ALBERT

Description: In anoxic environments, volatile methylated sulfides including methanethiol (MT) and dimethyl sulfide (DMS) link the pools of inorganic and organic carbon with the sulfur cycle. However, direct formation of methylated sulfides from reduction of dissolved inorganic carbon has previously not been demonstrated. During examination of the hydrogenotrophic microbial activity at different temperatures in the anoxic sediment from Lake Plußsee, DMS formation was detected at 55 °C and was enhanced when bicarbonate was supplemented. Addition of both bicarbonate and H2 resulted in the strongest stimulation of DMS production, and MT levels declined slightly. Addition of methyl-group donors such as methanol and syringic acid or methyl-group acceptors such as hydrogen sulfide did not enhance further accumulation of DMS and MT. The addition of 2-bromoethanesulfonate inhibited DMS formation and caused a slight MT accumulation. MT and DMS had average δ13C values of −55‰ and −62‰, respectively. Labeling with NaH13CO3 showed that incorporation of bicarbonate into DMS occurred through methylation of MT. H235S labeling demonstrated a microbially-mediated, but slow, process of hydrogen sulfide methylation that accounted for

Description: In anoxic environments, volatile methylated sulfides like methanethiol (MT) and dimethyl sulfide (DMS) link the pools of inorganic and organic carbon with the sulfur cycle. However, direct formation of methylated sulfides from reduction of dissolved inorganic carbon has previously not been demonstrated. When studying the effect of temperature on hydrogenotrophic microbial activity, we observed formation of DMS in anoxic sediment of Lake Plußsee at 55 °C. Subsequent experiments strongly suggested that the formation of DMS involves fixation of bicarbonate via a reductive pathway in analogy to methanogenesis and engages methylation of MT. DMS formation was enhanced by addition of bicarbonate and further increased when both bicarbonate and H2 were supplemented. Inhibition of DMS formation by 2-bromoethanesulfonate points to the involvement of methanogens. Compared to the accumulation of DMS, MT showed the opposite trend but there was no apparent 1:1 stoichiometric ratio between both compounds. Both DMS and MT had negative δ13C values of −62‰ and −55‰, respectively. Labeling with NaH13CO3 showed more rapid incorporation of bicarbonate into DMS than into MT. The stable carbon isotopic evidence implies that bicarbonate was fixed via a reductive pathway of methanogenesis, and the generated methyl coenzyme M became the methyl donor for MT methylation. Neither DMS nor MT accumulation were stimulated by addition of the methyl-group donors methanol and syringic acid or by the methyl-group acceptor hydrogen sulphide. The source of MT was further investigated in a H235S labeling experiment, which demonstrated a microbially-mediated process of hydrogen sulfide methylation to MT that accounted for only

Description: International Ocean Discovery Program (IODP) Expedition 385 drilled organic-rich sediments with sill intrusions on the flanking regions and in the northern axial graben in Guaymas Basin, a young marginal rift basin in the Gulf of California. Guaymas Basin is characterized by a widely distributed, intense heat flow and widespread off-axis magmatism expressed by a dense network of sill intrusions across the flanking regions, which is in contrast to classical mid-ocean ridge spreading centers. The numerous off-axis sills provide multiple transient heat sources that mobilize buried sedimentary carbon, in part as methane and other hydrocarbons, and drive hydrothermal circulation. The resulting thermal and geochemical gradients shape abundance, composition, and activity of the deep subsurface biosphere of the basin. Drill sites extend over the flanking regions of Guaymas Basin, covering a distance of ~81 km from the from the northwest to the southeast. Adjacent Sites U1545 and U1546 recovered the oldest and thickest sediment successions (to ~540 meters below seafloor [mbsf]; equivalent to the core depth below seafloor, Method A [CSF-A] scale), one with a thin sill (a few meters in thickness) near the drilled bottom (Site U1545), and one with a massive, deeply buried sill (~356–430 mbsf) that chemically and physically affects the surrounding sediments (Site U1546). Sites U1547 and U1548, located in the central part of the northern Guaymas Basin segment, were drilled to investigate a 600 m wide circular mound (bathymetric high) and its periphery. The dome-like structure is outlined by a ring of active vent sites called Ringvent. It is underlain by a remarkably thick sill at shallow depth (Site U1547). Hydrothermal gradients steepen at the Ringvent periphery (Holes U1548A–U1548C), which in turn shifts the zones of authigenic carbonate precipitation and of highest microbial cell abundance toward shallower depths. The Ringvent sill was drilled several times and yielded remarkably diverse igneous rock textures, sediment–sill interfaces, and hydrothermal alteration, reflected by various secondary minerals in veins and vesicles. Thus, the Ringvent sill became the target of an integrated sampling and interdisciplinary research effort that included geological, geochemical, and microbiological specialties. The thermal, lithologic, geochemical, and microbiological contrasts between the two deep northwestern sites (U1545 and U1546) and the Ringvent sites (U1547 and U1548) form the scientific centerpiece of the expedition. These observations are supplemented by results from sites that represent attenuated cold seepage conditions in the central basin (Site U1549), complex and disturbed sediments overlying sills in the northern axial trough (Site U1550), terrigenous sedimentation events on the southeastern flanking regions (Site U1551), and hydrate occurrence in shallow sediments proximal to the Sonora margin (Site U1552). The scientific outcomes of Expedition 385 will (1) revise long-held assumptions about the role of sill emplacement in subsurface carbon mobilization versus carbon retention, (2) comprehensively examine the subsurface biosphere of Guaymas Basin and its responses and adaptations to hydrothermal conditions, (3) redefine hydrothermal controls of authigenic mineral formation in sediments, and (4) yield new insights into many geochemical and geophysical aspects of both architecture and sill–sediment interaction in a nascent spreading center. The generally high quality and high degree of completeness of the shipboard datasets present opportunities for interdisciplinary and multidisciplinary collaborations during shore-based studies. In comparison to Deep Sea Drilling Project Leg 64 to Guaymas Basin in 1979, sophisticated drilling strategies (for example, the advanced piston corer [APC] and half-length APC systems) and numerous analytical innovations have greatly improved sample recovery and scientific yield, particularly in the areas of organic geochemistry and microbiology. For example, microbial genomics did not exist 40 y ago. However, these technical refinements do not change the fact that Expedition 385 will in many respects build on the foundations laid by Leg 64 for understanding Guaymas Basin, regardless of whether adjustments are required in the near future.

Description: Dissolved organic matter (DOM) in marine sediment pore waters derives largely from decomposition of particulate organic matter and its composition is influenced by various biogeochemical and oceanographic processes in yet undetermined ways. Here, we determine the molecular inventory of pore water DOM in marine sediments of contrasting depositional regimes with ultrahigh-resolution mass spectrometry and complementary bulk chemical analyses in order to elucidate the factors that shape DOM composition. Our sample sets from the Mediterranean, Marmara and Black Seas covered different sediment depths, ages and a range of marine environments with different (i) organic matter sources, (ii) balances of organic matter production and preservation, and (iii) geochemical conditions in sediment and water column including anoxic, sulfidic and hypersaline conditions. Pore water DOM had a higher molecular formula richness than overlying water with up to 11,295 vs. 2114 different molecular formulas in the mass range of 299–600 Da and covered a broader range of element ratios (H/C = 0.35–2.19, O/C = 0.03–1.19 vs. H/C = 0.56–2.13, O/C = 0.15–1.14). Formula richness was independent of concentrations of DOC and TOC. Near-surface pore water DOM was more similar to water column DOM than to deep pore water DOM from the same core with respect to formula richness and the molecular composition, suggesting exchange at the sediment–water interface. The DOM composition in the deeper sediments was controlled by organic matter source, selective decomposition of specific DOM fractions and early diagenetic molecule transformations. Compounds in pelagic sediment pore waters were predominantly highly unsaturated and N-bearing formulas, whereas oxygen-rich CHO-formulas and aromatic compounds were more abundant in pore water DOM from terrigenous sediments. The increase of S-bearing molecular formulas in the water column and pore waters of the Black Sea and the Mediterranean Discovery Basin was consistent with elevated HS- concentrations reflecting the incorporation of sulfur into biomolecules during early diagenesis. Sulfurization resulted in an increased average molecular mass of DOM and higher formula richness (up to 5899 formulas per sample). In sediments from the methanogenic zone in the Black Sea, the DOM pool was distinctly more reduced than overlying sediments from the sulfate-reducing zone. Bottom and pore water DOM from the Discovery Basin contained the highest abundances of aliphatic compounds in the entire dataset; a large fraction of abundant N-bearing formulas possibly represented peptide and nucleotide formulas suggesting preservation of these molecules in the life inhibiting environment of the Discovery Basin. Our unique data set provides the basis for a comprehensive understanding of the molecular signatures in pore water DOM and the turnover of sedimentary organic matter in marine sediments.