(Table T1) Dissolved sulfide concentration and d34S of dissolved sulfate and sulfide in pore waters of ODP Leg 204

We report dissolved sulfide sulfur concentrations and the sulfur isotopic composition of dissolved sulfate and sulfide in pore waters from sediments collected during Ocean Drilling Program Leg 204. Porewater sulfate is depleted rapidly as the depth to the sulfate/methane interface (SMI) occurs between 4.5 and 11 meters below seafloor at flank and basin locations. Dissolved sulfide concentration reaches values as high as 11.3 mM in Hole 1251E. Otherwise, peak sulfide concentrations lie between 3.2 and 6.1 mM and occur immediately above the SMI. The sulfur isotopic composition of interstitial sulfate generally becomes enriched in 34S with increasing sediment depth. Peak d34S-SO4 values occur just above the SMI and reach up to 53.1 per mil Vienna Canyon Diablo Troilite (VCDT) in Hole 1247B. d34S-Sigma HS values generally parallel the trend of d34S-SO4 values but are more depleted in 34S relative to sulfate, with values from -12.7 per mil to 19.3 per mil VCDT. Curvilinear sulfate profiles and carbon isotopic composition of total dissolved carbon dioxide at flank and basin sites strongly suggest that sulfate depletion is controlled by oxidation of sedimentary organic matter, despite the presence of methane gas hydrates in underlying sediments. Preliminary data from sulfur species are consistent with this interpretation for Leg 204 sediments at sites not located on or near the crest of Hydrate Ridge.

Biphytane and stable carbon isotopic values of sugars and glycerol from ODP Hole 204-1245D and 201-1229A

The membrane lipids diglycosyl-glycerol dibiphytanyl glycerol tetraethers (2G-GDGTs) in marine subsurface sediments are believed to originate from uncultivated benthic archaea, yet the production of 2G-GDGTs from subseafloor samples has not been demonstrated in vitro. In order to validate sedimentary biosynthesis of 2G-GDGTs, we performed a stable carbon isotope probing experiment on a subseafloor sample with six different 13C-labelled substrates (bicarbonate, methane, acetate, leucine, glucose and Spirulina platensis biomass). After 468 days of anoxic incubation, only glucose and S. platensis resulted in label uptake in lipid moieties of 2G-GDGTs, indicating incorporation of carbon from these organic substrates. The hydrophobic moieties of 2G-GDGTs showed minimal label incorporation, with up to 4 per mil 13C enrichment detected in crenarchaeol-derived tricyclic biphytane from the S. platensis-supplemented slurries. The 2G-GDGT-derived glucose or glycerol moieties also showed 13C incorporation (Dd13C = 18 - 38 per mil) in the incubations with glucose or S. platensis, consistent with a lipid salvage mechanism utilized by marine benthic archaea to produce new 2G-GDGTs. The production rates were nevertheless rather slow, even when labile organic matter was supplied. The 2G-GDGT turnover times of 1700 - 20 500 years were much longer than those estimated for subseafloor microbial communities, implying that sedimentary 2G-GDGTs as biomarkers of benthic archaea are cumulative records of past and present generations.

Molecular properties of gases of ODP Leg 204 sites

The recognition of finely disseminated gas hydrate in deep marine sediments heavily depends on various indirect techniques because this mineral quickly decomposes upon recovery from in situ pressure and temperature conditions. Here, we discuss molecular properties of closely spaced gas voids (formed as a result of core recovery) and gas hydrates from an area of relatively low gas flux at the flanks of the southern Hydrate Ridge offshore Oregon (ODP Sites 1244, 1245 and 1247). Within the gas hydrate occurrence zone (GHOZ), the concentration of ethane (C2) and propane (C3) in adjacent gas voids shows large variability. Sampled gas hydrates are enriched in C2 relative to void gases but do not contain C3. We suggest that the observed variations in the composition of void gases is a result of molecular fractionation during crystallization of structure I gas hydrate that contains C2 but excludes C3 from its crystal lattice. This hypothesis is used to identify discrete intervals of finely disseminated gas hydrate in cored sediments. Variations in gas composition help better constrain gas hydrate distribution near the top of the GHOZ along with variations in pore water chemistry and core temperature. Sediments near the base of the gas hydrate stability zone are relatively enriched in C2+ hydrocarbon gases. Complex and poorly understood geological and geochemical processes in these deeper sediments make the identification of gas hydrate based on molecular properties of void gases more ambiguous. The proposed technique appears to be a useful tool to better understand the distribution of gas hydrate in marine sediments and ultimately the role of gas hydrate in the global carbon cycle.