TOC, carbonate, opal composition and trace element concentration from ODP Holes 175-1082A and 175-1084A

Distinctive light-dark color cycles in sediment beneath the Benguela Current Upwelling System indicate repetitive alternations in sediment delivery and deposition. Geochemical proxies for paleoproductivity and for depositional conditions were employed to investigate the paleoceanographic processes involved in creating these cycles in three mid-Pleistocene intervals from ODP Sites 1082 and 1084. Concentrations of total organic carbon (TOC) vary between 3.5 and 17.1%. Concentrations of CaCO3 vary inversely to TOC and Al, which suggests that both carbonate dissolution and terrigenous dilution contribute to the light-dark cycles. Opal concentrations are independent of both TOC and CaCO3, therefore eliminating diatom production and lateral transport of shelf material as causes of the light-dark cycles. d13Corg and d15Ntot values do not vary across light-dark sediment intervals, implying that the extent of relative nutrient utilization did not change. The stable d15Ntot values represent a balanced change in nitrate supply and export production and therefore indicate that productivity was elevated during deposition of the TOC-rich layers. Parallel changes in concentrations of indicator trace elements and TOC imply that changes in organic matter delivery influenced geochemical processes on the seafloor by controlling consumption of pore water oxygen. Cu, Ni, and Zn are enriched in the darker sediment as a consequence of greater organic matter delivery. Redox-sensitive metals vary due to loss (Mn and Ba) or enrichment (Mo) under reducing conditions created by TOC oxidation. Organic matter delivery impacts subsequent geochemical changes such as carbonate dissolution, sulfate reduction and the concentration of metals. Thus, export production is considered ultimately responsible for the generation of the color cycles.

Siliceous phytoplankton in middle Eocene sediments of ODP Hole 207-1260A

The Middle Eocene diatom and silicoflagellate record of ODP Site 1260A (Demerara Rise) is studied quantitatively in order to throw light on the changes that siliceous phytoplankton communities experienced during a Middle Eocene warming event that occurred between 44.0 and 42.0 Ma. Both Pianka's overlap index, calculated per couple of successive samples, and cluster analysis, point to a number of significant turnover events highlighted by changes in the structure of floristic communities. The pre-warming flora, dominated by cosmopolitan species of the diatom genus Triceratium, is replaced during the warming interval by a new and more diverse assemblage, dominated by Paralia sulcata (an indicator of high productivity) and two endemic tropical species of the genus Hemiaulus. The critical warming interval is characterized by a steady increase in biogenic silica and a comparable increase in excess Ba, both reflecting an increase in productivity. In general, it appears that high productivity not only increased the flux of biogenic silica, but also sustained a higher diversity in the siliceous phytoplankton communities. The microflora preserved above the critical interval is once again of low diversity and dominated by various species of the diatom genus Hemiaulus. All assemblages in the studied material are characterized by the total absence of continental and benthic diatoms and the relative abundance of neritic forms, suggesting a transitional depositional environment between the neritic and the oceanic realms.

Rare earth element contents in deposits and minerals of the ocean floor

Current understanding of rare earth element (REE) geochemistry in the ocean is given in the book. Chemical properties determining REE migration ability in natural processes, sources of REE in the ocean, behavior of REE in river-sea mixing zones, fractionation of dissolved and particulate REE in ocean waters under aerobic and anaerobic conditions, distribution of REE in terrigenous, authigenic, hydrothermal and biogenic sediment components (clay, bone detritus, barite, phillipsite, Fe- and Mn-oxyhydroxides, Fe-Ca hydroxophosphate, diatoms and foraminiferas) are under consideration.

Late Miocene carbon isotope and paleoproductivity record

We examine whether or not a relationship exists between the late Miocene carbon isotope shift (~7.6-6.6 Ma) and marine productivity at four sites from the Indian and Pacific Oceans (Ocean Drilling Program Sites 721, 1146, 1172, and 846). We use a multiproxy approach based on benthic foraminiferal accumulation rates, elemental ratios, and dissolution indices, and we compare these data to benthic foraminiferal d13C values measured on the same samples. Although some of these sites have been targeted previously in studies of either the late Miocene/early Pliocene "biogenic bloom" (Sites 721 and 846) or the late Miocene carbon isotope shift (Site 1172), our records are the first to establish paired proxy records of carbon isotopes and paleoproductivity allowing a direct assessment of a potential link. Our results indicate that at all sites, productivity increased sometime during the d13C shift; at three sites (721, 1146, and 846), productivity increased at the beginning of the shift. The correlation coefficients derived from linear regression between micropaleontologically derived productivity and foraminiferal d13C values are relatively high during the time interval containing the late Miocene d13C shift (and statistically significant at three of the sites). Carbon flux and isotope mass balance considerations illustrate that transfer of organic matter between the terrestrial and marine reservoirs together with enhanced oceanic upwelling best approximates observed changes in carbon isotope records and paleoproductivity. We note that long-term trend in the Site 846 paleoproductivity record can be correlated to the long-term trend in the Site 848 eolian flux reconstructions of Hovan (1995, doi:10.2973/odp.proc.sr.138.132.1995) hinting at a link between strengthened wind regime and productivity during the late Miocene.

Composition of pore water and diagenetic carbonates of ODP Site 123-765

Degradation of organic matter in slightly organic-rich (1 wt% organic carbon) Neogene calcareous turbidites of the Argo Basin at Site 765 by sulfate reduction results in pore-water phosphate, ammonium, manganese, and carbonate alkalinity maxima. Pore-water calcium and magnesium decrease in the uppermost 100 meters below seafloor (mbsf) in response to the precipitation of calcian dolomite with an average composition of Ca1.15Mg0.83Fe0.02(CO3)2. Clear, euhedral dolomite rhombs range from <1 to 40 µm in diameter and occur in trace to minor amounts (<1-2 wt%) in Pleistocene to Pliocene sediment (62-210 mbsf) The abundance of dolomite increases markedly (2-10 wt%) in Miocene sediment (210-440 mbsf). The dolomite is associated with diagenetic sepiolite and palygorskite, as well as redeposited biogenic low-Mg calcite and aragonitic benthic foraminifers. Currently, dolomite is precipitating at depth within the pore spaces of the sediment, largely as a result of aragonite dissolution. The rate of aragonite dissolution, calculated from the pore-water strontium profile, is sufficient to explain the amount of dolomite observed at Site 765. A foraminiferal aragonite precursor is further supported by the carbon and oxygen isotopic compositions of the dolomite, which are fairly close to the range of isotopic compositions observed for Miocene benthic foraminifers. Dolomite precipitation is promoted by the degradation of organic matter by sulfate-reducing bacteria because the lower pore-water sulfate concentration reduces the effect of sulfate inhibition on the dolomite reaction and because the higher carbonate alkalinity increases the degree of saturation of the pore waters with dolomite. Organic matter degradation also results in the precipitation of pyrite and trace amounts of apatite (francolite), and the release of iron and manganese to the pore water by reduction of Fe and Mn oxides. Spherical, silt-sized aggregates of microcrystalline calcian rhodochrosite occur in trace to minor amounts in Lower Cretaceous sediment from 740 to 900 mbsf at Site 765. A negative carbon isotopic composition suggests that the rhodochrosite formed early in the sulfate reduction zone, but a depleted oxygen isotopic composition suggests that the rhodochrosite may have recrystallized at deeper burial depths.