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.

(Table S1) Stable oxygen isotope record of barite from DSDP Leg 85 sites

Oxygen isotopes in marine sulfate (d18O SO4) measured in marine barite show variability over the past 10 million years, including a 5per mil decrease during the Plio-Pleistocene, with near-constant values during the Miocene that are slightly enriched over the modern ocean. A numerical model suggests that sea level fluctuations during Plio-Pleistocene glacial cycles affected the sulfur cycle by reducing the area of continental shelves and increasing the oxidative weathering of pyrite. The data also require that sulfate concentrations were 10 to 20% lower in the late Miocene than today.

Strontium and neodymium isotope data for barite separates and pore waters, and isotope and concentration data for foraminifera and fish teeth from DSDP Leg 85 sediments

Strontium and neodymium isotopic data are reported for barite samples chemically separated from Late Miocene to Pliocene sediments from the eastern equatorial Pacific. At a site within a region of very high productivity close to the equator, 87Sr/86Sr ratios in the barite separates are indistinguishable from those of foraminifera and fish teeth from the same samples. However, at two sites north of the productivity maximum barite separates have slightly, but consistently lower (averaging 0.000062) ratios than the coexisting phases, although values still fall within the total range of published values for the contemporaneous seawater strontium isotope curve. We examine possible causes for this offset including recrystallization of the foraminifera, fish teeth or barite, the presence of non-barite contaminants, or incorporation of older, reworked deep-sea barite; the inclusion of a small amount of hydrothermal barite in the sediments seems most consistent with our data, although there are difficulties associated with adequate production and transportation of this phase. Barite is unlikely to replace calcite as a preferred tracer of seawater strontium isotopes in carbonate-rich sediments, but may prove a useful substitute in cases where calcite is rare or strongly affected by diagenesis. In contrast to the case for strontium, neodymium isotopic ratios in the barite separates are far from expected values for contemporary seawater, and appear to be dominated by an (unobserved) eolian component with high neodymium concentration and low 143Nd/144Nd. These results suggest that the true potential of barite as an indicator of paleocean neodymium isotopic ratios and REE patterns will be realized only when a more selective separation procedure is developed.

Interstitial water chemistry of DSDP Leg 85 sites

The concentration changes in pore waters of dissolved calcium, magnesium, sulfate, strontium, and silica and of alkalinity are controlled by diagenetic reactions occurring within the biogenic sediments of DSDP Sites 572, 573, and 574. Downcore increases in dissolved Sr2 + indicate recrystallization of calcite, and increases in dissolved SiO2 reflect dissolution of amorphous silica. Minor gradients in dissolved Ca(2+) and Mg(2+) suggest little if any influence from reactions involving volcanic sediments or basalt. Differences in interstitial water profiles showing the downhole trends of these chemical species mark variations in carbonate and silica diagenesis, sediment compositions, and sedimentation rate histories among the sites. The location and extent of carbonate diagenesis in these sediments are determined from Sr/Ca distributions between the interstitial waters and the bulk carbonate samples. Pore water strontium increases in the upper 100 to 250 m of sediment are assumed to reflect diffusion from underlying zones where calcite recrystallization has occurred. On the basis of calculations of dissolved strontium production and comparisons between observed and calculated "equilibrium" Sr/Ca ratios of the solids, approximately 30 to 50% of the carbonate has recrystallized in these deeper intervals. These estimates agree with the observed amounts of chalk at these sites. Variations in Sr/Ca ratios of these carbonates reflect differences in calcareous microfossil content, in diagenetic history, and, possibly, in changes in seawater Sr/Ca with time. Samples of porcelanite recovered below 300 m at Site 572 suggest formation at temperatures 20 to 30° C greater than ones estimated assuming oceanic geothermal gradients from sedimentary sections similar to those recovered on Leg 85. The higher temperatures may partially account for higher Sr/Ca ratios determined for recrystallized carbonates from this site.

Rock magnetism of pelagic sediments from DSDP Leg 85 sites

A detailed rock magnetic investigation has been carried out on Deep Sea Drilling Project (DSDP) pelagic sediments from the Central Equatorial Pacific. This comprises hysteresis and thermomagnetic measurements, Lowrie-Fuller test and, for the first time, ferromagnetic resonance (FMR). Nearly stochiometric magnetite in two grain size fractions, single domain (SD) and multi domain (MD), has been deduced to be the carrier of magnetic remanence. Comparatively strong paramagnetic contributions are carried by pyrite, being identified by X-ray analysis. The statistical analysis of paleomagnetic parameters (NRM, MDF, initial susceptibility, Königsberger ratio Q) from a large number (> 1000) of samples, supported by hysteresis measurements, indicates a latitude and sedimentation rate dependent ratio of SD/MD grains. Possible sources for the magnetic constituents are discussed in terms of bacterial, volcanic, meteoritic and authigenic origin.

Benthic foraminifera and phytodetritus species in sediments from DSDP Leg 85, and ODP Legs 113 and 143

From late middle Eocene through earliest Oligocene, high-latitude regions cooled, and by the end of the period, continental ice sheets existed in Antarctica. Diversity of planktonic microorganisms declined, and modern groups of terrestrial vertebrates originated. Coeval faunal changes in deep-sea benthic foraminifers have been related to cooling of deep waters and increased oxygenation. Cooling, however, occurred globally, whereas species richness declined at high latitudes and not in the tropics. The late Eocene and younger lower-diversity, high-latitude faunas typically contain common Epistominella exigua and Alabaminella weddellensis, opportunistic phytodetritus-exploiting species that indicate a seasonally fluctuating input of organic matter to the sea floor. We speculate that the species-richness gradient and increase in abundance of phytodetritus-exploiting species resulted largely from the onset of a more unpredictable and seasonally fluctuating food supply, especially at high latitudes.

Age models and stable isotope ratios from the Mid-Miocene

Mid-Miocene pelagic sedimentary sections can be correlated using intermediate and high resolution oxygen and carbon isotopic records of benthic foraminifera. Precision of a few tens of thousands of years is readily achievable at sites with high sedimentation rates, for example, Deep Sea Drilling Project sites 289 and 574. The mid-Miocene carbon isotope records are characterized by an interval of high d13C values between 17 and 13.5 Ma (the Monterey Excursion of Vincent and Berger 1985) upon which are superimposed a series of periodic or quasi-periodic fluctuations in d13C values. These fluctuations have a period of approximately 440 kyr, suggestive of the 413 kyr cycle predicted by Milankovitch theory. Vincent and Berger proposed that the Monterey Excursion was the result of increased organic carbon burial in continental margins sediments. The increased d13C values (called 13C maxima) superimposed on the generally high mid-Miocene signal coincide with increases in d18O values suggesting that periods of cooling and/or ice buildup were associated with exceptionally rapid burial of organic carbon and lowered atmospheric CO2 levels. It is likely that during the Monterey Excursion the ocean/atmosphere system became progressively more sensitive to small changes in insolation, ultimately leading to major cooling of deep water and expansion of continental ice. We have assigned an absolute chronology, based on biostratigraphic and magneto-biostratigraphic datum levels, to the isotope stratigraphy and have used that chronology to correlate unconformities, seismic reflectors, carbonate minima, and dissolution intervals. Intervals of sediment containing 13C maxima are usually better preserved than the overlying and underlying sediments, indicating that the d13C values of TCO2 in deep water and the corrosiveness of seawater are inversely correlated. This again suggests that the 13C maxima were associated with rapid burial of organic carbon and reduced levels of atmospheric CO2. The absolute chronology we have assigned to the isotopic record indicates that the major mid-Miocene deepwater cooling/ice volume expansion took 2 m.y. and was not abrupt as had been reported previously. The cooling appears abrupt at many sites because the interval is characterized by a number of dissolution intervals. The cooling was not monotonic, and the 2 m.y. interval included an episode of especially rapid cooling as well as a brief return to warmer conditions before the final phase of the cooling period. The increase in d18O values of benthic foraminifera between 14.9 and 12.9 Ma was greatest at deeper water sites and at sites closest to Antarctica. The data suggest that the d18O value of seawater increased by no more than about 1.1 per mil during this interval and that the remainder of the change in benthic d18O values resulted from cooling in Antarctic regions of deepwater formation. Equatorial planktonic foraminifera from sites 237 and 289 exhibit a series of 0.4 per mil steplike increases in d13C values. Only one of these increases in planktonic d13C is correlated with any of the features in the mid-Miocene benthic carbon isotope record.