Anaerobic oxidation of methane and sulphate reduction rates, hydrocarbons, sulphate and sulphide concentrations of sediment cores from the Larsen B embayment at the eastern site of the Antarctic Peninsula

First videographic indication of an Antarctic cold seep ecosystem was recently obtained from the collapsed Larsen B ice shelf, western Weddell Sea (Domack et al., 2005). Within the framework of the R/V Polarstern expedition ANTXXIII-8, we revisited this area for geochemical, microbiological and further videographical examinations. During two dives with ROV Cherokee (MARUM, Bremen), several bivalve shell agglomerations of the seep-associated, chemosynthetic clam Calyptogena sp. were found in the trough of the Crane and Evans glacier. The absence of living clam specimens indicates that the flux of sulphide and hence the seepage activity is diminished at present. This impression was further substantiated by our geochemical observations. Concentrations of thermogenic methane were moderately elevated with 2 µM in surface sediments of a clam patch, increasing up to 9 µM at a sediment depth of about 1 m in the bottom sections of the sediment cores. This correlated with a moderate decrease in sulphate from about 28 mM at the surface down to 23.4 mM, an increase in sulphide to up to 1.43 mM and elevated rates of the anaerobic oxidation of methane (AOM) of up to 600 pmol cm**-3 d**-1 at about 1 m below the seafloor. Molecular analyses indicate that methanotrophic archaea related to ANME-3 are the most likely candidates mediating AOM in sediments of the Larsen B seep.

Sulphate and d34S in pore waters and d13C, d18O and mineral composition of carbonate nodules from ODP Leg 188 sites

Carbon and oxygen isotopic compositions of authigenic carbonate nodules or layers reflect the diagenetic conditions at the time of nodule growth. The shallowest samples of carbonate nodules and dissolved inorganic carbon of pore water samples beneath the sulfate reduction zone (0-160 meters below seafloor [mbsf]) at Site 1165 have extremely negative d13C values (-50 per mil and -62 per mil, respectively). These negative d13C values indicate nodule formation in association with anaerobic methane oxidation coupled with sulfate reduction. The 34S of residual sulfate at Site 1165 shows only minor 34S enrichment (+6 per mil), even with complete sulfate reduction. This small degree of apparent 34S enrichment is due to extreme "open-system" sulfate reduction, with sulfate abundantly resupplied by diffusion from overlying seawater. Ten calcite nodules from Site 1165 contain minor quartz and feldspar and have d13C values ranging from -49.7 per mil to -8.2 per mil. The nodules with the most negative d13C values currently are at depths of 273 to 350 mbsf and must have precipitated from carbonate largely derived from subsurface anaerobic methane oxidation. The processes of sulfate reduction coupled with methane oxidation in sediments of Hole 1165B are indicated by characteristic concentration and isotopic (d34S and d13C) profiles of dissolved sulfate and bicarbonate. Three siderite nodules from Site 1166 contain feldspar and mica and one has significant carbonate-apatite. The siderite has d13C values ranging from -15.3 per mil to -7.6 per mil. These siderite nodules probably represent early diagenetic carbonate precipitation during microbial methanogenesis.

Interstitial water chemistry of ODP Leg 110 holes

Major-element compositions (Cl-, SO4[2-], Ca2+, Mg2+ , Li+ , K+, Na+ , Sr2+) of interstitial waters obtained from sediment cores along the ODP Leg 110 transect across the Northern Barbados accretionary prism have shown that a complex set of geochemical processes are of importance in this area. In the volcanic ash-rich Pleistocene-Pliocene sediments, alteration reactions involving volcanic ash lead to depletions of Mg2+ and K+. This process is confirmed by the much lower than contemporaneous seawater values of the 87Sr/86Sr ratios of dissolved strontium. In the deeper sediments recovered below the zone of decollement (Sites 671 and 672) large increases in Ca2+ and gradual decreases in Mg2+ , Na+, and d18O (H2O) indicate a potential contribution to the interstitial water chemistry by exchange with underlying basement rocks. This process has been hard to confirm because the drill holes were terminated well short of reaching basement. However, the concentration gradient pattern is consistent with observations in a large number of DSDP drill holes. Finally, but most importantly, low Cl- concentrations in the decollement zone and underlying sand layers, as well as in fault zones at Sites 673 and 674, indicate dilution of interstitial waters. The potential origins of the low Cl- concentrations are discussed, though we are not able to distinguish any mechanism in particular. Our evidence supports the concept of water migration along the decollement and through the underlying sandstones as well as along recent fault zones in the accretionary complex. Interstitial water concentration depth profiles are affected by faulting, thrusting, and overturn processes in the accretionary prism. These processes have caused a diminished diffusive exchange with the overlying ocean, thus explaining increased depletions in Mg2+ and SO4[2-] in sites farther onto the accretionary prism.

Annual variations in composition of the North Dvina River water

New data on elemental composition of particulate matter from the North Dvina River are presented. In May (period of snowmelt flood) it is similar to the upper layer of the continental crust due to active erosion of crust material in the catchment area. In August (summer low water period) impact of biogenic components increases and elevated concentrations of Cd, Sb, Mn, Zn, Pb, and Cu are observed. At other seasons no significant increase in heavy and rare earth element concentrations is observed.

Sulphate concentrations and sulphur isotopic composition in pore fluids from ODP Leg 168 sites

A numerical model of sulfate reduction and isotopic fractionation has been applied to pore fluid SO4**2- and d34S data from four sites drilled during Ocean Drilling Program (ODP) Leg 168 in the Cascadia Basin at 48°N, where basement temperatures reach up to 62°C. There is a source of sulfate both at the top and the bottom of the sediment column due to the presence of basement fluid flow, which promotes bacterial sulfate reduction below the sulfate minimum zone at elevated temperatures. Pore fluid d34S data show the highest values (135 per mil) yet found in the marine environment. The bacterial sulfur isotopic fractionation factor, a, is severely underestimated if the pore fluids of anoxic marine sediments are assumed to be closed systems and Rayleigh fractionation plots yield erroneous values for a by as much as 15 per mil in diffusive and advective pore fluid regimes. Model results are consistent with a = 1.077+/-0.007 with no temperature effect over the range 1.8 to 62°C and no effect of sulfate reduction rate over the range 2 to 10 pmol/ccm/day. The reason for this large isotopic fractionation is unknown, but one difference with previous studies is the very low sulfate reduction rates recorded, about two orders of magnitude lower than literature values that are in the range of µmol/ccm/day to tens of nmol/ccm/day. In general, the greatest 34S depletions are associated with the lowest sulfate reduction rates and vice versa, and it is possible that such extreme fractionation is a characteristic of open systems with low sulfate reduction rates.