(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.

Revised chronology of Neogene DSDP holes from the World Ocean

After nearly 30 years of growth in geochronologic knowledge, the originally published age models for many older deep sea marine sections have become badly outdated. In this report we present newly revised age models for Neogene sediments from 94 DSDP holes. Biostratigraphic data for planktonic foraminifers, calcareous nannofossils, diatoms and radiolarians, paleomagnetic and other stratigraphic data were compiled from the original Initial Reports volumes of DSDP. The Berggren et al. (1985 doi:10.1130/0016-7606(1985)96<1407:CG>2.0.CO;2) scale was used for the age of magnetic reversals, and a variety of recent papers were used to establish a standard modern set of calibrations for marine microfossil events to the magnetic reversal scale. New age vs depth plots were made for each hole, and for each a new line of correlation was created. All tabulated stratigraphic data, new age models, and age depth plots are given as appendices to the report.

Pacific Neogene carbonate accumulation rates

I have compiled CaCO3 mass accumulation rates (MARs) for the period 0-25 Ma for 144 Deep Sea Drilling Project and Ocean Drilling Program drill sites in the Pacific in order to investigate the history of CaCO3 burial in the world's largest ocean basin. This is the first synthesis of data since the beginning of the Ocean Drilling Program. Sedimentation rates, CaCO3 contents, and bulk density were estimated for 0.5 Myr time intervals from 0 to 14 Ma and for 1 Myr time intervals from 14 to 25 Ma using mostly data from Initial Reports volumes. There is surprisingly little coherence between CaCO3 MAR time series from different Pacific regions, although regional patterns exist. A transition from high to low CaCO3 MAR from 23-20 Ma is the only event common to the entire Pacific Ocean. This event is found worldwide. The most likely cause of lowered pelagic carbonate burial is a rising sea-level trend in the early Miocene. The central and eastern equatorial Pacific is the only region with adequate drill site coverage to study carbonate compensation depth (CCD) changes in detail for the entire Neogene. The latitude-dependent decrease in CaCO3 production away from the equator is an important defining factor of the regional CCD, which shallows away from the equatorial region. Examination of latitudinal transects across the equatorial region is a useful way to separate the effects of changes in carbonate production ('productivity') from changes in bottom water chemistry ('dissolution') upon carbonate burial.

Revised Cenozoic hiatus database

The differential effects of climate change, sea level, and water mass circulation on deposition/erosion of marine sediments can be constrained from the distribution of unconformities in the world's oceans. I identified temporal and depth patterns of hiatuses ("hiatus events") from a large and chronologically well constrained stratigraphic database of deep-sea sediments. The Paleogene is characterized by few, several million year long hiatuses. The most significant Cenozoic hiatus event spans most of the Paleocene. The Neogene is characterized by short, frequent hiatus events nearly synchronous in shallow and deep water sediments. Epoch boundaries are characterized by peaks in deep water hiatuses possibly caused by an increased circulation of corrosive bottom water and sediment dissolution. The Plio-Pleistocene is characterized by a gradual decrease in the frequency of hiatuses. Future studies will focus on the regional significance of the hiatus events and their possible causes.

Calcium carbonate global LGM Burial rate data

Global databases of calcium carbonate concentrations and mass accumulation rates in Holocene and last glacial maximum sediments were used to estimate the deep-sea sedimentary calcium carbonate burial rate during these two time intervals. Sparse calcite mass accumulation rate data were extrapolated across regions of varying calcium carbonate concentration using a gridded map of calcium carbonate concentrations and the assumption that accumulation of noncarbonate material is uncorrelated with calcite concentration within some geographical region. Mean noncarbonate accumulation rates were estimated within each of nine regions, determined by the distribution and nature of the accumulation rate data. For core-top sediments the regions of reasonable data coverage encompass 67% of the high-calcite (>75%) sediments globally, and within these regions we estimate an accumulation rate of 55.9 ± 3.6 x 10**11 mol/yr. The same regions cover 48% of glacial high-CaCO3 sediments (the smaller fraction is due to a shift of calcite deposition to the poorly sampled South Pacific) and total 44.1 ± 6.0 x 10**11 mol/yr. Projecting both estimates to 100 % coverage yields accumulation estimates of 8.3 x 10**12 mol/yr today and 9.2 x 10**12 mol/yr during glacial time. This is little better than a guess given the incomplete data coverage, but it suggests that glacial deep sea calcite burial rate was probably not considerably faster than today in spite of a presumed decrease in shallow water burial during glacial time.

Calcium carbonate preservation in the equatorial Pacific

The Pliocene-Pleistocene history of CaCO3 preservation in the central equatorial Pacific is reconstructed from a suite of deep-sea cores and is compared to fluctuations in global ice volume inferred from delta18O records. The results are highlighted by: (1) a strong covariation between CaCO3 preservation and ice volume over 104 to 106 year time scales; (2) a long-term increase in ice volume and CaCO3 preservation since 3.9 Ma demonstrated by a deepening of the lysocline and the carbonate critical depth; (3) a dramatic shift to greater CaCO3 preservation at 2.9 Ma; (4) distinctive ice-volume growth and CaCO3 preservation events at 2.4 Ma, which are associated with the significant intensification of northern hemisphere glaciation; (5) a mid-Pleistocene transition to 100-kyr cyclicity in both CaCO3 preservation and ice volume; and (6) a 600-kyr Brunhes dissolution cycle superimposed on the late Pleistocene glacial/interglacial 100-kyr cycles. CaCO3 preservation primarily reflects the carbonate chemistry of abyssal waters and is controlled by long-term (106 year) and short-term (104 to 105 year) biogeochemical cycling and by distinct paleoclimatic events. We attribute the long-term increase in CaCO3 preservation primarily to a fractionation of CaCO3 deposition from continental shelf to ocean basin, and secondarily to a gradual rise in the riverine and glaciofluvial flux of Ca++. On shorter time scales, the fluctuations in CaCO3 preservation slightly lag ice volume fluctuations and are attributed to climatically induced changes in the circulation and chemistry of Pacific deep water.