The Biogeochemical Sulfur Cycle of Marine Sediments

Microbial dissimilatory sulfate reduction to sulfide is a predominant terminal pathway of organic matter mineralization in the anoxic seabed. Chemical or microbial oxidation of the produced sulfide establishes a complex network of pathways in the sulfur cycle, leading to intermediate sulfur species and partly back to sulfate. The intermediates include elemental sulfur, polysulfides, thiosulfate, and sulfite, which are all substrates for further microbial oxidation, reduction or disproportionation. New microbiological discoveries, such as long-distance electron transfer through sulfide oxidizing cable bacteria, add to the complexity. Isotope exchange reactions play an important role for the stable isotope geochemistry and for the experimental study of sulfur transformations using radiotracers. Microbially catalyzed processes are partly reversible whereby the back-reaction affects our interpretation of radiotracer experiments and provides a mechanism for isotope fractionation. We here review the progress and current status in our understanding of the sulfur cycle in the seabed with respect to its microbial ecology, biogeochemistry, and isotope geochemistry

Thermodynamics and Kinetics of Sulfide Oxidation by Oxygen: A Look at Inorganically Controlled Reactions and Biologically Mediated Processes in the Environment

The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide oxidation kinetics improve when reduced iron and/or manganese are oxidized by oxygen to form oxidized metals which in turn oxidize sulfide. Biological sulfur oxidation relies on enzymes that have evolved to overcome these kinetic constraints to affect rapid sulfide oxidation. Here we review the available thermodynamic and kinetic data for H2S and HS• as well as O2, reactive oxygen species, nitrate, nitrite, and NOx species. We also present new kinetic data for abiotic sulfide oxidation with oxygen in trace metal clean solutions that constrain abiotic rates of sulfide oxidation in metal free solution and agree with the kinetic and thermodynamic calculations. Moreover, we present experimental data that give insight on rates of chemolithotrophic and photolithotrophic sulfide oxidation in the environment. We demonstrate that both anaerobic photolithotrophic and aerobic chemolithotrophic sulfide oxidation rates are three or more orders of magnitude higher than abiotic rates suggesting that in most environments biotic sulfide oxidation rates will far exceed abiotic rates due to the thermodynamic and kinetic constraints discussed in the first section of the paper. Such data reshape our thinking about the biotic and abiotic contributions to sulfide oxidation in the environment

Boiling-induced formation of colloidal gold in black smoker hydrothermal fluids

Gold colloids occur in black smoker fluids from the Niua South hydrothermal vent field, Lau Basin (South Pacific Ocean), confirming the long-standing hypothesis that gold may undergo colloidal transport in hydrothermal fluids. Six black smoker vents, varying in temperature from 250 °C to 325 °C, were sampled; the 325 °C vent was boiling at the time of sampling and the 250 °C fluids were diffusely venting. Native gold particles ranging from <50 nm to 2 μm were identified in 4 of the fluid samples and were also observed to precipitate on the sampler during collection from the boiling vent. Total gold concentrations (dissolved and particulate) in the fluid samples range from 1.6 to 5.4 nM in the high-temperature, focused flow vents. Although the gold concentrations in the focused flow fluids are relatively high, they are lower than potential solubilities prior to boiling and indicate that precipitation was boiling induced, with sulfide lost upon boiling to exsolution and metal sulfide formation. Gold concentrations reach 26.7 nM in the 250 °C diffuse flow sample, and abundant native gold particles were also found in the fluids and associated sulfide chimney and are interpreted to be a product of colloid accumulation and growth following initial precipitation upon boiling. These results indicate that colloid-driven precipitation as a result of boiling, the persistence of colloids after boiling, and the accumulation of colloids in diffuse flow fluids are important mechanisms for the enrichment of gold in seafloor hydrothermal systems

Large sulfur isotope fractionation by bacterial sulfide oxidation.

A sulfide-oxidizing microorganism, Desulfurivibrio alkaliphilus (DA), generates a consistent enrichment of sulfur-34 (34 S) in the produced sulfate of +12.5 per mil or greater. This observation challenges the general consensus that the microbial oxidation of sulfide does not result in large 34 S enrichments and suggests that sedimentary sulfides and sulfates may be influenced by metabolic activity associated with sulfide oxidation. Since the DA-type sulfide oxidation pathway is ubiquitous in sediments, in the modern environment, and throughout Earth history, the enrichments and depletions in 34 S in sediments may be the combined result of three microbial metabolisms: microbial sulfate reduction, the disproportionation of external sulfur intermediates, and microbial sulfide oxidation

The role of nanoparticles in mediating element deposition and transport at hydrothermal vents

Precipitation processes in hydrothermal fluids exert a primary control on the eventual distribution of elements, whether that sink is in the subseafloor, hydrothermal chimneys, near-field metalliferous sediments, or more distal in the ocean basin. Recent studies demonstrating abundant nanoparticles in hydrothermal fluids raise questions as to the importance of these nanoparticles relative to macro minerals, as well as the fate of such particles in hydrothermal systems. Here we evaluate the particle geochemistry of black smoker fluids from Niua South vent field, including nanoparticles and macro minerals, in order to consider how the processes of mineral precipitation affect mineral size and morphology, and how this mineral precipitation may dictate element sinks as hydrothermal fluids begin to mix with seawater. We find that the Niua vent fluids are dominated by sulfide and sulfate minerals, with the mineralogy of major and minor minerals changing with temperature, degree of mixing with seawater and rate of precipitation. The majority of particles are submicron in size, and sulfide minerals become larger and exhibit more crystalline morphology with increasing seawater content in the fluids. Minor minerals include gold and bismuth tellurides, and nanoparticulate chalcopyrite and nano-zinc sulfide occur. These findings are consistent with major mineral classes and precipitation processes observed in other systems, while providing further insight into the details of mineral precipitation at Niua including the separate and combined influences of boiling, mixing and cooling during hydrothermal fluid transport and initial interactions with seawater. This work demonstrates that boiling and rapid mixing encourages the formation of nanoparticles, whereas conductive cooling encourages particle growth. Further, these data demonstrate that the possible influence of nanoparticles in hydrothermal systems are not restricted to enhancing element transport, but may also include restricting mineral growth and affecting physicochemical properties of hydrothermal chimneys

Early diagenesis of iron and sulfur in Bornholm Basin sediments: the role of near-surface pyrite formation

Pyrite formation in marine sedimentary environments plays a key role in the global biogeochemical cycles of carbon, sulfur and iron, regulating Earth’s surface redox balance over geological time scales. The sulfur isotopic composition of pyrite is one of the major geochemical tools for investigating early diagenetic processes in modern marine sediments and substantive changes to the Earth’s surface environment in ancient sedimentary rocks. We studied sulfur–iron diagenesis and the sulfur isotopic evolution in sediments of the Bornholm Basin, southwestern Baltic Sea, to track the formation of pyrite in the near-surface sediments. Pyrite accumulation is observed with depth over the uppermost 100 cm before the extent of pyritization of the highly reactive iron pool (Fepy/FeHR) stays constant at ca. 0.9, suggesting that the use of a single iron-speciation parameter as a proxy for anoxic and sulfidic conditions needs to be supported by other independent indicators in sedimentary records. Stable sulfur isotopic analysis demonstrates that the bulk pools of elemental sulfur and iron monosulfide do not exchange isotopes completely with aqueous sulfide. We suggest that the reactions with polysulfide and aqueous sulfide are probably restricted to the surface of the solid-phase sulfur and iron-sulfur aggregates. Although pyrite is growing throughout the uppermost sediment column, the pyrite at depth has a sulfur isotopic composition similar to that of pyrite that formed near the sediment surface. To understand the isotopic discrepancy between pyrite and aqueous sulfide in the deeper sediments, we developed a simple diagenetic model, which reproduces the observed sulfur isotopic composition of pyrite well. Our results suggest that much of the pyrite is rapidly formed near the sediment–water interface, and its δ34S is not as influenced by the 34S-enriched pool of aqueous sulfide in the deeper part of the sediment, allowing 32S-enriched pyrite to be preserved in deeper sediments. This near-surface diagenesis and the associated isotopic pattern are possibly of relevance for many marine sediments with high organic matter content, and high aqueous sulfide but low reactive iron availability. Moreover, our sulfur isotopic data demonstrate that extremely slow pyritization is ongoing in the deep lacustrine clay sediments. These results have implications for the interpretation of sulfur–iron geochemical data in both modern and ancient settings as well as for improving reconstructions of ancient depositional environments and a better understanding of the marine sulfur cycle throughout Earth’s history

A communal catalogue reveals Earth's multiscale microbial diversity

Our growing awareness of the microbial world's importance and diversity contrasts starkly with our limited understanding of its fundamental structure. Despite recent advances in DNA sequencing, a lack of standardized protocols and common analytical frameworks impedes comparisons among studies, hindering the development of global inferences about microbial life on Earth. Here we present a meta-analysis of microbial community samples collected by hundreds of researchers for the Earth Microbiome Project. Coordinated protocols and new analytical methods, particularly the use of exact sequences instead of clustered operational taxonomic units, enable bacterial and archaeal ribosomal RNA gene sequences to be followed across multiple studies and allow us to explore patterns of diversity at an unprecedented scale. The result is both a reference database giving global context to DNA sequence data and a framework for incorporating data from future studies, fostering increasingly complete characterization of Earth's microbial diversity.Peer reviewe

A communal catalogue reveals Earth’s multiscale microbial diversity

Our growing awareness of the microbial world’s importance and diversity contrasts starkly with our limited understanding of its fundamental structure. Despite recent advances in DNA sequencing, a lack of standardized protocols and common analytical frameworks impedes comparisons among studies, hindering the development of global inferences about microbial life on Earth. Here we present a meta-analysis of microbial community samples collected by hundreds of researchers for the Earth Microbiome Project. Coordinated protocols and new analytical methods, particularly the use of exact sequences instead of clustered operational taxonomic units, enable bacterial and archaeal ribosomal RNA gene sequences to be followed across multiple studies and allow us to explore patterns of diversity at an unprecedented scale. The result is both a reference database giving global context to DNA sequence data and a framework for incorporating data from future studies, fostering increasingly complete characterization of Earth’s microbial diversity

Turnover Rates of Intermediate Sulfur Species (Sx2-, S0, S2O32-, S4O62-, SO32-) in Anoxic Freshwater and Sediments

The microbial reduction of sulfate to sulfide coupled to organic matter oxidation followed by the transformation of sulfide back to sulfate drives a dynamic sulfur cycle in a variety of environments. The oxidative part of the sulfur cycle in particular is difficult to constrain because the eight electron oxidation of sulfide to sulfate occurs stepwise via a suite of biological and chemical pathways and produces a wide variety of intermediates (Sx2-, S0, S2O32-, S4O62-, and SO32-), which may in turn be oxidized, reduced or disproportionated. Although the potential processes affecting these intermediates are well-known from microbial culture and geochemical studies, their significance and rates in the environment are not well constrained. In the study presented here, time-course concentration measurements of intermediate sulfur species were made in amended freshwater water column and sediment incubation experiments in order to constrain consumption rates and processes. In sediment incubations, consumption rates were Scolloidal0&gt;Sx2-&gt;SO32-≈ S4O62-&gt; S2O32-, which is consistent with previous measurements of SO32-, S4O62-, and S2O32- consumption rates in marine sediments. In water column incubations, however, the relative reactivity was Scolloidal0&gt;SO32-&gt;Sx2-&gt; S2O32-&gt; S4O62-. Consumption of thiosulfate, tetrathionate and sulfite was primarily biological, whereas it was not possible to distinguish between abiotic and biological polysulfide consumption in either aqueous or sediment incubations. Scolloidal0 consumption in water column experiments was biologically mediated, however, rapid sedimentary consumption was likely due to reactions with iron minerals. These experiments provide important constraints on the biogeochemical reactivity of intermediate sulfur species and give further insight into the diversity of biological and geochemical processes that comprise (cryptic) environmental sulfur cycling