(Table 2) Composition of the deapest pore fluids from ODP Holes 168-1030B and 168-1031A

On the eastern flank of the Juan de Fuca Ridge, reaction between upwelling basement fluid and sediment alters hydrothermal fluxes of Ca, SiO2(aq), SO4, PO4, NH4, and alkalinity. We used the Global Implicit Multicomponent Reactive Transport (GIMRT) code to model the processes occurring in the sediment column (diagenesis, sediment burial, fluid advection, and multicomponent diffusion) and to estimate net seafloor fluxes of solutes. Within the sediment section, the reactions controlling the concentrations of the solutes listed above are organic matter degradation via SO4 reduction, dissolution of amorphous silica, reductive dissolution of amorphous Fe(III)-(hydr)oxide, and precipitation of calcite, carbonate fluorapatite, and amorphous Fe(II)-sulfide. Rates of specific discharge estimated from pore-water Mg profiles are 2 to 3 mm/yr. At this site the basement hydrothermal system is a source of NH4, SiO2(aq), and Ca, and a sink of SO4, PO4, and alkalinity. Reaction within the sediment column increases the hydrothermal sources of NH4 and SiO2(aq), increases the hydrothermal sinks of SO4 and PO4, and decreases the hydrothermal source of Ca. Reaction within the sediment column has a spatially variable effect on the hydrothermal flux of alkalinity. Because the model we used was capable of simulating the observed pore-water chemistry by using mechanistic descriptions of the biogeochemical processes occurring in the sediment column, it could be used to examine the physical controls on hydrothermal fluxes of solutes in this setting. Two series of simulations in which we varied fluid flow rate (1 to 100 mm/yr) and sediment thickness (10 to 100 m) predict that given the reactions modeled in this study, the sediment section will contribute most significantly to fluxes of SO4 and NH4 at slow flow rates and intermediate sediment thickness and to fluxes of SiO2(aq) at slow flow rates and large sediment thickness. Reaction within the sediment section could approximately double the hydrothermal sink of PO4 over a range of flow rates and sediment thickness, and could slightly decrease (by

Geochemistry of pore fluids from ODP Leg 134 sites

Depending on the temperature and the extent of diagenetic alteration of fluid chemistry, fluid flow at convergent margins may transfer important quantities of heat and mass between the crust and seawater, thereby influencing global mass, isotopic and heat budgets. In the North Aoba Basin, an intra-arc basin located at the New Hebrides Island Arc, alteration of volcanic ash to clay minerals and zeolites forms a CaCl2 brine, perhaps in less than 1 to 3 m.y. The brine results from an exchange of Ca for Na, K, and Mg, and an increase in Cl concentrations to a maximum of 1241 mM. The Cl increase is partly due to the transfer of H2O from the pore fluid into authigenic minerals, but water mass balances, d18O-Cl correlations, and Br/Cl ratios suggest that there is a source of Cl in the sediments. Concentration profiles indicate that Li is transferred from the fluid to solid phase at depths <300 meters below seafloor (mbsf), but at greater depths it is transferred from the solid to fluid phase, at temperatures possibly as low as 25°C. In the accretionary wedge extensive fluid flow appears to be confined to highly faulted regions. Although Cl concentrations less than seawater value are common at convergent margins, the New Hebrides margin contains little low-Cl fluid. Br/Cl ratios suggest the low-Cl fluid is from dilution, and d18O values indicate the water may be derived from mineral dehydration and mixing with meteoric water. The New Hebrides margin exhibits few surface manifestations of venting (e.g., sulfide-oxidizing benthic biological communities, carbonate crusts, mud volcanoes) and thus fluid fluxes may be smaller than at many other margins.

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.

Respiration rate and ammonium excretion data for the squat lobster Pleuroncodes monodon measured during METEOR cruise M93

Sampling was conducted during RV Meteor cruise M93 in austral summer 2013 in an area from 11ºS to 14ºS and approximately 120 km offshore to within 10 km of the Peruvian coast. Specimens were collected using a Hydrobios Multinet Maxi (0.5 m2 mouth opening, 330 µm mesh size, 9 nets) and a WP-2 net (Hydrobios, 0.26 m2 mouth opening, 200 µm mesh size). P. monodon were identified according to http://researchdata.museum.vic.gov.au/squatlobster/delta/deltakey.html. Specimens were transferred into filtered, well-oxygenated seawater immediately after the catch and maintained for 4 to 16 hours prior to physiological experiments. Maintenance and physiological experiments were conducted at 13°C as the temperature observed at 100 to 200 m depth in the OMZ ranged from 13.7 to 12.7°C.

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.

Phosphate d18O pore-water profiles of sediment core GeoB11807-2 and GeoB11804-4

Phosphorus cycling in the ocean is influenced by biological and geochemical processes that are reflected in the oxygen isotope signature of dissolved inorganic phosphate (Pi). Extending the Pi oxygen isotope record from the water column into the seabed is difficult due to low Pi concentrations and small amounts of marine porewaters available for analysis. We obtained porewater profiles of Pi oxygen isotopes using a refined protocol based on the original micro-extraction designed by Colman (2002). This refined and customized method allows the conversion of ultra-low quantities (0.5 - 1 µmol) of porewater Pi to silver phosphate (Ag3PO4) for routine analysis by mass spectrometry. A combination of magnesium hydroxide co-precipitation with ion exchange resin treatment steps is used to remove dissolved organic matter, anions, and cations from the sample before precipitating Ag3PO4. Samples as low as 200 µg were analyzed in a continuous flow isotope ratio mass spectrometer setup. Tests with external and laboratory internal standards validated the preservation of the original phosphate oxygen isotope signature (d18OP) during micro extraction. Porewater data on d18OP has been obtained from two sediment cores of the Moroccan margin. The d18OP values are in a range of +19.49 to +27.30 per mill. We apply a simple isotope mass balance model to disentangle processes contributing to benthic P cycling and find evidence for Pi regeneration outbalancing microbial demand in the upper sediment layers. This highlights the great potential of using d18OP to study microbial processes in the subseafloor and at the sediment water interface.