Biogenic sedimentation of DSDP Site 85-574

The equatorial Pacific is an important part of the global carbon cycle and has been affected by climate change through the Cenozoic (65 Ma to present). We present a Miocene (12-24 Ma) biogenic sediment record from Deep Sea Drilling Project (DSDP) Site 574 and show that a CaCO3 minimum at 17 Ma was caused by elevated CaCO3 dissolution. When Pacific Plate motion carried Site 574 under the equator at about 16.2 Ma, there is a minor increase in biogenic deposition associated with passing under the equatorial upwelling zone. The burial rates of the primary productivity proxies biogenic silica (bio-SiO2) and biogenic barium (bio-Ba) increase, but biogenic CaCO3 decreases. The carbonate minimum is at ~17 Ma coincident with the beginning of the Miocene climate optimum; the transient lasts from 18 to 15 Ma. Bio-SiO2 and bio-Ba are positively correlated and increase as the equator was approached. Corg is poorly preserved, and is strongly affected by changing carbonate burial. Terrestrial 232Th deposition, a proxy for aeolian dust, increases only after the Site 574 equator crossing. Since surface production of bio-SiO2, bio-Ba, and CaCO3 correlate in the modern equatorial Pacific, the decreased CaCO3 burial rate during the Site 574 equator crossing is driven by elevated CaCO3 dissolution, representing elevated ocean carbon storage and elevated atmospheric CO2. The length of the 17 Ma CaCO3 dissolution transient requires interaction with a 'slow' part of the carbon cycle, perhaps elevated mantle degassing associated with the early stages of Columbia River Basalt emplacement.

Calcareous nannofossil biostratigraphy of ODP Hole 108-667A and DSDP Site 85-574

Detailed quantitative analyses of selected calcareous nannofossil species were used to determine the placement of zonal boundaries. In Hole 667A in the equatorial Atlantic Ocean, Zones CP19 through CN5 were recognized, whereas at Site 574 in the equatorial Pacific Ocean, only the CN4/CN5 boundary could be determined. Boundaries were identified by sharp rises and declines in abundance at the beginnings and ends, respectively, of index fossil ranges. The sharp rise in abundance at the beginning of the range of Triquetrorhabdulus rugosus provided a good datum level in both regions; the same is true for the sharp decline in abundance at the end of the range of Cyclicargolithus floridanus. The last occurrence of Helicosphaera ampliaperta was used to mark the CN3/CN4 boundary in Hole 667A, while at Site 574, H. ampliaperta was absent. The abundance pattern of Triquetrorhabdulus carinatus obtained from Hole 667A makes it impossible to observe a distinct disappearance level. Age/depth plots reveal uniform sedimentation rates at both sites during early Miocene times. At Site 667 in the Atlantic the mean sedimentation rate was 14.90 m/m.y., and at Site 574 in the Pacific it was 16.17 m/m.y. during this same period. One new nannofossil species, Triquetrorhabdulus rioensis, is described; and one species, Triquetrorhabdulus serratus, is recombined.

Stable oxygen isotope ratios of marine barite from Cenozoic sediments

We report new data on oxygen isotopes in marine sulfate (delta18O[SO4]), measured in marine barite (BaSO4), over the Cenozoic. The delta18O[SO4] varies by 6x over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The delta18O[SO4] does not co-vary with the delta18O[SO4], emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the delta18O[SO4] over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The delta18O[SO4] also does not co-vary with the d18O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the delta18O[SO4] to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the delta18O[SO4]. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.

Late Eocene to Recent deep-sea benthic foraminifera from the Central equatorial Pacific Ocean

Benthic foraminifers were studied in upper Eocene to Recent core-catcher samples from DSDP Sites 573, 574, and 575. The sites are on a north-south transect from the equator to about 05°N at about 133°W, water depth 4300 to 4600 m. At Site 574 additional samples were used to study the Eocene/Oligocene boundary in detail. About 200 specimens were counted per sample. The fauna is highly diverse (about 50 to 70 species per sample) and is of low dominance. The diversity is not related to age or sub-bottom depth. Many species are cosmopolitan and probably have wide environmental tolerances. Fluctuations in frequency of some taxa (e.g., Nuttallides umbonifera, Epistominella exigua, and Uvigerina spp.) cannot be correlated from one site to another. Several common species (e.g. Oridorsalis umbonatus and Globocassidulina subglobosa) range from late Eocene to Recent. First and last appearances are generally difficult to define precisely because many species are rare. For some species these datums differ from one site to another, but several datum levels are within 1 m.y. at all sites. First and last appearances are most numerous in two intervals, the late Eocene to early Oligocene (about 32 to 37 Ma) and the early to middle Miocene (about 13 to 18.5 Ma). Isotopic events occur within each of these periods of benthic faunal change, but the isotopic events have a shorter duration and start after the initiation of the changes in the fauna. Changes in deep-sea benthic faunal composition are not directly related to short-term oceanographic changes as expressed in isotopic records.

(Table S1) Calcium isotope ratios of Pacific Ocean sediments

Multiple lines of evidence have shown that the isotopic composition and concentration of calcium in seawater have changed over the past 28 million years. A high-resolution, continuous seawater calcium isotope ratio curve from marine (pelagic) barite reveals distinct features in the evolution of the seawater calcium isotopic ratio suggesting changes in seawater calcium concentrations. The most pronounced increase in the d44/40Ca value of seawater (of 0.3 per mil) occurred over roughly 4 million years following a period of low values around 13 million years ago. The major change in marine calcium corresponds to a climatic transition and global change in the carbon cycle and suggests a reorganization of the global biogeochemical system.

Monitoring phase behavior of sub- and supercritical CO2 confined in porous fractal silica with 85% porosity

Phase behavior of CO2 confined in porous fractal silica with volume fraction of SiO2 φs = 0.15 was investigated using small-angle neutron scattering (SANS) and ultrasmall-angle neutron scattering (USANS) techniques. The range of fluid densities (0<(FCO2)bulk<0.977 g/cm3) and temperatures (T=22 °C, 35 and 60 °C) corresponded to gaseous, liquid, near critical and supercritical conditions of the bulk fluid. The results revealed formation of a dense adsorbed phase in small pores with sizes D<40 A° at all temperatures. At low pressure (P <55 bar, (FCO2)bulk <0.2 g/cm3) the average fluid density in pores may exceed the density of bulk fluid by a factor up to 6.5 at T=22 °C. This “enrichment factor” gradually decreases with temperature, however significant fluid densification in small pores still exists at temperature T=60°C, i.e., far above the liquid-gas critical temperature of bulk CO2 (TC=31.1 °C). Larger pores are only partially filled with liquid-like adsorbed layer which coexists with unadsorbed fluid in the pore core. With increasing pressure, all pores become uniformly filled with the fluid, showing no measurable enrichment or depletion of the porous matrix with CO2.