Phosphorus components and barite in untreated and in carbonate-free sediments of ODP Hole 199-1221C

We determined changes in equatorial Pacific phosphorus (µmol P/g) and barite (BaSO4; wt%) concentrations at high resolution (2 cm) across the Paleocene/Eocene (P/E) boundary in sediments from Ocean Drilling Program (ODP) Leg 199 Site 1221 (153.40 to 154.80 meters below seafloor [mbsf]). Oxide-associated, authigenic, and organic P sequentially extracted from bulk sediment were used to distinguish reactive P from detrital P. We separated barite from bulk sediment and compared its morphology with that of modern unaltered biogenic barite to check for diagenesis. On a CaCO3-free basis, reactive P concentrations are relatively constant and high (323 µmol P/g or ~1 wt%). Barite concentrations range from 0.05 to 5.6 wt%, calculated on a CaCO3-free basis, and show significant variability over this time interval. Shipboard measurements of P and Ba in bulk sediments are systematically lower (by ~25%) than shore-based concentrations and likely indicate problems with shipboard standard calibrations. The presence of Mn oxides and the size, crystal morphology, and sulfur isotopes of barite imply deposition in sulfate-rich pore fluids. Relatively constant reactive P, organic C, and biogenic silica concentrations calculated on a CaCO3-free basis indicate generally little variation in organic C, reactive P, and biogenic opal burial across the P/E boundary, whereas variable barite concentrations indicate significant changes in export productivity. Low barite Ba/reactive P ratios before and immediately after the Benthic Extinction Event (BEE) may indicate efficient nutrient burial, and, if nutrient burial and organic C burial are linked, high relative organic C burial that could temporarily drawdown CO2 at this site. This interpretation requires postdepositional oxidation of organic C because organic C to reactive P ratios are low throughout the section. After the BEE, higher barite Ba/reactive P ratios combined with higher barite Ba concentrations may imply that higher export productivity was coupled with unchanged reactive P burial, indicating efficient nutrient and possibly also organic C recycling in the water column. If the nutrient recycling is decoupled from organic C, the high export production could be indicative of drawdown of CO2. However, the observation that organic C burial is not high where barite burial is high may imply that either C sequestration was restricted to the deep ocean and thus occurred only on timescales of the deep ocean mixing or that postdepositional oxidation (burn down) of organic matter affected the sediments. The decoupling of barite and opal may result from low opal preservation or production that is not diatom based.

Carbonat-free sediment components of ODP Leg 115 holes

From the equatorial Indian Ocean, carbonate-free portions of sediment samples of Paleocene to Miocene calcareous oozes and chalks from Sites 707, 709, and 711 were studied using X-ray diffraction measurements and the scanning electron microscope. Downhole variations in biogenic opal, quartz, barite, and clinoptilolite were investigated. The abundance patterns of these major mineral phases show several similarities and may be used for additional lithologic correlations. Variations in biogenic opal contents reflect biogenic silica productivity. Beside the general pattern, a succession in biogenic silica decrease through time is generally recorded since the Oligocene. This succession started earliest at northernmost Site 711 and latest at southernmost Site 707, including Site 709 within these two. Opal-A variations as well as the barite distribution may be influenced by the paleoposition of the sites in relation to the high-productivity zone, which today lies south of the equator. Authigenic clinoptilolite apparently formed in two different modes. In deeper sediment intervals, clinoptilolite was the last mineral phase formed associated with enhanced silica diagenesis. In late Oligocene to middle Miocene sediments, clinoptilolite was the only authigenic silica phase encountered where otherwise strong opal dissolution was observed. The sponge spicules showed special dissolution features probably related to microbiological activity. Silica concretions mainly composed of opal-CT and authigenic quartz occur in carbonate-rich environments and are formed during later diagenesis when burial depth causes the sediments to reach higher temperatures. Opal-CT concretions in carbonate-free siliceous oozes were found at Site 711 and are probably formed during an early stage of silica diagenesis.