Organic carbon and calcium carbonate concentrations of K/T boundary samples from southern Tethyan margin location (Table 1)

Regional consequences of the biotic extinctions and of the changes in biological productivity that occurred at the time of the Cretaceous/Tertiary (K/T) boundary were investigated by comparison of organic matter in sediments from three southern Tethyan margin locations. Organic matter characterization comprised Rock-Eval pyrolysis and organic carbon measurements. Low concentrations of organic matter precluded additional detailed determinations. At all three locations, the organic matter has been microbially reworked and evidently was deposited in oxygenated marine environments.

Calcium carbonate, sedimentation and mass accumulation rates at DSDP Site 85-572

At Site 572, located at 1°N, 114° W (3903 m water depth), we recovered a continuous hydraulic piston cored section of upper Miocene to upper Pleistocene pelagic sediments. The sediment is composed of biogenic carbonate and silica with nonbiogenic material as a minor component. Detailed analysis of the calcium carbonate content shows that the degree of variability in carbonate deposition apparently changed markedly between the late Miocene and Pliocene at this equatorial Pacific site. During this interval carbonate mass accumulation rates decreased from 2.6 to 0.8 g/cm**2 per 10**3 yr. If we assume that variations in CaCO3 content reflect changes in the degree of dissolution, then the detailed carbonate analysis would suggest that the degree of variability in carbonate deposition decreases by a factor of 5 as the dominant wavelength of variations increases significantly. However, if the variability in carbonate concentration is described in terms of changes in mean mass accumulation, calculations then suggest that relatively small changes in noncarbonate rates may be important in controlling the observed carbonate records. In addition, the analysis suggests that the degree of variability observed in pelagic carbonate data may in part reflect total accumulation rates. Intervals with high sedimentation rates show lower amplitude variations in concentration than intervals with lower sedimentation rates for the same degree of change in the carbonate accumulation rate.

Late Pliocene carbonate mineralogy of ODP Hole 133-818B

Shedding of shallow carbonate material toward the deep slopes and basin floors is clearly tied to the position of the carbonate bank tops relative to the photic zone. The onset of bank shedding in periplatform sediments can record either the flooding of the bank tops within the photic zone during a rise in sea level following a period of exposure, referred to in the literature as the "highstand shedding" scenario, or the reentry of the bank tops into the photic zone during a lowering of sea level following a period of drowning, referred to as the "lowstand shedding" scenario. Results from Leg 133 post-cruise research on the Pliocene sequences, drilled in six sites within different slope settings of the Queensland Plateau, seem to point out that the latter "lowstand shedding" scenario can be applied to this particular carbonate system. At the Queensland Plateau sites, the early Pliocene (5.2-3.5 Ma) and the earliest part of the late Pliocene (3.5-2.9 Ma) age sequences were characterized, especially in the ôdeepö Sites 811 and 817, by pelagic sediments (foraminifers and coccoliths) and by typically pelagic sedimentation rates not exceeding 20 mm/k.y. The earliest part of the late Pliocene age section was characterized by well-developed hardgrounds in the "shallow" Sites 812 and 814 and by normal pelagic sediments mixed with reworked phosphatized planktonic foraminifers in Site 813. Finally, the early part of the late Pliocene (2.9-2.4 Ma) section was characterized by high sedimentation rates, related to the shedding and admixture into the pelagic sediments of bank-derived materials. These bank-derived materials consist of either diagenetically unaltered fine aragonite with traces of dolomite in Site 818 or micritic calcite resulting from seafloor and/or shallow burial alteration in the deepest Sites 817 and 811. The highest sedimentation rates (163 mm/k.y.) were recorded in Site 818, drilled nearest the modern carbonate bank of Tregrosse Reef. The sedimentation rates decrease with increasing distance from Tregrosse Reef - 120 mm/k.y. in Site 817 and 47.5 mm/k.y. in Site 811. The initial appearance of fine aragonite in Site 818, corresponding to the transition from pelagic to periplatform sedimentation rates, has been dated at 2.9 Ma. This Pliocene sediment pattern on the Queensland Plateau is different from the pattern observed in sediments from two earlier ODP legs (i.e., Leg 101 in the Bahamas and in Leg 115 in the Maldives), where aragonite-rich sediments, characterized by high periplatform sedimentation rates, were observed in the lower Pliocene section (5.2-3.5 Ma), whereas the upper Pliocene (3.5-1.6 Ma) sediments are more pelagic in nature and are characterized by low sedimentation rates or major hiatuses. These Pliocene periplatform sequences in the Bahamas and in the Maldives and late Quaternary age periplatform sequences worldwide have pointed out that "highstand shedding" was the typical response of carbonate platforms to fluctuations in sea level, just opposite to a "lowstand shedding" response to sea-level fluctuations, typical of siliciclastic shelves. Assuming that the envelope of Haq et al.'s (1987) sea-level curve, showing a well-defined lowering of sea level between 3.5 and 2.9 Ma, can also be applied to the southwest Pacific Ocean, based on a high-resolution Pliocene d18O record from the Ontong Java Plateau recently published by Jansen et al. (1993, doi:10.2973/odp.proc.sr.130.028.1993), the Pliocene periplatform sequences on the Queensland Plateau would have recorded the reentry of the bank tops into the photic zone during a general lowering of sea level, following an interval characterized by high sea level, during which the shallow carbonate system on the Queensland Plateau was drowned. The early Pliocene age (5.2-3.5 Ma) sediments deposited on the Queensland Plateau, an established interval of eustatic sea-level highstand, are typically pelagic in character. In addition, relatively cold surface temperatures (estimated to have ranged from 18° to 20°C by Isern et al. [this volume]) might have also stressed the reefs during early Pliocene time and contributed to the drowning of the Queensland Plateau carbonate system during the late Miocene and early Pliocene. Differential and relatively high subsidence rates, inferred by variations in paleodepth of water (based upon benthic foraminifer assemblages; Katz and Miller, this volume) may also have influenced the drowning of the carbonate bank tops on the Queensland Plateau during the late Miocene and early Pliocene. The sediments of early late Pliocene age (2.9-2.4 Ma), a well-established interval of lowering of sea level, are clearly periplatform and cyclic in nature. High-frequency (~40 k.y.) aragonite cycles, well-developed between 2.9 and 2.45 Ma, correlate with the planktonic high-resolution Pliocene d18O record from the Ontong Java Plateau, a good sea-level proxy (Jansen et al., in press). Contrary to late Quaternary age aragonite cycles from the Bahamas, the Nicaragua Rise, the Maldives, and the Queensland Plateau, the late Pliocene aragonite cycles in Hole 818B display high levels of aragonite during glacial stages and, therefore, lowstands of sea level. In addition, sediments deposited during the earliest part of the late Pliocene (3.5-2.9 Ma), transition between the early Pliocene highstand and the late Pliocene lowering in sea level, have recorded the first evidence of a fall in sea level, by (1) the occurrence of synchronous submarine hardgrounds in the two shallowest sites (Sites 812 and 814), (2) the deposition of reworked material from the shallower part of the slope into the intermediate Sites 813 and 818, and (3) the deposition of pelagic sediments in the deepest Sites 817 and 817. In summary, contrary to previous findings, the Pliocene periplatform sediments on the Queensland Plateau appear to have recorded a regional shedding of shallow carbonate bank tops during an interval of sea-level lowering, a good illustration of the "carbonate lowstand shedding" scenario, occurring during the reentry of previously drowned carbonate bank tops into the photic zone related to a decrease in sea level.

Pliocene-Plistocene deposition of carbonate and organic carbon in ODP Hole 159-959C

During Ocean Drilling Program (ODP) Leg 159, four sites (Sites 959-962) were drilled along a depth transect on the Côte d'Ivoire/Ghana Transform Margin. In this study, the Pliocene-Pleistocene history of carbonate and organic carbon accumulation at Hole 959C is reconstructed for the eastern equatorial Atlantic off the Ivory Coast/Ghana based on bulk carbonate, sand fraction, organic carbon, and other organic geochemical records (d13Corg, marine organic matter percentages derived from organic petrology, hydrogen index, C/N). Pliocene-Pleistocene sedimentation off the Ivory Coast/Ghana was strongly affected by low mean sedimentation rates, which are attributed to persistently enhanced bottom-water velocities related to the steep topography of the transform margin. Sand fraction and bulk carbonate records reveal typical glacial/interglacial cycles, preserved, however, with low time resolution. Intermediate carbonate accumulation rates observed throughout the Pliocene-Pleistocene suggest intense winnowing and sediment redistribution superimposed by terrigenous dilution. 'Atlantic-type' sand and carbonate cycles, consistent with records from pelagic areas of the eastern equatorial Atlantic, are encountered at Hole 959C prior to about 0.9 Ma. Total organic carbon (TOC) records are frequently inversely correlated to carbonate contents, indicating mainly productivity-driven carbonate dissolution related to changes in paleoproductivity. During Stages 22-24, 20, 16, 12, 8, and 4, sand and carbonate records reveal a 'Pacific-type' pattern, showing elevated contents during glacials commonly in conjunction with enhanced TOC records. Formation of 'Pacific-type' patterns off the Ivory Coast/Ghana is attributed to drastically increased bottom-water intensities along the transform margin in accordance with results reported from the Walvis Ridge area. Short-term glacial/interglacial changes in paleoproductivity off the Ivory Coast/Ghana are to some extend recognizable during glacials prior to 1.7 Ma and interglacial Stages 21, 19, 13, 9, and 1. Enhanced coastal upwelling during interglacials is attributed to local paleoclimatic and oceanographic conditions off the Ivory Coast/Ghana. Quantitative estimates of marine organic carbon based on organic petrologic and d13Corg records reveal an offset in concentration ranging from 15% to 60%. Highest variabilities of both records are recorded since ~0.9 Ma. Discrepancies between the isotopic and microscopic records are attributed to an admixture of C4 plant debris approaching the eastern equatorial Atlantic via atmospheric dust. Terrestrial organic material likely originated from the grass-savannah-covered Sahel zone in central Africa. Estimated C4 plant concentrations and accumulation rates range from 10% to 37% and from almost zero to 0.006 g/cm**2/k.y., respectively. The strongest eolian supply to the northern Gulf of Guinea is indicated between 1.9 and 1.68 Ma and during glacial isotopic Stages 22-24, 20, 14, and 12. The presence of grass-type plant debris is further supported by organic petrologic studies, which reveal well-preserved cell tissues of vascular plants or tube-shaped, elongated terrestrial macerals showing different levels of oxidation.

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 and bulk grain-size record for ODP Leg 130 holes

A major goal of Ocean Drilling Program (ODP) Leg 130 was to drill four sites down the northeastern flank of the Ontong Java Plateau to collect a series of continuous sedimentary sequences that would provide a depth transect of Neogene sediments. In particular, the study of the sediments recovered along the depth transect is expected to yield high-resolution stratigraphic, geochemical, and physical properties records across intervals of major paleoceanographic changes by evaluating variations of primary sedimentological and paleoceanographic indicators (e.g., carbonates, isotopes, grain size, microfossil assemblages, etc.). This data report presents the results of highresolution (3-5 Ka sample intervals) analyses of carbonate concentration and bulk sediment grain size at Sites 803-806 for the time interval from 2 Ma to the present.

Quaternary carbonate and stable isotope record of ODP Holes 133-817A and 133-818B

The Quaternary history of metastable CaCO3 input and preservation within Antarctic Intermediate Water (AAIW) was examined by studying sediments from ODP Holes 818B (745 mbsl) and 817A (1015 mbsl) drilled in the Townsville Trough on the southern slope of the Queensland Plateau. These sites lie within the core of modern AAIW, and near the aragonite saturation depth (~1000 m). Thus, they are well positioned to monitor chemical changes that may have occurred within this watermass during the past 1.6 m.y. The percent of fine aragonite content, percent of fine magnesian calcite content, and percent of whole pteropods (>355 µm) were used to separate the fine aragonite input signal from the CaCO3 preservation signal. Stable d18O and d13C isotopic ratios were determined for the planktonic foraminifer Globigerinoides sacculifer and, in Hole 818B, for the benthic foraminifer Cibicidoides spp. to establish the oxygen isotope stratigraphy and to study the relationship between intermediate and shallow water d13C of Sum CO2 and the relationship between benthic foraminiferal d13C and CaCO3 preservation within intermediate waters of the Townsville Trough. Data were converted from depth to age using oxygen isotope stratigraphy, nannostratigraphy, and foraminiferal biostratigraphy. Several long hiatuses and the absence of magnetostratigraphy did not permit time series analysis. The principal results of the CaCO3 preservation study include the following (1) a general increase in CaCO3 preservation between 0.9 and 1.6 Ma; (2) a CaCO3 dissolution maximum near 0.9 Ma, primarily expressed in the Hole 818B fine aragonite record; (3) an abrupt and permanent increase of fine aragonite content between 0.86 and 0.875 Ma in both Holes 818B and 817A probably reflecting a dramatic increase of fine carbonate sediment production on the Queensland Plateau; (4) an improvement in CaCO3 preservation near 0.87 Ma, which accompanied the increase of sediment input, indicated by the first appearance of whole pteropods in the deeper Hole 817A and a "spike" in the percent whole pteropods in Hole 818B; (5) a period of strong CaCO3 dissolution during the mid-Brunhes Chron from 0.36 to 0.41 Ma; and (6) a complex CaCO3 preservation pattern between 0.36 Ma and the present characterized by a general increase in CaCO3 preservation through time with good preservation during interglacial stages and poor preservation during glacial stages. The long-term aragonite preservation histories for Holes 818B and 817A appear to be similar in general shape, although different in detail, to CaCO3 preservation records from the deep Indian and central equatorial Pacific oceans as well as from intermediate water sites in the Bahamas and the Maldives. All of these areas have experienced CaCO3 dissolution at about 0.9 Ma and during the mid-Brunhes Chron. However, the late Quaternary (0 to 0.36 Ma) glacial to interglacial preservation pattern in Holes 818B and 817A is out of phase with CaCO3 preservation records for sediments deposited in Pacific deep and bottom waters. The sharp increase in bank production and export from the Queensland Plateau and the coincident improvement of CaCO3 preservation between 0.86 and 0.875 Ma may have been synchronous with the initiation of the Great Barrier Reef and roughly coincides with an increase in carbonate accumulation on the Bahama banks, in the western North Atlantic Ocean, and on Mururoa atoll, in the central South Pacific Ocean. The development of these reef systems during the middle Quaternary may be related to the transition in the frequency and amplitude of global sea level change from 41 k.y. low amplitude cycles prior to 0.9 Ma to 100 k.y. high amplitude cycles after 0.73 Ma. Carbon isotopic analyses show that benthic foraminiferal d13C values (Cibicidoides spp.) have been heavier than planktonic foraminiferal d13C values (G. sacculifer) throughout most of the last 0.54 m.y., which may indicate that 13C-enriched intermediate water (AAIW) occupied the Townsville Trough during much of the late Quaternary. Furthermore, both planktonic and benthic foraminiferal d13C values are often observed to be heaviest during interglacial to glacial transitions, and lightest during glacial to interglacial transitions. We suggest that this pattern is the result of changes in the preformed d13C of Sum CO2 of AAIW and may reflect changes in nutrient utilization by primary producers in Antarctic surface waters, changes in the d13C of upwelled Circumpolar Deep Water, or changes in the extent and/or temperature of equilibration between surface water and atmospheric CO2 within the Antarctic Polar Frontal Zone (the source area for AAIW). Finally, the poor correlation between percent of whole pteropods (aragonite preservation) and d13C of Cibicidoides spp. may be the result of a decoupling of d13C from CO2 due to the numerous and complex variables that combine to produce the preformed d13C of AAIW.

Sand fraction, carbonate and organic carbon contents of ODP Hole 175-1085A

Site 1085 is located on the continental rise of southwest Africa at a water depth of 1713 m off the mouth of the Orange River in the Cape Basin. The site is part of the suite of locations drilled during Leg 175 on the Africa margin to reconstruct the onset and evolution of the elevated biological productivity associated with the Benguela Current upwelling system (Wefer, Berger, Richter, et al., 1998, doi:10.2973/odp.proc.ir.175.1998). Three sediment samples were collected per section from Cores 170-1085A-28H through 45X (251-419 mbsf) to provide a survey of the sediment record of paleoproductivity from the middle late Miocene to the early Pliocene (~8.7-4.7 Ma), which is a period that includes the postulated northward migration and intensification of the Benguela Current and the establishment of modern circulation off southwest Africa (Siesser, 1980; Diester-Haass et al., 1992; Berger et al., 1998). Core 170-1085A-30H (270-279 mbsf) had essentially no recovery; this coring gap was filled with samples from Cores 170-1085B-29H and 30H (261-280 mbsf). The results of measurements of multiple paleoproductivity proxies are summarized in this report. Included in these proxies are the radiolarian, foraminiferal, and echinoderm components of the sand-sized sediment fraction. Opal skeletons of radiolarians (no diatoms were found) relate to paleoproductivity and water mass chemistry (Summerhayes et al., 1995, doi:10.1016/0079-6611(95)00008-5; Lange and Berger, 1993, doi:10.2973/odp.proc.sr.130.011.1993; Nelson et al., 1995, doi:10.1029/95GB01070). The accumulation rates of benthic foraminifers are useful proxies for paleoproductivity (Herguera and Berger, 1991, doi:10.1130/0091-7613(1991)019<1173:PFBFAG>2.3.CO;2; Nees, 1997, doi:10.1016/S0031-0182(97)00012-6; Schmiedl and Mackensen, 1997, doi:10.1016/S0031-0182(96)00137-X) because these fauna subsist on organic matter exported from the photic zone. Echinoderms also depend mainly on food supply from the photic zone (Gooday and Turley, 1990), and their accumulation rates are an additional paleoproductivity proxy. Concentrations of calcium carbonate (CaCO3) and organic carbon in sediment samples are fundamental measures of paleoproductivity (e.g., Meyers, 1997, doi:10.1016/S0146-6380(97)00049-1). In addition, organic matter atomic carbon/nitrogen (C/N) ratios and delta13C values can be used to infer the origin of the organic matter contained within the sediments and to explore some of the factors affecting its preservation and accumulation (Meyers, 1994, doi:10.1016/0009-2541(94)90059-0).

Carbonate cements and fluid circulation of ODP Leg 116 samples

The carbonate cements found in Sites 717-719 of ODP Leg 116 correspond to the precipitation of inorganic calcite due to circulation of hot fluid associated with intraplate deformation in the central Indian Ocean. A first burst of hydrothermal activity may have occurred 7.5-9 Ma and a second burst less than 0.5 Ma. These fluids were probably derived from the basaltic basement and the immediately overlying sediments.