(Table 1) Peak intensities and stable carbon and oxygen isotope ratios of various diagenetic carbonates of ODP Site 128-799

Abundant and various diagenetic carbonates were recovered from a 1084-m-thick, Quaternary to lower Miocene section at ODP Site 799 in the Japan Sea. Petrographic, XRD, SEM, EDS-chemical, and isotopic analyses revealed wide variations in occurrence and textural relations and complex mineralogy and chemistry. Diagenetic carbonates include calcite, calcium-rich rhodochrosite, iron- and manganese-rich magnesite, iron- and manganese-rich dolomite and ankerite, and iron- and manganeserich lansfordite (hydrous Mg-carbonate). Rhodochrosite commonly occurs as small, solid nodules and semi-indurated, thin layers in bioturbated, mottled sediments of Units I and II (late Miocene to Quaternary). Lansfordite occurs as unindurated nodules and layers in Unit II (late Miocene and Pliocene), whereas magnesite forms indurated beds a few centimeters thick in slightly bioturbated-to-faintly laminated sediments of Unit III (middle and late Miocene). Some rhodochrosite nodules have dark-colored, pyritic cores, and some pyrite-rhodochrosite nodules are overgrown by and included within magnesite beds. Dolomite and ankerite tend to form thick beds (>10 cm) in bedded to laminated sediments of Units III, IV, and V (early to late Miocene). Calcite occurs sporadically throughout the Site 799 sediments. The d18O values of carbonates and the interstitial waters, and the measured geothermal gradient indicate that almost all of the Site 799 carbonates are not in isotopic equilibrium with the ambient waters, but were precipitated in the past when the sediments were at shallower depths. Depths of precipitation obtained from the d18O of carbonates span from 310 to 510 mbsf for magnesite and from 60 to 580 mbsf for dolomite-ankerite. Rhodochrosite and calcite are estimated to have formed within sediments at depths shallower than 80 mbsf. Diagenetic history in the Site 799 sediments have been determined primarily by the environment of deposition; in particular, by the oxidation-reduction state of the bottom waters and the alkalinity level of the interstitial waters. Under the well-oxygenated bottom-water conditions in the late Miocene and Pliocene, manganese initially accumulated on the seafloor as hydrogenous oxides and subsequently was mobilized and reprecipitated as rhodochrosite within the shallow sulfate-reduction, sub-oxic zone. Precipitation of lansfordite occurred in the near-surface sediments with abundant organic carbon and an extremely high alkalinity during the latest Miocene and Pliocene. The lansfordite was transformed to magnesite upon burial in the depth interval 310 to 510 mbsf. Dolomite first precipitated at shallow depths in Mn-poor, anoxic, moderately biocalcareous sediments of early to late Miocene. With increasing temperature and depth, the dolomite recrystallized and reequilibrated with ambient waters at depths below about 400 mbsf.

(Table 1) Downcore age and bulk geochemistry of sediment core GS7202-35

The distribution of redox-sensitive metals in sediments is potentially a proxy for past ocean ventilation and productivity, but deconvolving these two major controls has proved difficult to date. Here we present a 740 kyr long record of trace element concentrations from an archived sediment core collected at ~15°S on the western flank of the East Pacific Rise (EPR) on 1.1 Myr old crust and underlying the largest known hydrothermal plume in the world ocean. The downcore trace element distribution is controlled by a variable diagenetic overprint of the inferred primary hydrothermal plume input. Two main diagenetic processes are operating at this site: redox cycling of transition metals and ferrihydrite to goethite transition during aging. The depth of oxidation in these sediments is controlled by fluctuations in the relative balance of bottom water oxygen and electron donor input (organic matter and hydrothermal sulfides). These fluctuations induce apparent variations in the accumulation of redox-sensitive species with time. Subsurface U and P peaks in glacial age sediments, in this and other published data sets along the southern EPR, indicate that basin-wide changes in deep ocean ventilation, in particular at glacial-interglacial terminations II, III, IV, and V, alter the depth of the oxidation front in the sediments. These basin-wide changes in the deep Pacific have significant implications for carbon partitioning in the ocean-atmosphere system, and the distribution of redox-sensitive metals in ridge crest sediment can be used to reconstruct past ocean conditions at abyssal depths in the absence of alternative proxy records.