Calcium carbonate in sediments at DSDP Leg 92

The carbonate contents of sediments recovered at Leg 92 Sites 597, 598, and 601 were determined at 5-cm intervals. The long-term record of carbonate variation at Sites 597 and 598 shows the effect of decreasing dilution by hydrothermal phases as the sites moved away from the ridge crest at which they formed. Superimposed on this trend are high-amplitude variations in carbonate content. In the lower portions of Sites 597 and 598 the high-amplitude variations have a duration of a few hundred thousand years. The upper portion of the sediment column at both sites was deposited below the lysocline, and high-amplitude variations in this interval represent 1 to 2 m.y. The data suggest that only very intense carbonate dissolution events can be identified reliably at sites with low accumulation rates. At sites like Site 598, where the sedimentation rate is higher, the details of carbonate variation can be correlated with the carbonate lithostratigraphies developed for sites in the equatorial and North Pacific oceans.

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.

Carbonate and Aluminium accumulation in the central equatorial Pacific Ocean

We examined the flux of Al to sediment accumulating beneath the zone of elevated productivity in the central equatorial Pacific Ocean, along a surface sediment transect at 135°W as well as downcore for a 650 kyr record at 1.3°N, 133.6°W. Across the surface transect, a pronounced, broadly equatorially symmetric increase in Al accumulation is observed, relative to Ti, with Al/Ti ratios reaching values 3-4 times that of potential detrital sources. The profile parallels biogenic accumulation and the modeled flux of particulate 234Th, suggesting rapid and preferential adsorptive removal of Al from seawater by settling biogenic particles. Normative calculations confirm that most Al is unsupported by the terrigenous fraction. The observed distributions are consistent with previous observations of the relative and absolute behavior of Al and Ti in seawater, and we can construct a reasonable mass balance between the amount of seawater-sourced Al retained in the sediment and the amount of seawater Al available in the overlying column. The close tie between Al/Ti and biogenic accumulation (as opposed to concentration) emphasizes that biogenic sedimentary Al/Ti responds to removal-transport phenomena and not bulk sediment composition. Thus, in these sediments dominated by the biogenic component, the bulk Al/Ti ratio reflects biogenic particle flux, and by extension, productivity of the overlying seawater. The downcore profile of Al/Ti at 1.3°N displays marked increases during glacial episodes, similar to that observed across the surface transect, from a background value near Al/Ti of average upper crust. The excursions in Al/Ti are stratigraphically coincident with maxima in both bulk and CaCO3 accumulation and the excess Al appears to not be preferentially affiliated with opaline or organic phases. Consistent with the similar behavioral removal of Al and 234Th, the latter of which responds to the total particle flux, the Al flux reflects carbonate accumulation only because carbonate comprises the dominant flux in these particular deposits. These results collectively indicate that (1) Al in biogenic sediment and settling biogenic particles is strongly affected by a component adsorbed from seawater. Therefore, the common tenet that Al is dominantly associated with terrestrial particulate matter, and the subsequent use of Al distributions to calculate the abundance and flux of terrestrial material in settling particles and sediment, needs to be reevaluated. (2) The Al/Ti ratio in biogenic sediment can be used to trace the productivity of the overlying water, providing a powerful new paleochemical tool to investigate oceanic response to climatic variation. (3) The close correlation between the Al/Ti productivity signal and carbonate maxima downcore at 1.3°N suggests that the sedimentary carbonate maxima in the central equatorial Pacific Ocean record increased productivity during glacial episodes.

Carbonate accumulation rates of the Ninetyeast Ridge, Indian Ocean

More than 95% of the carbon lost from the "blue-ocean" reservoir to the sedimentary sink appears to be transferred as skeletal CaCO3, produced in the surface waters. This skeletal CaCO3 carries a productivity signal which is much better preserved in the underlying pelagic carbonate sediments than that of the refractory organic carbon accompanying it. Here, we develop a new method to quantify this signal in terms of organic carbon paleoproductivity, using the sedimentary mass accumulation rates of pelagic carbonate. These are converted into carbonate transit-paleofluxes, which are then translated into the corresponding transit-fluxes of organic carbon, via the carbonate to organic carbon ratios reported from deep-moored sediment trap experiments in modern blue-ocean environments. Paleoproductivity can then be estimated quantitatively by using published algorithms describing the relationship between the export production of particulate organic carbon at depth and primary productivity in the euphotic zone. Although our approach seems rather straightforward, it contains several pitfalls, the effects of which are highlighted by an example comprising three Paleocene/Oligocene to Recent pelagic carbonate sequences drilled during ODP Leg 121 in the eastern Indian Ocean. Although some extreme values are likely due to errors, such as poorly constrained datum levels and dissolution peaks, the results for the Quaternary and Neogene correlate well from site to site and are within the productivity range of present-day low to medium latitude open oceans. Our method may provide an opportunity to actually quantify blue-ocean primary productivity in sedimentary carbonate environments, but requires validation by other, more established ones.

Accumulation rates, carbon composition and Eocene carbonate compensation depths of ODP Sites 199-1218 and 199-1219

CaCO3, Corg, and biogenic SiO2 were measured in Eocene equatorial Pacific sediments from Sites 1218 and 1219, and bulk oxygen and carbon isotopes were measured on selected intervals from Site 1219. These data delineate a series of CaCO3 events that first appeared at ~48 Ma and continued to the Eocene/Oligocene boundary. Each event lasted 1-2 m.y. and is separated from the next by a low CaCO3 interval of a similar time span. The largest of these carbonate accumulation events (CAE-3) is in Magnetochron 18. It began at ~42.2 Ma, lasted until ~40.3 Ma, and was marked by higher than average productivity. The end of CAE-3 was abrupt and was associated with a large-scale carbon transfer to the oceans prior to warming of high-latitude regions. Changes in carbonate compensation depth associated with CAE excursions were small in the early part of the middle Eocene but increased to as much as 800 m by the late middle Eocene before decreasing into the late Eocene. Oxygen isotope data indicate that the carbonate events are associated with cooling conditions and may mark small glaciations in the Eocene.

Late Cenozoic carbonate accumulation rates of ODP Leg 115 samples

The principal paleoceanographic objective of Ocean Drilling Program Leg 115 was to collect a suite of materials that would allow reconstruction of the dynamic features of the late Cenozoic carbonate system in the equatorial Indian Ocean. This goal was achieved with the recovery of sediments from a closely spaced depth transect (1541-4428 m) of five sites (Sites 707 through 711) from on and around the Mascarene Plateau that record the last 50 m.y. of pelagic deposition. More than 2200 measurements of carbonate content are combined here with a highly resolved bio- and magnetostratigraphy to produce the first detailed compilation of bulk, carbonate, and noncarbonate mass accumulation rates (MARs) from the Indian Ocean. These results allow us to recognize three major depositional intervals, each characterized by a distinct depth-dependent pattern of carbonate accumulation: (1) the Paleogene, a time of moderate accumulation rates (0.4-0.7 g/cm**2/1000 yr) and reduced between-site accumulation differences; (2) the early and middle Miocene, a period characterized by greatly reduced carbonate MARs (typically <0.2 g/cm**2/1000 yr) at all sites and a shallow carbonate compensation depth; and (3) the late Miocene to Holocene, a time span marked by the highest bulk and carbonate accumulation rates of the last 50 Ma (1.6-1.8 g/cm**2/1000 yr), and the first appearance of substantial contrasts in carbonate accumulation as a function of the water depth of the drill site. The fundamentally different character of the carbonate system during each of these intervals must represent a regional response to the complex evolution of late Cenozoic oceans and climate.