyrite δ34 S patterns in these dynamic systems. Here, we present diurnal porewater sulfide δ34 S trends and δ34 S values of pyrite and iron monosulfides from Middle Island Sinkhole, Lake Huron. The sediment-water interface of this sinkhole hosts a low-oxygen cyanobacterial mat ecosystem, which serves as a useful location to explore preservation of sedimentary pyrite δ34 S signatures in early Earth environments. Porewater sulfide δ34 S values vary by up to ~25‰ throughout the day due to light-driven changes in surface microbial community activity that propagate downwards, affecting porewater geochemistry as deep as 7.5 cm in the sediment. Progressive consumption of the sulfate reservoir drives δ34 S variability, instead of variations in average cell-specific sulfate reduction rates and/or sulfide oxidation at different depths in the sediment. The δ34 S values of pyrite are similar to porewater sulfide δ34 S values near the mat surface. We suggest that oxidative sulfur cycling and other microbial activity promote pyrite formation in and immediately adjacent to the microbial mat and that iron geochemistry limits further pyrite formation with depth in the sediment. These results imply that primary δ34 S signatures of pyrite deposited in organic-rich, iron-poor microbial mat environments capture information about microbial sulfur cycling and environmental conditions at the mat surface and are only minimally affected by deeper sedimentary processes during early diagenesis.

Catchment-scale microbial sulfate reduction (MSR) of acid mine drainage (AMD) revealed by sulfur isotopes.

Laboratory experiments and point observations, for instance in wetlands, have shown evidence that microbial sulfate reduction (MSR) can lower sulfate and toxic metal concentrations in acid mine drainage (AMD). We here hypothesize that MSR can impact the fate of AMD in entire catchments. To test this, we developed a sulfur isotope fractionation and mass-balance method, and applied it at multiple locations in the catchment of an abandoned copper mine (Nautanen, northern Sweden). Results showed that MSR caused considerable, catchment-scale immobilization of sulfur corresponding to a retention of 27 ± 15% under unfrozen conditions in the summer season, with local values ranging between 13 ± 10% and 53 ± 18%. Present evidence of extensive MSR in Nautanen, together with previous evidence of local MSR occurring under many different conditions, suggest that field-scale MSR is most likely important also at other AMD sites, where retention of AMD may be enhanced through nature-based solutions. More generally, the developed isotope fractionation analysis scheme provides a relatively simple tool for quantification of spatio-temporal trends in MSR, answering to the emerging need of pollution control from cumulative anthropogenic pressures in the landscape, where strategies taking advantage of MSR can provide viable options.