Pore water and solid-phase data from site Scharendijke (Lake Grevelingen, NL)

Will be submitted by the author

Total phospholipid fatty acid concentrations structrures of ODP Hole 191-1179 samples (Table 1)

Sediment samples ranging from 0.05 to 278 m below sea floor (mbsf) at a Northwest Pacific deep-water (5564 mbsl) site (ODP Leg 191, Site 1179) were analyzed for phospholipid fatty acids (PLFAs). Total PLFA concentrations decreased by a factor of three over the first meter of sediment and then decreased at a slower rate to approximately 30 mbsf. The sharp decrease over the first meter corresponds to the depth of nitrate and Mn(IV) reduction as indicated by pore water chemistry. PLFA-based cell numbers at site 1179 had a similar depth profile as that for Acridine orange direct cell counts previously made on ODP site 1149 sediments which have a similar water depth and lithology. The mole percentage of straight chain saturated PLFAs increases with depth, with a large shift between the 0.95 and 3.95 mbsf samples. PLFA stable carbon isotope ratios were determined for sediments from 0.05 to 4.53 mbsf and showed a general trend toward more depleted d13C values with depth. Both of these observations may indicate a shift in the bacterial community with depth across the different redox zones inferred from pore water chemistry data. The PLFA 10me16:0, which has been attributed to the bacterial genera Desulfobacter in many marine sediments, showed the greatest isotopic depletion, decreasing from -20 to -35 per mil over the first meter of sediment. Pore water chemistry suggested that sulfate reduction was absent or minimal over this same sediment interval. However, 10me16:0 has been shown to be produced by recently discovered anaerobic ammonium oxidizing (anammox) bacteria which are known chemoautotrophs. The increasing depletion in d13C of 10me16:0 with the unusually lower concentration of ammonium and linear decrease of nitrate concentration is consistent with a scenario of anammox bacteria mediating the oxidation of ammonium via nitrite, an intermediate of nitrate reduction.

(Table 3) Isotopic composition of pyrite sulfur and carbonate carbon in carbonate nodules and host sediments from Core DM9-666, Gulf of California

Isotopic-geochemical study revealed presence of mantle He (3He/4He up to 223x10**-8) in gases from mud volcanoes of Eastern Georgia. This fact confirms that the Middle Kura basin fill encloses an intrusive body previously distinguished from geophysical data. Wide variations of carbon isotopic composition d13C in CH4 and CO2 and chemical composition of gas and water at temporally constant 3He/4He ratio indicate their relation with crustal processes. Unusual direct correlations of 3He/4He ratio with concentrations of He and CH4 and 40Ar/36Ar ratio can be explained by generation of gas in the Cenozoic sequence of the Middle Kura basin.

Methane and sulphate consumption in different habitats of the Håkon Mosby Mud Volcano (HMMV)

The Hakon Mosby Mud Volcano is a highly active methane seep hosting different chemosynthetic communities such as thiotrophic bacterial mats and siboglinid tubeworm assemblages. This study focuses on in situ measurements of methane fluxes to and from these different habitats, in comparison to benthic methane and oxygen consumption rates. By quantifying in situ oxygen, methane, and sulfide fluxes in different habitats, a spatial budget covering areas of 10-1000 -m diameter was established. The range of dissolved methane efflux (770-2 mmol m-2 d-1) from the center to the outer rim was associated with a decrease in temperature gradients from 46°C to < 1°C m-1, indicating that spatial variations in fluid flow control the distribution of benthic habitats and activities. Accordingly, total oxygen uptake (TOU) varied between the different habitats by one order of magnitude from 15 mmol m-2 d-1 to 161 mmol m-2 d-1. High fluid flow rates appeared to suppress benthic activities by limiting the availability of electron acceptors. Accordingly, the highest TOU was associated with the lowest fluid flow and methane efflux. This was most likely due to the aerobic oxidation of methane, which may be more relevant as a sink for methane as previously considered in submarine ecosystems.

Geochemical and biogeochemical parameters of Black Sea waters and suspended matter

The monograph focuses on the analysis of data addressing the problem of H2S contamination and oxic-anoxic interface in the Black Sea. Regularities of the fine structure of vertical distribution of oxygen, hydrogen sulfide, biogenic elements, organic substances, suspended matter, and metals of the iron-manganese group in the area of contact of aerobic and anaerobic waters have been revealed. Also effects of biochemical, physico-chemical and dynamic processes on their vertical distribution have been examined. Sulfate reduction in seawater and bottom sediments has been studied. Quantitative estimates of H2S fluxes at the water - bottom sediment and O2-H2S interfaces have been done. Features of H2S oxidation have been studied, its budget in the Black Sea has been calculated. Multiyear spatial-temporal variability of the oxic-anoxic interface has been investigated.

Chemical composition and stable sulfur isotope record of Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO4[2-]-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO4[2-] and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO4[2-]-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with delta34S = +15 to +33 per mil at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO4[2-] diffusing downward into the SO4[2-]-CH4 transition has an isotopic composition of +19 per mil, close to the +23 per mil of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO4[2-] (+43 per mil) and H2S (-15 per mil) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth's history.

Pore-water chemistry of ODP Leg 114 holes

Pore-water samples were recovered at five sites from ODP Leg 114 in the subantarctic South Atlantic Ocean and analyzed for pH, alkalinity, chloride, sulfate, fluoride, silica, magnesium, calcium, strontium, potassium, lithium, and barium. At sites in the East Georgia Basin and on the Islas Orcadas Rise, Ca increases and Mg decreases linearly downhole with a DeltaMg/DeltaCa ratio reflecting conservative diffusive exchange and basalt basement reactions. At sites on the west flank of the Mid-Atlantic Ridge and on the Meteor Rise, Ca gradients are nonlinear, and nonconservative DeltaMg/DeltaCa ratios reflect alteration reactions of abundant silicic volcanic ash in the sediment. K decreases linearly downhole at all sites, reflecting uptake by basement and the absence of significant sediment-hosted reactions. SO4 decreases and alkalinity increases downhole are due to a slight sulfate reduction at all sites except at Site 701. Sr increases downhole at all sites except Site 701, with DeltaSr/DeltaCa ratios reflecting diffusive exchange with basement. At Site 704 on the Meteor Rise, there is intense Sr production during carbonate recrystallization in the upper 200 mbsf. Below 200 mbsf at Site 704, the ion concentration product of SrSO4 is constant, suggesting Sr control by celestite solubility. Li and F concentrations display complex behavior related to sedimentary reactions, probably calcite recrystallization (Li uptake and F release).

Chemical analysis of water samples of station M1_1207, Red Sea (Table 1-3)

Two water samples and two sediment samples taken in 1965 by the R. V. "Meteor" in the area of the hot salt brine of the Atlantis II-Deep were chemically investigated, and in addition the sediment samples were subjected to X-ray and optical analysis. The investigation of the sulfur-isotope-ratios showed the same values for all water samples. This information combined with the Ca-sulfate solubility data leads us to conclude that, for the most part, the sulfate content of the salt brine resulted from mixing along the boundary with the normal seawater. In this boundary area gypsum or anhydrite is formed which sinks down to the deeper layers of the salt brine where it is redisolved when the water becomes undersaturated. In the laboratory, formation of CaS04 precipitate resulted from both the reheating of the water sample from the uppermost zone of the salt brine to the in-situ-temperature as well as by the mixing of the water sample with normal Red Sea water. The iron and manganese delivered by the hot spring is separated within the area of the salt brine by their different redox-potentials. Iron is sedimented to a high amount within the salt brine, while, as evidenced by its small amounts in all sediment samples, the more easily reducible manganese is apparently carried out of the area before sedimentation can take place. The very good layering of the salt brine may be the result of the rough bottom topography with its several progressively higher levels allowing step-like enlargements of the surface areas of each successive layer. Each enlargement results in larger boundary areas along which more effective heat transfer and mixing with the next layer is possible. In the sediment samples up to 37.18% Fe is found, mostly bound as very poorly crystallized iron hydroxide. Pyrite is present in only very small amounts. We assume that the copper is bound mostly as sulfide, while the zinc is most likely present in an other form. The sulfur-isotope-investigations indicate that the sulfur in the sediment, bound as pyrite and sulfides, is not a result of bacterical sulfate-reduction in the iron-rich mud of the Atlantis II-Deep, but must have been brought up with the hot brine.

(Table 2) Concentrations and D/L values for three amino acids in bulk foraminifera from ODP Sites 182-1126 and 182-1127

A number of studies have shown that methanogens are active in the presence of sulfate under some conditions. This phenomenon is especially exemplified in carbonate sediments of the southern Australian continental margin. Three sites cored during Ocean Drilling Program (ODP) Leg 182 in the Great Australian Bight have high concentrations of microbially-generated methane and hydrogen sulfide throughout almost 500 m of sediments. In these cores, the sulfate-reducing and methanogenic zones overlap completely; that is, the usual sulfate-methane transition zone is absent. Amino acid racemization data show that the gassy sediments consist of younger carbonates than the low-gas sites. High concentrations of the reduced gases also occur in two ODP sites on the margin of the Bahamas platform, both of which have similar sedimentary conditions to those of the high-gas sites of Leg 182. Co-generation of these reduced gases results from an unusual combination of conditions, including: (1) a thick Quaternary sequence of iron-poor carbonate sediments, (2) a sub-seafloor brine, and (3) moderate amounts of organic carbon. The probable explanation for the co-generation of hydrogen sulfide and methane in all these sites, as well as in other reported environments, is that methanogens are utilizing non-competitive substrates to produce methane within the sulfate-reducing zone. Taken together, these results form the basis of a new model for sulfate reduction and methanogenesis in marine sediments. The biogeochemical end-members of the model are: (1) minimal sulfate reduction, (2) complete sulfate reduction followed by methanogenesis, and (3) overlapping sulfate reduction and methanogenesis with no transition zone.

Gas hydrate investigation at the Amsterdam mud volcano

We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C1/C2+ ratios <35 and d13C-CH4 values of -50.6 per mil. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas-sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO42- and Ba2+ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.