Biogeochemical Sulfur Cycle Research Articles

An improved pyrite pretreatment protocol for kinetic and isotopic studies.

BackgroundPyrite is one of the most abundant and widespread of the sulfide minerals with a central role in biogeochemical cycles of iron and sulfur. Due to its diverse roles in the natural and anthropogenic sulfur cycle, pyrite has been extensively studied in various experimental investigations of the kinetics of its dissolution and oxidation, the isotopic fractionations associated with these reactions, the microbiological processes involved, and the effects of pyrite on human health. Elemental sulfur (S0) is a common product of incomplete pyrite oxidation. Preexisting S0 impurities as unaccounted reaction products are a source of experimental uncertainty, as are adhered fine grains of pyrite and its oxidation products. Removal of these impurities is, therefore, desirable.A robust standardized pretreatment protocol for removal of fine particles and oxidation impurities from pyrite is lacking. Here we describe a protocol for S0 and fine particle removal from the surface of pyrite by rinsing in acid followed by repeated ultrasonication with warm acetone.ResultsOur data demonstrate the presence of large fractions of S0 on untreated pyrite particle surfaces, of which only up to 60% was removed by a commonly used pretreatment method described by Moses et al. (GCA 51:1561-1571, 1987). In comparison, after pretreatment by the protocol proposed here, approximately 98% S0 removal efficiency was achieved. Additionally, the new procedure was more efficient at removal of fine particles of adhered pyrite and its oxidation products and did not appear to affect the particle size distribution, the specific surface area, or the properties of grain surfaces.ConclusionsThe suggested pyrite pretreatment protocol is more efficient in removal of impurities from pyrite grains, and provides multiple advantages for both kinetic and isotopic investigations of pyrite transformations under various environmental conditions.Electronic supplementary materialThe online version of this article (doi:10.1186/s12932-014-0010-0) contains supplementary material, which is available to authorized users.

Genomic insights into the uncultured genus 'Candidatus Magnetobacterium' in the phylum Nitrospirae.

Magnetotactic bacteria (MTB) of the genus 'Candidatus Magnetobacterium' in phylum Nitrospirae are of great interest because of the formation of hundreds of bullet-shaped magnetite magnetosomes in multiple bundles of chains per cell. These bacteria are worldwide distributed in aquatic environments and have important roles in the biogeochemical cycles of iron and sulfur. However, except for a few short genomic fragments, no genome data are available for this ecologically important genus, and little is known about their metabolic capacity owing to the lack of pure cultures. Here we report the first draft genome sequence of 3.42 Mb from an uncultivated strain tentatively named 'Ca. Magnetobacterium casensis' isolated from Lake Miyun, China. The genome sequence indicates an autotrophic lifestyle using the Wood-Ljungdahl pathway for CO2 fixation, which has not been described in any previously known MTB or Nitrospirae organisms. Pathways involved in the denitrification, sulfur oxidation and sulfate reduction have been predicted, indicating its considerable capacity for adaptation to variable geochemical conditions and roles in local biogeochemical cycles. Moreover, we have identified a complete magnetosome gene island containing mam, mad and a set of novel genes (named as man genes) putatively responsible for the formation of bullet-shaped magnetite magnetosomes and the arrangement of multiple magnetosome chains. This first comprehensive genomic analysis sheds light on the physiology, ecology and biomineralization of the poorly understood 'Ca. Magnetobacterium' genus.

Mapping sub-sea-floor communities

Subsurface Microbes The sea floor is teeming with microbes, whose sheer numbers produce a major effect on the global biogeochemical cycles of carbon, sulfur, and other important nutrients. Bowles et al. constructed a map showing how deeply sulfates penetrate marine sediments worldwide and how

Links between sulphur oxidation and sulphur-oxidising bacteria abundance and diversity in soil microcosms based onsoxBfunctional gene analysis

Sulphur-oxidising bacteria (SOB) play a key role in the biogeochemical cycling of sulphur in soil ecosystems. However, the ecology of SOB is poorly understood, and there is little knowledge about the taxa capable of sulphur oxidation, their distribution, habitat preferences and ecophysiology. Furthermore, as yet there are no conclusive links between SOB community size or structure and rates of sulphur oxidation. We have developed a molecular approach based on primer design targeting the soxB functional gene of nonfilamentous chemolithotrophic SOB that allows assessment of both abundance and diversity. Cloning and sequencing revealed considerable diversity of known soxB genotypes from agricultural soils and also evidence for previously undescribed taxa. In a microcosm experiment, abundance of soxB genes increased with sulphur oxidation rate in soils amended with elemental sulphur. Addition of elemental sulphur to soil had a significant effect in the soxB gene diversity, with the chemolithotrophic Thiobacillus-like Betaproteobacteria sequences dominating clone libraries 6 days after sulphur application. Using culture-independent methodology, the study provides evidence for links between abundance and diversity of SOB and sulphur oxidation. The methodology provides a new tool for investigation of the ecology and role of SOB in soil sulphur biogeochemistry.

First Rotation Biomass Production and Nutrient Cycling within Short-Rotation Coppice Willow Plantations in Saskatchewan, Canada

Although numerous studies have quantified different social, economic, energetic, and environmental benefits associated with short-rotation coppice (SRC) willow plantations, comprehensive assessments of nutrient cycling are rare. The objective of this study was to examine the biomass production and attendant biogeochemical cycling of nitrogen (N), phosphorus (P), potassium (K), sulfur (S), calcium (Ca), and magnesium (Mg) during the initial 4-year rotation of six willow varieties grown at four locations along a 500 km north-south pedoclimatic gradient within Saskatchewan, Canada. Nutrient budgets consisted of quantifying various nutrient inputs (e.g., atmospheric deposition and soil mineral weathering), outputs (e.g., fine and coarse root biomass, leaf biomass, harvested biomass, leaching, and denitrification), and transfers (e.g., soil organic matter mineralization, canopy exchange, leaf litter decomposition, and fine root turnover) associated with the plant available soil nutrient pool. Total above- and below-ground production during the rotation was approximately 40 Mg ha−1, with calculated soil nutrient budget deficits (i.e., nutrient outputs > inputs + transfers) of 17, 39, 112, 271, and 74 kg ha−1 for N, P, K, Ca, and Mg, respectively, averaged across the varieties and sites, but a soil S surplus of 60 kg ha−1. While soil nutrient budget deficits varied among sites, there were no significant differences (P > 0.05) among willow varieties. Despite the relatively low nutrient-demanding nature of willow and negligible leaching or denitrification losses, nutrient export in harvested biomass over multiple rotations will require soil nutrient amendments to maintain SRC willow productivity, particularly N and P, albeit a fraction of the amount required for annual agronomic crops.

Dimethylsulfide metabolism in marine isolates and their role in the biogeochemical cycling of sulfur (575.8)

Microbial degradation is a major sink for dimethylsulfide (DMS), a volatile organosulfur compound which has been implicated in climate control and the biogeochemical cycling of sulfur. While the majority of marine bacteria which are capable of growth on DMS are members of the Methylophaga genus and belong to the Gammaproteobacteria class, recent studies have demonstrated that bacteria belonging to the Alphaproteobacteria class are also able to metabolize DMS. For example, a DMS monooxygenase, which carries out the first step in the DMS degradation pathway, was recently isolated from Hyphomicrobium sulfonivorans, the first enzyme of its kind to be isolated and characterized.1 The enzyme is a member of the flavin‐linked monooxygenases of the luciferase family and is most closely related to nitrilotriacetate monooxygenases. This work reports on the DMS monooxygenase activity of several bacteria isolated from Mount Hope Bay, RI.Grant Funding Source: NSF

Microbial communities in uranium mine tailings and mine water sediment from Jaduguda U mine, India: A culture independent analysis

Microbial diversity within uranium mine tailings and mine water sediment from the Jaduguda uranium mine, India was characterized by metagenome-derived 16S rRNA gene clone libraries. Samples from fresh tailings (JFT244), abandoned (vegetated) tailings (JOT245) and mine water sediment (J1-5) having wide ranges of pH (5.7 to 10.4), nitrogen, phosphorus and organic carbon [150–5700 ppm, 800–9100 ppm and 0.18–6.5% (w/w)] and elevated metals (Ni, Cu, Zn and U) were used to explore the inhabitant bacterial and archaeal community structures. Consistent to the sample's physicochemical properties, up to four orders of magnitude variation in bacterial CFU counts was observed. The data showed that with increasing metal and decreasing nutrient (organic C, N, P, etc.) contents, microbial diversity indices decrease within the samples. Culture-independent analyses revealed predominance of phyla Proteobacteria and/or Acidobacteria within the samples along with members of Actinobacteria, Cyanobacteria, Chloroflexi, Genera incertae sedis OP10, Firmicutes and Planctomycete as relatively minor groups. Abundance of Crenarchaeota in tailings samples and Euryachaeota in mine water sediment was noted. Diversity of dissimilatory sulfate reductase gene (dsr) was studied. Putative metabolic properties as derived from taxonomy and phylogenetic lineages indicated presence of chemolithotrophic and heteotrophic aerobic and anaerobic organisms capable of nitrogen fixation, nitrate reduction and biogeochemical cycling of metals, sulfur and methane. The data indicated that indigenous microbial populations are capable of maintaining self-sustenance in these highly hazardous environments and possess catalytic potential for their use in in situ bioremediation.

Sulphoglycolysis in Escherichia coli K-12 closes a gap in the biogeochemical sulphur cycle

Sulphoquinovose (SQ, 6-deoxy-6-sulphoglucose) has been known for 50 years as the polar headgroup of the plant sulpholipid in the photosynthetic membranes of all higher plants, mosses, ferns, algae and most photosynthetic bacteria. It is also found in some non-photosynthetic bacteria, and SQ is part of the surface layer of some Archaea. The estimated annual production of SQ is 10,000,000,000 tonnes (10 petagrams), thus it comprises a major portion of the organo-sulphur in nature, where SQ is degraded by bacteria. However, despite evidence for at least three different degradative pathways in bacteria, no enzymic reaction or gene in any pathway has been defined, although a sulphoglycolytic pathway has been proposed. Here we show that Escherichia coli K-12, the most widely studied prokaryotic model organism, performs sulphoglycolysis, in addition to standard glycolysis. SQ is catabolised through four newly discovered reactions that we established using purified, heterologously expressed enzymes: SQ isomerase, 6-deoxy-6-sulphofructose (SF) kinase, 6-deoxy-6-sulphofructose-1-phosphate (SFP) aldolase, and 3-sulpholactaldehyde (SLA) reductase. The enzymes are encoded in a ten-gene cluster, which probably also encodes regulation, transport and degradation of the whole sulpholipid; the gene cluster is present in almost all (>91%) available E. coli genomes, and is widespread in Enterobacteriaceae. The pathway yields dihydroxyacetone phosphate (DHAP), which powers energy conservation and growth of E. coli, and the sulphonate product 2,3-dihydroxypropane-1-sulphonate (DHPS), which is excreted. DHPS is mineralized by other bacteria, thus closing the sulphur cycle within a bacterial community.

An improved pyrite pretreatment protocol for kinetic and isotopic studies

BackgroundPyrite is one of the most abundant and widespread of the sulfide minerals with a central role in biogeochemical cycles of iron and sulfur. Due to its diverse roles in the natural and anthropogenic sulfur cycle, pyrite has been extensively studied in various experimental investigations of the kinetics of its dissolution and oxidation, the isotopic fractionations associated with these reactions, the microbiological processes involved, and the effects of pyrite on human health. Elemental sulfur (S0) is a common product of incomplete pyrite oxidation. Preexisting S0 impurities as unaccounted reaction products are a source of experimental uncertainty, as are adhered fine grains of pyrite and its oxidation products. Removal of these impurities is, therefore, desirable.A robust standardized pretreatment protocol for removal of fine particles and oxidation impurities from pyrite is lacking. Here we describe a protocol for S0 and fine particle removal from the surface of pyrite by rinsing in acid followed by repeated ultrasonication with warm acetone.ResultsOur data demonstrate the presence of large fractions of S0 on untreated pyrite particle surfaces, of which only up to 60% was removed by a commonly used pretreatment method described by Moses et al. (GCA 51:1561-1571, 1987). In comparison, after pretreatment by the protocol proposed here, approximately 98% S0 removal efficiency was achieved. Additionally, the new procedure was more efficient at removal of fine particles of adhered pyrite and its oxidation products and did not appear to affect the particle size distribution, the specific surface area, or the properties of grain surfaces.ConclusionsThe suggested pyrite pretreatment protocol is more efficient in removal of impurities from pyrite grains, and provides multiple advantages for both kinetic and isotopic investigations of pyrite transformations under various environmental conditions.

Transformations of dimethylsulfide.

Dimethylsulfide (DMS) is a naturally occurring chemical that is part of the biogeochemical sulfur cycle and has been implicated in climate-relevant atmospheric processes. In addition, DMS occurs in soil environments as well as in food stuff as a flavor compound and it can also be associated with disease states such as halitosis. A major environmental source of DMS is the marine algal osmoprotectant dimethylsulfoniopropionate (DMSP). A variety of bacterial enzyme systems lead either to the production of DMS from DMSP or dimethylsulfoxide (DMSO) or its oxidation to, e.g., DMSO. The interconversion of DMS and DMSO is catalyzed by molybdenum-containing metalloenzymes that have been very well studied, and recently another enzyme system, an NADH-dependent, flavin-containing monooxygenase, that produces formaldehyde and methanethiol from DMS has also been described.DMS conversions are not limited to a specialized group of bacteria - evidence for DMS-based metabolism exists for heterotrophic, autotrophic and phototrophic bacteria and there is also evidence for the occurrence of this type of sulfur compound conversion in Archaea.

Regulation of atmospheric oxygen during the Proterozoic

Many studies suggest that oxygen has remained near modern levels throughout the Phanerozoic, but was much less abundant from the “Great Oxygenation Event” around 2.4 Ga until the late Neoproterozoic around 600 Ma (Kump, 2008). Using a simple model, we show that the maintenance of atmospheric pO2 at ∼1% of present atmospheric levels (PAL) is inconsistent with modern biogeochemical cycling of carbon, sulfur and iron unless new feedbacks are included. Low oxygen conditions are stable in our model if the flux of phosphorus to the oceans was greatly reduced during the Proterozoic. We propose a mechanism to reduce this flux through the scavenging of phosphate ions with an “iron trap” driven by greater surface mobility of ferrous iron in a low pO2 world. Incorporating this feedback leads to two stable equilibria for atmospheric oxygen, the first quantitative hypothesis to explain both Proterozoic and Phanerozoic O2 concentrations.

Geomicrobiology of Acid Mine Drainage in the weathering zone of pyrite-bearing schists in the Rudawy Janowickie Mountains (Poland)

This paper presents the geomicrobiological analysis of acid water reservoirs and Acid Mine Drainage (AMD) developed in the weathering zone of pyrite-bearing schists near the closed-down pyrite mine in Wieściszowice (south-western Poland ). The analysis was focused on two reservoirs characterized by different physical and chemical properties (pH, redox potential, content of sulphates and heavy metals). The study is the first thorough report on the geomicrobiological relationships taking place in the AMD setting in Wieściszowice and enables a description of the microbiological processes that significantly influence biogeochemical cycles of sulfur and iron in the analyzed water reservoirs. The reservoir water also harbors numerous big, organized microbial structures in the form of streamers. Samples of these structures were studied in detail using optical and electron microscopy, as well as microbiological cultivation and molecular methods. According to the obtained results, the slime streamers from the Wieściszowice mine are characterized by the co-occurrence of typical chemolithoautotrophic microorganisms oxidizing sulphur and iron together with sulphate reducing bacteria. The presence of these structures probably depends on the occurrence of iron (II) in the surrounding environment.

Paleoarchean sulfur cycle and biogeochemical surface conditions on the early Earth, Barberton, South Africa

This study presents the first multiple sulfur isotope dataset on sulfides from the ca. 3.5–3.2 Ga Onverwacht Group in the Paleoarchean Barberton Greenstone Belt (BGB) of South Africa. In situ δ34SCDT and Δ33S values of pyrite (n=568) are reported from a wide range of hydrothermal, volcanic and sedimentary environments and are used to explore Mid-Archean biogeochemical sulfur cycling. Samples are from fresh drill core collected by the Barberton Scientific Drilling Project that intercepted cherts, metabasalts and sheared ultramafics of the ∼3.3–3.35 Ga Kromberg Formation; the sedimentary units of the ∼3.432 Ga Noisy formation; and the unconformably underlying metabasaltic pillow lavas of the ∼3.472 Ga Hooggenoeg Formation.Pyrite in quartz-carbonate-veins in the lower diamictite of the Noisy sequence records the largest range and most negative δ34SCDT values so far reported from an Archean terrain (δ34SCDT=−55.04 to +27.46‰). The Noisy sediments also contain detrital and diagenetic pyrites with a significant variation in Δ33S of between −0.62 to +1.4‰ and δ34SCDT of between −7.00 and +12.6‰, interpreted to reflect tectonic exposure of these early sediments to atmospheric – shallow marine conditions. Early marine pyrites from the Kromberg Cherts also display strong positive Δ33S values up to +2.50‰ with narrow range in δ34SCDT values (−6.00 to +1.50‰), whereas hydrothermal veins in the basal ultramafic shear zones preserve magmatic values (∼0‰). This study reveals a potential proto-tectonic control on atmospheric, geodynamic and hydrothermal environments available for early sulfate reducing and/or methanogenic microbes in the Paleoarchean.No evidence for microbial sulfate reduction or disproportionation was identified in the Kromberg Cherts, despite previous morphological claims for microbial life. Highly variable and negative δ34SCDT values were found in the Noisy turbidites and Hooggenoeg pillow lava breccia supporting the presence of microbial sulfate reduction in early tectono-sedimentary basins and in the Paleoarchean sub-seafloor, respectively. In light of current controversies surrounding sulfur isotope studies in similar-aged rocks of the Pilbara Craton (West Australia), we argue that microbial elemental sulfur disproportionation was not a preferred metabolic pathway on the Paleoarchean earth.

Multiple sulfur and carbon isotope composition of sediments from the Belingwe Greenstone Belt (Zimbabwe): A biogenic methane regulation on mass independent fractionation of sulfur during the Neoarchean?

To explore the linkage between mass-independent sulfur isotope fractionation (MIF-S) and δ13Corg excursions during the Neoarchean, as well as the contemporary redox state and biogeochemical cycling of carbon and sulfur, we report the results of a detailed carbon and multiple sulfur (δ34S, δ33S, δ36S) isotopic study of the ∼2.7Ga Manjeri and ∼2.65Ga Cheshire formations of the Ngezi Group (Belingwe Greenstone Belt, Zimbabwe).Multiple sulfur isotope data show non-zero Δ33S and Δ36S values for sediments older than 2.4Ga (i.e. prior to the Great Oxidation Event, GOE), indicating MIF-S thought to be associated with low atmospheric oxygen concentration. However, in several 2.7–2.5Ga Neoarchean localities, small-scale variations in MIF-S signal (magnitude) seem to correlate with negative excursion in δ13Corg, possibly reflecting a global connection between the relative reaction rate of different MIF-S source reaction and sulfur exit channels and the biogenic flux of methane into the atmosphere during periods of localized, microbiologically mediated, shallow surface-water oxygenation.The Manjeri Formation black shales studied here display a wide range of δ13Corg between −35.4‰ and −16.2‰ (average of −30.3±6.0‰, 1σ), while the Cheshire Formation shales have δ13Corg between −47.7‰ and −35.1‰ (average −41.3±3‰, 1σ). The δ34S values of sedimentary sulfides from Manjeri Formation vary between −15.15‰ and +2.37‰ (average −1.71±4.76‰, 1σ), showing very small and mostly negative Δ33S values varying from −0.58‰ to 0.87‰ (average 0.02±0.43‰, 1σ). Cheshire Formation black shale sulfide samples measured in this study have δ34S values ranging from −2.11‰ to 2.39‰ (average 0.25±1.08‰, 1σ) and near zero and solely positive Δ33S anomalies between 0.14‰ and 1.17‰ (average 0.56±0.29‰, 1σ). Moreover, Δ36S/Δ33S in the two formations are comparable with a slope of −1.38 (Manjeri Formation) and −1.67 (Cheshire Formation), respectively. This differs from the Archean reference line (i.e. −0.9).The sulfur and carbon isotopic signatures recorded here likely reflect different environmental conditions and/or ecosystems within the sampled Cheshire and Manjeri formations paleofacies. The differences in carbon isotopes in different sedimentological facies are interpreted as recording different metabolic pathways, including photosynthesis, methanogenesis and methanotrophy. Low δ13Corg values in the Cheshire Formation black shales suggest a strong influence of methanotrophy (likely preceded by bacterial methanogenesis), while the large range of Manjeri Formation δ34S may record bacterial sulfate reduction. The C and multiple S isotopic variations recorded here may imply different patterns of C and S fractionation, perhaps dependent on variations in the biogenic egress of methane to the atmosphere.

Sulfur biogeochemistry of cold seeps in the Green Canyon region of the Gulf of Mexico

Cold seeps in the Gulf of Mexico provide a natural laboratory to study biogeochemical cycling of sulfur, carbon, and oxygen at hydrate- and hydrocarbon-rich deep marine settings with obvious additional relevance to studies of diverse modern and ancient seeps. Of particular interest are the sulfur isotope signatures of microbial sulfate reduction coupled to anaerobic oxidation of methane and other non-methane liquid and gaseous hydrocarbons.Whereas most of the published sulfur isotope data from cold seep systems pertain to pore-water species, our study integrates both solid and dissolved sulfur: acid-volatile sulfides (SAVS), pyrite (Spy), elemental sulfur (S°), dissolved sulfate and ΣH2S. Modeled and 35SO42− reduction rates and δ13C and δ18O data for authigenic carbonates are integrated within this sulfur framework. Our results indicate extreme variability over narrow spatial and temporal scales within short distances (meters) from active seeps. High rates of microbial sulfate reduction can lead to complete consumption of the sulfate within the upper few centimeters of burial, while meters away the sulfate profile shows little depletion. Such small-scale variability must reflect the structure and temporal dynamics of hydrocarbon migration in the presence of low amounts of background organic matter. Our past work demonstrated that electron donors other than methane drive significant levels of microbial activity at these seeps, and very recent work has demonstrated that oxidation of higher chain volatile hydrocarbons can contribute to the high levels of microbial activity. These findings are consistent with our new results.Elevated concentrations of pyrite and diagenetic carbonate relative to background sediments are diagnostic of active seepage, yet the S isotopes tell more complex stories. Low levels of the transient, ‘instantaneous’ products of S cycling—AVS and S°—show high δ34S values that increase with depth. Most of the pyrite formation, however, seems to be very early as limited by the availability of reactive Fe phases. As such, δ34S values for pyrite at ancient seeps can show consistently low δ34S values that undersell the full intensity of microbial sulfate reduction. Low sedimentation rates, and the resulting low detrital iron fluxes, may in fact limit our ability to recognize seeps in the geologic record using only δ34S compositions for pyrite.

Production, preservation, and biological processing of mass-independent sulfur isotope fractionation in the Archean surface environment

Mass-independent fractionation of sulfur isotopes (S MIF) in Archean and Paleoproterozoic rocks provides strong evidence for an anoxic atmosphere before ~2,400 Ma. However, the origin of this isotopic anomaly remains unclear, as does the identity of the molecules that carried it from the atmosphere to Earth's surface. Irrespective of the origin of S MIF, processes in the biogeochemical sulfur cycle modify the primary signal and strongly influence the S MIF preserved and observed in the geological record. Here, a detailed model of the marine sulfur cycle is used to propagate and distribute atmospherically derived S MIF from its delivery to the ocean to its preservation in the sediment. Bulk pyrite in most sediments carries weak S MIF because of microbial reduction of most sulfur compounds to form isotopically homogeneous sulfide. Locally, differential incorporation of sulfur compounds into pyrite leads to preservation of S MIF, which is predicted to be most highly variable in nonmarine and shallow-water settings. The Archean ocean is efficient in diluting primary atmospheric S MIF in the marine pools of sulfate and elemental sulfur with inputs from SO2 and H2S, respectively. Preservation of S MIF with the observed range of magnitudes requires the S MIF production mechanism to be moderately fractionating ( 20-40‰). Constraints from the marine sulfur cycle allow that either elemental sulfur or organosulfur compounds (or both) carried S MIF to the surface, with opposite sign to S MIF in SO2 and H2SO4. Optimal progress requires observations from nonmarine and shallow-water environments and experimental constraints on the reaction of photoexcited SO2 with atmospheric hydrocarbons.

Salt marsh vegetation as a carbonyl sulfide (COS) source to the atmosphere

Carbonyl sulfide (COS) is the most abundant and longest-lived reduced sulfur compound in the atmosphere; changes in its atmospheric concentration could significantly affect global climate and the biogeochemical sulfur cycle. The largest sink of COS in the troposphere is its destruction in plant leaves by the enzymes involved in photosynthesis. In this study, net fluxes of COS were measured from a coastal salt marsh on a subtropical barrier island on the Texas shore of the Gulf of Mexico. We find net emissions from sites with the common salt marsh plant Batis maritima compared to the net uptake from vegetated plots of most previously investigated biomes. The magnitude of the COS production from vegetated plots in this study was twice the emissions of soil-only salt marsh plots. This is the first time that emissions of COS have been found to be significantly enhanced by the presence of vegetation compared to soil alone. COS fluxes exceeded +110 pmol m−2 s−1 for non-inundated plots during daytime hours and were correlated with soil temperature at the depth of 5 cm. Tidal flooding inhibited soil COS exchange; however, we found continued net emissions from emergent B. maritima. This study suggests that emissions of COS resulted from interactions with the plants themselves, which would mean that B. maritima can mediate the production of atmospheric COS.

Dynamic sulfur and carbon cycling through the end-Ordovician extinction revealed by paired sulfate–pyrite δ34S

Geochemical records of the end-Ordovician Hirnantian Stage show parallel positive excursions in the stable isotope compositions of sedimentary pyrite sulfur (δ34Spyr), organic carbon (δ13Corg), and carbonate carbon (δ13Ccarb); these isotope excursions coincide with the end Ordovician glaciation and mass extinction. A relative increase in pyrite burial (fpyr) attributed to marine anoxia has been invoked to explain the sulfur isotope excursion and link oceanic redox conditions to the extinction of marine fauna. An increase in fpyr would necessarily generate a parallel excursion of equal magnitude in the isotopic composition of coeval marine sulfate (δ34SSO4). Here we present new high-resolution paired sulfur isotope data from carbonate-associated sulfate (δ34SCAS) and pyrite from the Hirnantian Stage of western Anticosti Island (Québec, Canada). These data document a positive 20‰ enrichment in δ34Spyr (comparable in magnitude to previous reports), but no parallel excursion in δ34SCAS. This pattern provides new constraints on the origin of the δ34Spyr excursion and the nature of carbon–sulfur coupling through Hirnantian time. Specifically, these observations preclude enhanced pyrite burial as the cause of the Hirnantian δ34Spyr excursion and suggest the possible role of anoxia in the mass extinction may need to be reevaluated. Rather, the global δ34Spyr excursion is best explained by a transient reduction in the isotopic fractionations expressed during microbial sulfur cycling (εpyr). The εpyr record shows a strong inverse correlation with δ13C, suggesting a mechanistic link between carbon cycling and processes controlling εpyr during the Hirnantian. Changes in sea level or marine redox state associated with glaciation could further impact the expression of the biological fractionation (e.g., through syndepositional sediment reworking and/or chemocline migration and resultant restricted exchange of porewater sulfate). The magnitude of isotopic fractionation during microbial sulfate reduction is partially controlled by metabolic rates, which are sensitive to the abundance, type, and lability of metabolically relevant substrates. Environmental change associated with the end Ordovician glaciation may have elevated the flux of organic material to marine sediments or caused an increase in physical reworking of sediments, leading to increased microbial sulfate reduction rates and reduced εpyr. As such, the Hirnantian δ34Spyr excursion may be viewed as a dynamic biological response to global climate change, highlighting the connections between the carbon and sulfur biogeochemical cycles.

Conserving energy with sulfate around 100 °C – structure and mechanism of key metal enzymes in hyperthermophilic Archaeoglobus fulgidus

Sulfate-reducing bacteria and archaea are important players in the biogeochemical sulfur cycle. ATP sulfurylase, adenosine 5'-phosphosulfate reductase and dissimilatory sulfite reductase are the key enzymes in the energy conserving process of SO4(2-) → H2S reduction. This review summarizes recent advances in our understanding of the activation of sulfate to adenosine 5'-phosphosulfate, the following reductive cleavage to SO3(2-) and AMP, and the final six-electron reduction of SO3(2-) to H2S in the hyperthermophilic archaeon Archaeoglobus fulgidus. Structure based mechanisms will be discussed for these three enzymes which host unique metal centers at their catalytic sites.

Fractionation of sulfur isotopes by Desulfovibrio vulgaris mutants lacking hydrogenases or type I tetraheme cytochrome c3

The sulfur isotope effect produced by sulfate reducing microbes is commonly used to trace biogeochemical cycles of sulfur and carbon in aquatic and sedimentary environments. To test the contribution of intracellular coupling between carbon and sulfur metabolisms to the overall magnitude of the sulfur isotope effect, this study compared sulfur isotope fractionations by mutants of Desulfovibrio vulgaris Hildenborough. We tested mutant strains lacking one or two periplasmic (Hyd, Hyn-1, Hyn-2, and Hys) or cytoplasmic hydrogenases (Ech and CooL), and a mutant lacking type I tetraheme cytochrome (TpI-c3). In batch culture, wild-type D. vulgaris and its hydrogenase mutants had comparable growth kinetics and produced the same sulfur isotope effects. This is consistent with the reported redundancy of hydrogenases in D. vulgaris. However, the TpI-c3 mutant (ΔcycA) exhibited slower growth and sulfate reduction rates in batch culture, and produced more H2 and an approximately 50% larger sulfur isotope effect, compared to the wild type. The magnitude of sulfur isotope fractionation in the CycA deletion strain, thus, increased due to the disrupted coupling of the carbon oxidation and sulfate reduction pathways. In continuous culture, wild-type D. vulgaris and the CycA mutant produced similar sulfur isotope effects, underscoring the influence of environmental conditions on the relative contribution of hydrogen cycling to the electron transport. The large sulfur isotope effects associated with the non-ideal stoichiometry of sulfate reduction in this study imply that simultaneous fermentation and sulfate reduction may be responsible for some of the large naturally-occurring sulfur isotope effects. Overall, mutant strains provide a powerful tool to test the effect of specific redox proteins and pathways on sulfur isotope fractionation.