Geochemistry of phosphate and glauconites of ODP Leg 128 samples

Glauconites and phosphates have been detected in almost all investigated samples at Sites 798 (uppermost Miocene or lower Pliocene to Pleistocene) and 799 (early middle Miocene to Pleistocene). Autochthonous occurrences appear in very minor quantities (generally below 0.2%) throughout the drilled sequences, whereas allochthonous accumulations are limited to the lower Pliocene or uppermost Miocene sequence at Site 798 (glauconites) and to the upper and middle Miocene sequence at Site 799 (upper and middle Miocene: glauconites; middle Miocene: phosphates). X-ray fluorescence, microprobe, and bulk chemical analyses indicate high variabilities in cations and anions and generally low oxide totals. This is probably related to the substitution of phosphate and fluoride aniors by hydroxide and carbonate anions in phosphates and to the depletion of iron, aluminum, and potassium cations and the enrichment in hydroxide and crystal water in glauconites. Gradients in pore-water contents of dissolved phosphate and fluoride at Sites 798 and 799 suggest a depth of phosphate precipitation between 30 and 50 mbsf, with fluoride as the limiting element for phosphate precipitation at Site 798. Phosphate and fluoride appear to be balanced at Site 799. Crude extrapolations indicate that the Japan-Sea sediments may have taken up approximately 7.2*10**10 g P total/yr during the Neogene and Pleistocene. This amount corresponds to approximately 0.3% of the estimated present-day global transfer of phosphorus into the sediments and suggests that the Japan Sea constitutes an average sink for this element. The two main carriers of phosphorus into the present Japan Sea are the Tshushima and the Liman currents, importing approximately 6.6*10**10 g P and 5.7*10**10 g P per year, respectively. Bulk chemical analyses suggest that at least 36% of P total in the sediments is organically bound phosphorus. This rather high value, which corresponds to the measured Japan-Sea deep-water P organic/P total ratios, probably reflects rapid transport of organic phosphorus into the depth of the Japan Sea.

Corrected index properties for ODP Leg 127 and 128 sites

During Legs 127 and 128, we found a systematic error in the index property measurements, in that the wet bulk density, grain density, and porosity did not satisfy well-established interrelationships. We have found that an almost constant difference exists between the weight of water lost during drying and the volume of water lost. This discrepancy is independent of volume or water content of the sample. The water losses should be equal because the density of water is close to 1.0 g/cm**3. The pycnometer wet volume measurement has been identified as the source of the systematic error. The wet volume on average is 0.2 cm**3 too low. For the rare cases when the water content is negligible, there is no offset. The source of the wet volume error results from the partial vapor pressure of water in the pycnometer cell. Newly corrected tables of index properties measured during Legs 127 and 128 are included. The corrected index properties are internally consistent. The data are in better agreement with theoretical models that relate the index properties to other physical properties, such as thermal conductivity and acoustic velocity. In future, a standard volume sampler should be used, or the wet volume should be calculated from the dry volume and the water loss by weight.

Geochemistry of sediments and interstitial waters of ODP Sites 128-798 and128-799

Interstitial waters in sediments below 400 (Site 798) and 435 meters below seafloor (Site 799) have chloride concentrations of 516-527 and 501-515 mM, respectively, lower than the 540 mM of the modern-day Japan Sea. The chemical composition of interstitial waters, bulk sediments, clay-size sediment fraction, and carbonate nodules from Oki Ridge (Site 798) and Kita-Yamato Trough (Site 799), Japan Sea, reflect in-situ diagenetic processes superimposed on geochemical signals that may indicate freshening of Miocene local marginal basin waters. Interstitial waters at both sites exhibit changes in chemical composition which coincide with the occurrence of low-porosity and high-bulk density layers composed of dolomite and opal-CT, which impede diffusive communication with the overlying interstitial waters. Based on interstitial water stable isotope evidence and mass-balance calculations of chloride dilution, diagenetic reactions that involve the release of structural bound water from opal-A and/or clay minerals contribute to the observed geochemical signals, but cannot account for all the measured chloride dilution.

(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.