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.

Pore-water chemistry of ODP sites 111-677 and 111-678

Sites 677 and 678 were drilled on ODP Leg 111 to test hypotheses about the nature and pattern of hydrothermal circulation on a mid-ocean ridge flank. Together with earlier results from DSDP Site 501/504 and several heatflow and piston coring surveys covering a 100-km**2 area surrounding the three drill sites, they confirm that hydrothermal circulation persists in this 5.9-m.y.-old crust, both in basement and through the overlying sediments (Langseth et al., 1988, doi:10.2973/odp.proc.ir.111.102.1988). Profiles of sediment pore-water composition with depth at the three drill sites show both vertical and horizontal gradients. The shapes of the profiles and their variation from one site to another result from a combination of vertical and horizontal diffusion, convection, and reaction in the sediments and basement. Chemical species that are highly reactive in the siliceous-calcareous biogenic sediments include bicarbonate (alkalinity), ammonium, sulfate, manganese, calcium, strontium, lithium, silica, and possibly potassium. Reactions include bacterial sulfate reduction, mobilization of Mn2+, precipitation of CaCO3, and recrystallization of calcareous and siliceous oozes to chalk, limestone, and chert. Species with profiles more affected by reaction in basaltic basement than in the sediments include Mg, Ca, Na, K, and oxygen isotopes. Reaction in basement at 60?C and at higher temperatures has produced a highly altered basement formation water that is uniform in composition over distances of several kilometers. As inferred from the composition of the basal sediment pore water at the three sites, this uniformity extends from up flow zone to downflow zone in basement and the sediments. It exists in spite of large variations in heat flow and depth to basement, apparently as a result of homogenization by hydrothermal circulation in basement. Profiles for chlorinity, Na, Mg, and other species in the sediment pore waters confirm that Site 678, drilled on a localized heatflow high identified by Langseth et al. (1988), is a site of long-lived upwelling of warm water from basement through the sediments at velocities of 1 to 2 mm/yr. The upflow through the anomalously thin sediments is apparently localized above an uplifted fault block in basement. This site and other similar sites in the survey area give rise to lateral diffusion and possibly flow through the sediments, which produces lateral gradients in sediment pore-water composition at sites such as 501/504. The complementary pore-water profiles at the low-heatflow Site 677 2 km to the south indicate that downflow is occurring through the sediments there, at comparable rates of 1 to 2 mm/yr.

Carbonate mineralogy and stable isotope composition of cool-water bryozoans from sediments of ODP Leg 182 sites

The carbon and oxygen isotopic compositions of selected bryozoan skeletons from upper Pleistocene bryozoan mounds in the Great Australian Bight (Ocean Drilling Program Leg 182; Holes 1129C, 1131A, and 1132B) were determined. Cyclostome bryozoans, Idmidronea spp. and Nevianipora sp., have low to intermediate magnesian calcite skeletons (1.5-10.0 and 0.9-6.4 molar percentage [mol%] MgCO3, respectively), but a considerable number include marine cements. The cheilostome Adeonellopsis spp. are biminerallic, principally aragonite, with some high magnesian calcite (HMC) (6.6-12.1 mol% MgCO3). The HMC fraction of Adeonellopsis has lower d13C and similar d18O values compared with the aragonite fraction. Reexamination of modern bryozoan isotopic composition shows that skeletons of Adeonellopsis spp. and Nevianipora sp. form close to oxygen isotopic equilibrium with their ambient water. Therefore, changes in glacial-interglacial oceanographic conditions are preserved in the oxygen isotopic profiles. The bryozoan oxygen isotopic profiles are correlated well with marine isotope Stages 1-8 in Holes 1129C and 1132B and to Stages 1-4(?) in Hole 1131A. The horizons of the bryozoan mounds that yield skeletons with heavier oxygen isotopic values can be correlated with isotope Stages 2, 4(?), 6, and 8 in Hole 1129C; Stages 2 and 4(?) in Hole 1131A; and Stages 2, 4, 6, and 8 in Hole 1132B. These results provide supporting evidence for a model for bryozoan mound formation, in which the mounds were formed during intensified upwelling and increased trophic resources during glacial periods.