Description: We present high resolution profiles for the methane concentration and the carbon isotope composition of methane from surface sediments and from the sediment-water transition in the Black Sea. At shallow water sites methane migrates from the sediment into the water column, and the magnitude of this upward migrating flux depends on the depth of the sulfate-methane transition (SMT) in the sediment. The isotope data reveal that the sediments at shallow water sites are a source for methane depleted in 13C relative to the isotope composition of methane in the water column. At deep water sites the methane concentration first decreases with depth in the sediment to reach lowest values at the Unit I to Unit II transition. Below this transition the concentration increases again. Numerical modeling of methane concentration and isotope data shows that high methane oxidation rates occur in the surface sediment layer, indicating that the removal of methane in the surface sediments is not related to the anaerobic oxidation of methane coupled to sulfate reduction that occurs a few meters deep in the sediment, at the SMT. Instead, near-surface methane consumption in the euxinic Black Sea sediments appears to be related to lithological stratification. Furthermore, a map of the diffusive methane fluxes in the Black Sea surface sediments indicates that approximately half of the Black Sea seafloor acts as a sink for methane and thus limits the flux of methane to the atmosphere.

Description: Ulva is the dominant genus in the green tide events and is considered to have efficient CO2 concentrating mechanisms (CCMs). However, little is understood regarding the impacts of ocean acidification on the CCMs of Ulva and the consequences of thalli's acclimation to ocean acidification in terms of responding to environmental factors. Here, we grew a cosmopolitan green alga, Ulva linza at ambient (LC) and elevated (HC) CO2 levels and investigated the alteration of CCMs in U. linza grown at HC and its responses to the changed seawater carbon chemistry and light intensity. The inhibitors experiment for photosynthetic inorganic carbon utilization demonstrated that acidic compartments, extracellular carbonic anhydrase (CA) and intracellular CA worked together in the thalli grown at LC and the acquisition of exogenous carbon source in the thalli could be attributed to the collaboration of acidic compartments and extracellular CA. Contrastingly, when U. linza was grown at HC, extracellular CA was completely inhibited, acidic compartments and intracellular CA were also down-regulated to different extents and thus the acquisition of exogenous carbon source solely relied on acidic compartments. The down-regulated CCMs in U. linza did not affect its responses to changes of seawater carbon chemistry but led to a decrease of net photosynthetic rate when thalli were exposed to increased light intensity. This decrease could be attributed to photodamage caused by the combination of the saved energy due to the down-regulated CCMs and high light intensity. Our findings suggest future ocean acidification might impose depressing effects on green tide events when combined with increased light exposure.

Description: Ocean margin sediments have been considered as important sources of dissolved organic carbon (DOC) to the deep ocean, yet the contribution from advective settings has just started to be acknowledged. Here we present evidence showing that near-surface heating of sediment in the Guaymas Basin, a young extensional depression, causes mass production and discharge of reactive dissolved organic matter (DOM). In the sediment heated up to ~100 °C, we found unexpectedly low DOC concentrations in the pore waters, reflecting the combined effect of thermal desorption and advective fluid flow. Heating experiments suggested DOC production to be a rapid, abiotic process with the DOC concentration increasing exponentially with temperature. The high proportions of total hydrolyzable amino acids and presence of chemical species affiliated with activated hydrocarbons, carbohydrates and peptides indicate high reactivity of the DOM. Model simulation suggests that at the local scale, near-surface heating of sediment creates short and massive DOC discharge events that elevate the bottom-water DOC concentration. Because of the heterogeneous distribution of high heat flow areas, the expulsion of reactive DOM is spotty at any given time. We conclude that hydrothermal heating of young rift sediments alter deep-ocean budgets of bioavailable DOM, creating organic-rich habitats for benthic life.

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.