Formation of Large Native Sulfur Deposits Does Not Require Molecular Oxygen

Large native (i.e., elemental) sulfur deposits can be part of caprock assemblages found on top of or in lateral position to salt diapirs and as stratabound mineralization in gypsum and anhydrite lithologies. Native sulfur is formed when hydrocarbons come in contact with sulfate minerals in presence of liquid water. The prevailing model for native sulfur formation in such settings is that sulfide produced by sulfate-reducing bacteria is oxidized to zero-valent sulfur in presence of molecular oxygen (O2). Although possible, such a scenario is problematic because: (1) exposure to oxygen would drastically decrease growth of microbial sulfate-reducing organisms, thereby slowing down sulfide production; (2) on geologic timescales, excess supply with oxygen would convert sulfide into sulfate rather than native sulfur; and (3) to produce large native sulfur deposits, enormous amounts of oxygenated water would need to be brought in close proximity to environments in which ample hydrocarbon supply sustains sulfate reduction. However, sulfur stable isotope data from native sulfur deposits emplaced at a stage after the formation of the host rocks indicate that the sulfur was formed in a setting with little solute exchange with the ambient environment and little supply of dissolved oxygen. We deduce that there must be a process for the formation of native sulfur in absence of an external oxidant for sulfide. We hypothesize that in systems with little solute exchange, sulfate-reducing organisms, possibly in cooperation with other anaerobic microbial partners, drive the formation of native sulfur deposits. In order to cope with sulfide stress, microbes may shift from harmful sulfide production to non-hazardous native sulfur production. We propose four possible mechanisms as a means to form native sulfur: (1) a modified sulfate reduction process that produces sulfur compounds with an intermediate oxidation state, (2) coupling of sulfide oxidation to methanogenesis that utilizes methylated compounds, acetate or carbon dioxide, (3) ammonium oxidation coupled to sulfate reduction, and (4) sulfur comproportionation of sulfate and sulfide. We show these reactions are thermodynamically favorable and especially useful in environments with multiple stressors, such as salt and dissolved sulfide, and provide evidence that microbial species functioning in such environments produce native sulfur. Integrating these insights, we argue that microbes may form large native sulfur deposits in absence of light and external oxidants such as O2, nitrate, and metal oxides. The existence of such a process would not only explain enigmatic occurrences of native sulfur in the geologic record, but also provide an explanation for cryptic sulfur and carbon cycling beneath the seabed

An archaeal biomarker record of paleoenvironmental change across the onset of the Messinian salinity crisis in the absence of evaporites (Piedmont Basin, Italy)

Abstract A sudden change from normal marine to extreme paleoenvironmental conditions occurred approximately 6 Ma ago in the Mediterranean Basin at the onset of the late Miocene Messinian salinity crisis, one of the most severe ecological crises in Earth history. Strong evaporation and tectonics led to hypersaline conditions, resulting in widespread deposition of evaporites and the apparent annihilation of the marine metazoan biosphere. In contrast to the prominent occurrence of evaporites elsewhere in the Mediterranean, evaporites did not form in the deeper part of some marginal basins at the onset of the crisis. The strata of the Pollenzo section (Piedmont Basin, NW Italy) studied here were deposited in such a paleogeographic setting. Instead of evaporites, a cyclic succession of organic-rich shales and carbonates formed during the early phase of the crisis in the study area. These sediments record a sharp increase in the contents of archaeal molecular fossils that are mostly represented by isoprenoidal dialkyl glycerol diethers (DGDs) and isoprenoidal glycerol dialkyl glycerol tetraethers (GDGTs). Such an expansion of archaeal biomass is best explained by a change of the archaeal communities at the onset of the Messinian salinity crisis. In particular, the appearance of molecular fossils of extremophilic archaea, mostly producing DGDs (archaeol and extended archaeol), suggests the emergence of halophilic archaea. At the same time, lipids of planktonic Thaumarchaeota, especially crenarchaeol, are present across the entire section, suggesting the local persistence of normal marine conditions. In agreement with the sudden appearance of tetrahymanol in the upper part of the section, the persistence of crenarchaeol indicates the establishment of water column stratification after the advent of the Messinian salinity crisis. To further investigate the Piedmont Basin paleoenvironmental conditions, we test the Archaeol Caldarchaeol Ecometric (ACE), a proxy developed for identifying high paleosalinities in waters and possibly in sediments. Despite high ACE values found for the Messinian salinity crisis samples, these values are in contrast with the absence of any lithological evidence for high salinities as well with other biomarker-independent information, indicating low to normal seawater salinities. This apparent contradiction is likely explained by the complexity of the sources of archaeal lipids, especially of caldarchaeol and archaeol, limiting the utility of the ACE for the reconstruction of paleosalinities for Messinian strata

Fueled by methane: deep-sea sponges from asphalt seeps gain their nutrition from methane-oxidizing symbionts

Sponges host a remarkable diversity of microbial symbionts, however, the benefit their microbes provide is rarely understood. Here, we describe two new sponge species from deep-sea asphalt seeps and show that they live in a nutritional symbiosis with methane-oxidizing (MOX) bacteria. Metagenomics and imaging analyses revealed unusually high amounts of MOX symbionts in hosts from a group previously assumed to have low microbial abundances. These symbionts belonged to the Marine Methylotrophic Group 2 clade. They are host-specific and likely vertically transmitted, based on their presence in sponge embryos and streamlined genomes, which lacked genes typical of related free-living MOX. Moreover, genes known to play a role in host–symbiont interactions, such as those that encode eukaryote-like proteins, were abundant and expressed. Methane assimilation by the symbionts was one of the most highly expressed metabolic pathways in the sponges. Molecular and stable carbon isotope patterns of lipids confirmed that methane-derived carbon was incorporated into the hosts. Our results revealed that two species of sponges, although distantly related, independently established highly specific, nutritional symbioses with two closely related methanotrophs. This convergence in symbiont acquisition underscores the strong selective advantage for these sponges in harboring MOX bacteria in the food-limited deep sea

From ether to acid: a plausible degradation pathway of glycerol dialkyl glycerol tetraethers

Glycerol dialkyl glycerol tetraethers (GDGTs) are ubiquitous microbial lipids with extensive demonstrated and potential roles as paleoenvironmental proxies. Despite the great attention they receive, comparatively little is known regarding their diagenetic fate. Putative degradation products of GDGTs, identified as hydroxyl and carboxyl derivatives, were detected in lipid extracts of marine sediment, seep carbonate, hot spring sediment and cells of the marine thaumarchaeon Nitrosopumilus maritimus. The distribution of GDGT degradation products in environmental samples suggests that both biotic and abiotic processes act as sinks for GDGTs. More than a hundred newly recognized degradation products afford a view of the stepwise degradation of GDGT via (1) ether bond hydrolysis yielding hydroxyl isoprenoids, namely, GDGTol (glycerol dialkyl glycerol triether alcohol), GMGD (glycerol monobiphytanyl glycerol diether), GDD (glycerol dibiphytanol diether), GMM (glycerol monobiphytanol monoether) and bpdiol (biphytanic diol); (2) oxidation of isoprenoidal alcohols into corresponding carboxyl derivatives and (3) chain shortening to yield C39and smaller isoprenoids. This plausible GDGT degradation pathway from glycerol ethers to isoprenoidal fatty acids provides the link to commonly detected head-to-head linked long chain isoprenoidal hydrocarbons in petroleum and sediment samples. The problematic C80to C82tetraacids that cause naphthenate deposits in some oil production facilities can be generated from H-shaped glycerol monoalkyl glycerol tetraethers (GMGTs) following the same process, as indicated by the distribution of related derivatives in hydrothermally influenced sediments.Seventh Framework Programme (European Commission) (ERC Grant 247153

Late Cretaceous (Maastrichtian) shallow water hydrocarbon seeps from Snow Hill and Seymour Islands, James Ross Basin, Antarctica

Fossil hydrocarbon seeps are present in latest Cretaceous (Maastrichtian) volcaniclastic shallow shelf sediments exposed on Snow Hill and Seymour Islands, James Ross Basin, Antarctica. The seeps occur in the Snow Hill Island Formation on Snow Hill Island and are manifest as large-sized, cement-rich carbonate bodies, containing abundant thyasirid bivalves and rarer ammonites and solemyid bivalves. These bodies have typical seep cement phases, with δ13C values between 20.4 and 10.7‰ and contain molecular fossils indicative of terrigenous organic material and the micro-organisms involved in the anaerobic oxidation of methane, including methanotrophic archaea and sulphate-reducing bacteria. On Seymour Island the seeps occur as micrite-cemented burrow systems in the López de Bertodano Formation and are associated with thyasirid, solemyid and lucinid bivalves, and background molluscan taxa. The cemented burrows also have typical seep cement phases, with δ13C values between 58.0 and 24.6‰. There is evidence from other data that hydrocarbon seepage was a common feature in the James Ross Basin throughout the Maastrichtian and into the Eocene. The Snow Hill and Seymour Island examples comprise the third known area of Maastrichtian hydrocarbon seepage. But compared to most other ancient and modern seep communities, the James Ross Basin seep fauna is of very low diversity, being dominated by infaunal bivalves, all of which probably had thiotrophic chemosymbionts, but which were unlikely to have been seep obligates. Absent from the James Ross Basin seep fauna are ‘typical’ obligate seep taxa from the Cretaceous and the Cenozoic. Reasons for this may have been temporal, palaeolatitudinal, palaeobathymetric, or palaeoecological

Resource partitioning among brachiopods and bivalves at ancient hydrocarbon seeps: A hypothesis

Brachiopods were thought to have dominated deep-sea hydrothermal vents and hydrocarbon seeps for most of the Paleozoic and Mesozoic, and were believed to have been outcompeted and replaced by chemosymbiotic bivalves during the Late Cretaceous. But recent findings of bivalve-rich seep deposits of Paleozoic and Mesozoic age have questioned this paradigm. By tabulating the generic diversity of the dominant brachiopod and bivalve clades-dimerelloid brachiopods and chemosymbiotic bivalves-from hydrocarbon seeps through the Phanerozoic, we show that their evolutionary trajectories are largely unrelated to one another, indicating that they have not been competing for the same resources. We hypothesize that the dimerelloid brachiopods generally preferred seeps with abundant hydrocarbons in the bottom waters above the seep, such as oil seeps or methane seeps with diffusive seepage, whereas seeps with strong, advective fluid flow and hence abundant hydrogen sulfide were less favorable for them. At methane seeps typified by diffusive seepage and oil seeps, oxidation of hydrocarbons in the bottom water by chemotrophic bacteria enhances the growth of bacterioplankton, on which the brachiopods could have filter fed. Whereas chemosymbiotic bivalves mostly relied on sulfide-oxidizing symbionts for nutrition, for the brachiopods aerobic bacterial oxidation of methane and other hydrocarbons played a more prominent role. The availability of geofuels (i.e. the reduced chemical compounds used in chemosynthesis such as hydrogen sulfide, methane, and other hydrocarbons) at seeps is mostly governed by fluid flow rates, geological setting, and marine sulfate concentrations. Thus rather than competition, we suggest that geofuel type and availability controlled the distribution of brachiopods and bivalves at hydrocarbon seeps through the Phanerozoic

Nitrogen uptake by methanotrophic consortia in deep-water gas hydrate-bearing sediments

Methane-consuming microbes inhabiting marine methane seeps have recently been found to have the capacity to assimilate inorganic nitrogen, suggesting a previously unaccounted role in the global nitrogen cycle. Despite ex-situ experimental observations, definitive evidence of this process under in-situ conditions remains elusive, hindering the complete understanding of the controlling factors and magnitude of this process. We present the isotopic variations of organic carbon δ13Corg and total nitrogen δ15N values in two sediment cores collected from the gas hydrate-bearing Håkon Mosby Mud Volcano, SW Barents Sea (72°N, ∼1260 m water depth). We identified a stratigraphic interval containing methane-derived carbonates directly overlying a gas hydrate layer at 67 cm and typified by δ13Corg and δ15N as low as −42.0‰ and 1.2‰, respectively. Stable isotope mixing models confirm in-situ nitrogen uptake by methanotrophic consortia, contributing to up to 49.1 wt% of the local bulk sedimentary organic matter – a finding calling for reevaluation of the role of methane seeps in the oceanic nitrogen cycl

Catshark egg capsules from a Late Eocene deep-water methane-seep deposit in western Washington State, USA

Fossil catshark egg capsules, Scyliorhinotheca goederti gen. et sp. nov., are reported from a Late Eocene deep−water methane−seep calcareous deposit in western Washington State, USA. The capsules are preserved three−dimensionally and some show mineralized remnants of the ribbed capsule wall consisting of small globular crystals that are embedded in a microsparitic matrix. The globules are calcitic, but a strontium content of 2400–3000 ppm suggests that they were origi− nally aragonitic. The carbonate enclosing the egg capsules, and the capsule wall itself, show 13C values as low as −36.5‰, suggesting that formation was induced by the anaerobic oxidation of methane and hence in an anoxic environ− ment. We put forward the following scenario for the mineralization of the capsule wall: (i) the collagenous capsules expe− rienced a sudden change from oxic to anoxic conditions favouring an increase of alkalinity; (ii) this led to the precipitation of aragonitic globules within the collagenous capsule wall; (iii) subsequently the remaining capsule wall was mineralized by calcite or aragonite; (iv) finally the aragonitic parts of the wall recrystallized to calcite. The unusual globular habit of the early carbonate precipitates apparently represents a taphonomic feature, resulting from mineralization mediated by an organic matrix. Taphonomic processes, however, are at best contributed to an increase of alkalinity, which was mostly driven by methane oxidation at the ancient seep sit

(Table 1) List of samples with carbonate mineralogy, stable isotope, and accessory-mineral information

Petrographic and stable-isotope (d13C, d18O) patterns of carbonates from the Logatchev Hydrothermal Field (LHF), the Gakkel Ridge (GR), and a Late Devonian outcrop from the Frankenwald (Germany) were compared in an attempt to understand the genesis of carbonate minerals in marine volcanic rocks. Specifically, were the carbonate samples from modern sea floor settings and the Devonian analog of hydrothermal origin, low-temperature abiogenic origin (as inferred for aragonite in serpentinites from elsewhere on the Mid-Atlantic Ridge), or biogenic origin? Aragonite is the most abundant carbonate mineral in serpentinites from the two modern spreading ridges and occurs within massive sulfides of the LHF. The precipitation and preservation of aragonite suggests high Mg2+ and sulfate concentrations in fluids. Values of d18OPDB as high as +5.3 per mill for serpentinite-hosted aragonite and as high as +4.2 per mill for sulfide-hosted aragonite are consistent with precipitation from cold seawater. Most of the corresponding d13C values indicate a marine carbon source, whereas d13C values for sulfide-hosted aragonite as high as +3.6 per mill may reflect residual carbon dioxide in the zone of methanogenesis. Calcite veins from the LHF, by contrast, have low d18OPDB (-20.0 per mill to -16.1 per mill) and d13C values (-5.8 per mill to -4.5 per mill), indicative of precipitation from hydrothermal solutions (~129°-186°C) dominated by magmatic CO2. Calcite formation was probably favored by fluid rock interactions at elevated temperatures, which tend to remove solutes that inhibit calcite precipitation in seawater (Mg2+ and sulfate). Devonian Frankenwald calcites show low d18O values, reflecting diagenetic and metamorphic overprinting. Values of d13C around 0 per mill for basalt-hosted calcite indicate seawater-derived inorganic carbon, whereas d13C values for serpentinite-hosted calcite agree with mantle-derived CO2 (for values as low as -6 per mill) with a contribution of amagmatic carbon (for values as low as -8.6 per mill), presumably methane. Secondary mineral phases from the LHF for which a biogenic origin appears feasible include dolomite dumbbells, clotted carbonate, and a network of iron- and silica-rich filaments